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Infrared and Raman Spectroscopy of Polymers Report 134 Volume 12, Number 2, 2001 J.L. Koenig

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Infrared and Raman Spectroscopy of Polymers

Report 134

Volume 12, Number 2, 2001

J.L. Koenig

RAPRA REVIEW REPORTS

A Rapra Review Report comprises three sections, as follows:

1. A commissioned expert review, discussing a key topic of current interest, and referring to the References andAbstracts section. Reference numbers in brackets refer to item numbers from the References and Abstractssection. Where it has been necessary for completeness to cite sources outside the scope of the Rapra Abstractsdatabase, these are listed at the end of the review, and cited in the text as a.1, a.2, etc.

2. A comprehensive References and Abstracts section, resulting from a search of the Rapra Abstracts database.The format of the abstracts is outlined in the sample record below.

3. An index to the References and Abstracts section, derived from the indexing terms which are added to theabstracts records on the database to aid retrieval.

Item 1Macromolecules

33, No.6, 21st March 2000, p.2171-83EFFECT OF THERMAL HISTORY ON THE RHEOLOGICALBEHAVIOR OF THERMOPLASTIC POLYURETHANESPil Joong Yoon; Chang Dae HanAkron,University

The effect of thermal history on the rheological behaviour of ester- andether-based commercial thermoplastic PUs (Estane 5701, 5707 and 5714from B.F.Goodrich) was investigated. It was found that the injectionmoulding temp. used for specimen preparation had a marked effect on thevariations of dynamic storage and loss moduli of specimens with timeobserved during isothermal annealing. Analysis of FTIR spectra indicatedthat variations in hydrogen bonding with time during isothermal annealingvery much resembled variations of dynamic storage modulus with timeduring isothermal annealing. Isochronal dynamic temp. sweep experimentsindicated that the thermoplastic PUs exhibited a hysteresis effect in theheating and cooling processes. It was concluded that the microphaseseparation transition or order-disorder transition in thermoplastic PUs couldnot be determined from the isochronal dynamic temp. sweep experiment.The plots of log dynamic storage modulus versus log loss modulus variedwith temp. over the entire range of temps. (110-190C) investigated. 57 refs.

GOODRICH B.F.USA

Accession no.771897

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Companies ororganisationsmentioned

Abstract

Authors andaffiliation

Source oforiginal article

Title

Previous Titles Still AvailableVolume 1Report 3 Advanced Composites, D.K. Thomas, RAE, Farnborough.

Report 4 Liquid Crystal Polymers, M.K. Cox, ICI, Wilton.

Report 5 CAD/CAM in the Polymer Industry, N.W. Sandlandand M.J. Sebborn, Cambridge Applied Technology.

Report 8 Engineering Thermoplastics, I.T. Barrie, Consultant.

Report 11 Communications Applications of Polymers,R. Spratling, British Telecom.

Report 12 Process Control in the Plastics Industry,R.F. Evans, Engelmann & Buckham Ancillaries.

Volume 2Report 13 Injection Moulding of Engineering Thermoplastics,

A.F. Whelan, London School of Polymer Technology.

Report 14 Polymers and Their Uses in the Sports and LeisureIndustries, A.L. Cox and R.P. Brown, RapraTechnology Ltd.

Report 15 Polyurethane, Materials, Processing and Applications,G. Woods, Consultant.

Report 16 Polyetheretherketone, D.J. Kemmish, ICI, Wilton.

Report 17 Extrusion, G.M. Gale, Rapra Technology Ltd.

Report 18 Agricultural and Horticultural Applications ofPolymers, J.C. Garnaud, International Committee forPlastics in Agriculture.

Report 19 Recycling and Disposal of Plastics Packaging,R.C. Fox, Plas/Tech Ltd.

Report 20 Pultrusion, L. Hollaway, University of Surrey.

Report 21 Materials Handling in the Polymer Industry,H. Hardy, Chronos Richardson Ltd.

Report 22 Electronics Applications of Polymers, M.T.Goosey,Plessey Research (Caswell) Ltd.

Report 23 Offshore Applications of Polymers, J.W.Brockbank,Avon Industrial Polymers Ltd.

Report 24 Recent Developments in Materials for FoodPackaging, R.A. Roberts, Pira Packaging Division.

Volume 3Report 25 Foams and Blowing Agents, J.M. Methven, Cellcom

Technology Associates.

Report 26 Polymers and Structural Composites in CivilEngineering, L. Hollaway, University of Surrey.

Report 27 Injection Moulding of Rubber, M.A. Wheelans,Consultant.

Report 28 Adhesives for Structural and EngineeringApplications, C. O’Reilly, Loctite (Ireland) Ltd.

Report 29 Polymers in Marine Applications, C.F.Britton,Corrosion Monitoring Consultancy.

Report 30 Non-destructive Testing of Polymers, W.N. Reynolds,National NDT Centre, Harwell.

Report 31 Silicone Rubbers, B.R. Trego and H.W.Winnan,Dow Corning Ltd.

Report 32 Fluoroelastomers - Properties and Applications,D. Cook and M. Lynn, 3M United Kingdom Plc and3M Belgium SA.

Report 33 Polyamides, R.S. Williams and T. Daniels,T & N Technology Ltd. and BIP Chemicals Ltd.

Report 34 Extrusion of Rubber, J.G.A. Lovegrove, NovaPetrochemicals Inc.

Report 35 Polymers in Household Electrical Goods, D.Alvey,Hotpoint Ltd.

Report 36 Developments in Additives to Meet Health andEnvironmental Concerns, M.J. Forrest, RapraTechnology Ltd.

Volume 4Report 37 Polymers in Aerospace Applications, W.W. Wright,

University of Surrey.

Report 39 Polymers in Chemically Resistant Applications,D. Cattell, Cattell Consultancy Services.

Report 41 Failure of Plastics, S. Turner, Queen Mary College.

Report 42 Polycarbonates, R. Pakull, U. Grigo, D. Freitag, BayerAG.

Report 43 Polymeric Materials from Renewable Resources,J.M. Methven, UMIST.

Report 44 Flammability and Flame Retardants in Plastics,J. Green, FMC Corp.

Report 45 Composites - Tooling and Component Processing,N.G. Brain, Tooltex.

Report 46 Quality Today in Polymer Processing, S.H. Coulson,J.A. Cousans, Exxon Chemical International Marketing.

Report 47 Chemical Analysis of Polymers, G. Lawson, LeicesterPolytechnic.

Volume 5Report 49 Blends and Alloys of Engineering Thermoplastics,

H.T. van de Grampel, General Electric Plastics BV.

Report 50 Automotive Applications of Polymers II,A.N.A. Elliott, Consultant.

Report 51 Biomedical Applications of Polymers, C.G. Gebelein,Youngstown State University / Florida Atlantic University.

Report 52 Polymer Supported Chemical Reactions, P. Hodge,University of Manchester.

Report 53 Weathering of Polymers, S.M. Halliwell, BuildingResearch Establishment.

Report 54 Health and Safety in the Rubber Industry, A.R. Nutt,Arnold Nutt & Co. and J. Wade.

Report 55 Computer Modelling of Polymer Processing,E. Andreassen, Å. Larsen and E.L. Hinrichsen, Senter forIndustriforskning, Norway.

Report 56 Plastics in High Temperature Applications,J. Maxwell, Consultant.

Report 57 Joining of Plastics, K.W. Allen, City University.

Report 58 Physical Testing of Rubber, R.P. Brown, RapraTechnology Ltd.

Report 59 Polyimides - Materials, Processing and Applications,A.J. Kirby, Du Pont (U.K.) Ltd.

Report 60 Physical Testing of Thermoplastics, S.W. Hawley,Rapra Technology Ltd.

Volume 6Report 61 Food Contact Polymeric Materials, J.A. Sidwell,

Rapra Technology Ltd.

Report 62 Coextrusion, D. Djordjevic, Klöckner ER-WE-PA GmbH.

Report 63 Conductive Polymers II, R.H. Friend, University ofCambridge, Cavendish Laboratory.

Report 64 Designing with Plastics, P.R. Lewis, The Open University.

Report 65 Decorating and Coating of Plastics, P.J. Robinson,International Automotive Design.

Report 66 Reinforced Thermoplastics - Composition, Processingand Applications, P.G. Kelleher, New Jersey PolymerExtension Center at Stevens Institute of Technology.

Report 67 Plastics in Thermal and Acoustic Building Insulation,V.L. Kefford, MRM Engineering Consultancy.

Report 68 Cure Assessment by Physical and ChemicalTechniques, B.G. Willoughby, Rapra Technology Ltd.

Report 69 Toxicity of Plastics and Rubber in Fire, P.J. Fardell,Building Research Establishment, Fire Research Station.

Report 70 Acrylonitrile-Butadiene-Styrene Polymers,M.E. Adams, D.J. Buckley, R.E. Colborn, W.P. Englandand D.N. Schissel, General Electric Corporate Researchand Development Center.

Report 71 Rotational Moulding, R.J. Crawford, The Queen’sUniversity of Belfast.

Report 72 Advances in Injection Moulding, C.A. Maier,Econology Ltd.

Volume 7

Report 73 Reactive Processing of Polymers, M.W.R. Brown,P.D. Coates and A.F. Johnson, IRC in Polymer Scienceand Technology, University of Bradford.

Report 74 Speciality Rubbers, J.A. Brydson.

Report 75 Plastics and the Environment, I. Boustead, BousteadConsulting Ltd.

Report 76 Polymeric Precursors for Ceramic Materials,R.C.P. Cubbon.

Report 77 Advances in Tyre Mechanics, R.A. Ridha, M. Theves,Goodyear Technical Center.

Report 78 PVC - Compounds, Processing and Applications,J.Leadbitter, J.A. Day, J.L. Ryan, Hydro Polymers Ltd.

Report 79 Rubber Compounding Ingredients - Need, Theoryand Innovation, Part I: Vulcanising Systems,Antidegradants and Particulate Fillers for GeneralPurpose Rubbers, C. Hepburn, University of Ulster.

Report 80 Anti-Corrosion Polymers: PEEK, PEKK and OtherPolyaryls, G. Pritchard, Kingston University.

Report 81 Thermoplastic Elastomers - Properties and Applications,J.A. Brydson.

Report 82 Advances in Blow Moulding Process Optimization,Andres Garcia-Rejon,Industrial Materials Institute,National Research Council Canada.

Report 83 Molecular Weight Characterisation of SyntheticPolymers, S.R. Holding and E. Meehan, RapraTechnology Ltd. and Polymer Laboratories Ltd.

Report 84 Rheology and its Role in Plastics Processing,P. Prentice, The Nottingham Trent University.

Volume 8

Report 85 Ring Opening Polymerisation, N. Spassky, UniversitéPierre et Marie Curie.

Report 86 High Performance Engineering Plastics,D.J. Kemmish, Victrex Ltd.

Report 87 Rubber to Metal Bonding, B.G. Crowther, RapraTechnology Ltd.

Report 88 Plasticisers - Selection, Applications and Implications,A.S. Wilson.

Report 89 Polymer Membranes - Materials, Structures andSeparation Performance, T. deV. Naylor, The SmartChemical Company.

Report 90 Rubber Mixing, P.R. Wood.

Report 91 Recent Developments in Epoxy Resins, I. Hamerton,University of Surrey.

Report 92 Continuous Vulcanisation of Elastomer Profiles,A. Hill, Meteor Gummiwerke.

Report 93 Advances in Thermoforming, J.L. Throne, SherwoodTechnologies Inc.

Report 94 Compressive Behaviour of Composites,C. Soutis, Imperial College of Science, Technologyand Medicine.

Report 95 Thermal Analysis of Polymers, M. P. Sepe, Dickten &Masch Manufacturing Co.

Report 96 Polymeric Seals and Sealing Technology, J.A. Hickman,St Clair (Polymers) Ltd.

Volume 9

Report 97 Rubber Compounding Ingredients - Need, Theoryand Innovation, Part II: Processing, Bonding, FireRetardants, C. Hepburn, University of Ulster.

Report 98 Advances in Biodegradable Polymers, G.F. Moore &S.M. Saunders, Rapra Technology Ltd.

Report 99 Recycling of Rubber, H.J. Manuel and W. Dierkes,Vredestein Rubber Recycling B.V.

Report 100 Photoinitiated Polymerisation - Theory andApplications, J.P. Fouassier, Ecole Nationale Supérieurede Chimie, Mulhouse.

Report 101 Solvent-Free Adhesives, T.E. Rolando, H.B. FullerCompany.

Report 102 Plastics in Pressure Pipes, T. Stafford, RapraTechnology Ltd.

Report 103 Gas Assisted Moulding, T.C. Pearson, Gas Injection Ltd.

Report 104 Plastics Profile Extrusion, R.J. Kent, TangramTechnology Ltd.

Report 105 Rubber Extrusion Theory and Development,B.G. Crowther.

Report 106 Properties and Applications of ElastomericPolysulfides, T.C.P. Lee, Oxford Brookes University.

Report 107 High Performance Polymer Fibres, P.R. Lewis,The Open University.

Report 108 Chemical Characterisation of Polyurethanes,M.J. Forrest, Rapra Technology Ltd.

Volume 10

Report 109 Rubber Injection Moulding - A Practical Guide,J.A. Lindsay.

Report 110 Long-Term and Accelerated Ageing Tests on Rubbers,R.P. Brown, M.J. Forrest and G. Soulagnet,Rapra Technology Ltd.

Report 111 Polymer Product Failure, P.R. Lewis,The Open University.

Report 112 Polystyrene - Synthesis, Production and Applications,J.R. Wünsch, BASF AG.

Report 113 Rubber-Modified Thermoplastics, H. Keskkula,University of Texas at Austin.

Report 114 Developments in Polyacetylene - Nanopolyacetylene,V.M. Kobryanskii, Russian Academy of Sciences.

Report 115 Metallocene-Catalysed Polymerisation, W. Kaminsky,University of Hamburg.

Report 116 Compounding in Co-rotating Twin-Screw Extruders,Y. Wang, Tunghai University.

Report 117 Rapid Prototyping, Tooling and Manufacturing,R.J.M. Hague and P.E. Reeves, Edward MackenzieConsulting.

Report 118 Liquid Crystal Polymers - Synthesis, Properties andApplications, D. Coates, CRL Ltd.

Report 119 Rubbers in Contact with Food, M.J. Forrest andJ.A. Sidwell, Rapra Technology Ltd.

Report 120 Electronics Applications of Polymers II, M.T. Goosey,Shipley Ronal.

Volume 11

Report 121 Polyamides as Engineering Thermoplastic Materials,I.B. Page, BIP Ltd.

Report 122 Flexible Packaging - Adhesives, Coatings andProcesses, T.E. Rolando, H.B. Fuller Company.

Report 123 Polymer Blends, L.A. Utracki, National ResearchCouncil Canada.

Report 124 Sorting of Waste Plastics for Recycling, R.D. Pascoe,University of Exeter.

Report 125 Structural Studies of Polymers by Solution NMR,H.N. Cheng, Hercules Incorporated.

Report 126 Composites for Automotive Applications, C.D. Rudd,University of Nottingham.

Report 127 Polymers in Medical Applications, B.J. Lambert andF.-W. Tang, Guidant Corp., and W.J. Rogers, Consultant.

Report 128 Solid State NMR of Polymers, P.A. Mirau,Lucent Technologies.

Report 129 Failure of Polymer Products Due to Photo-oxidation,D.C. Wright.

Report 130 Failure of Polymer Products Due to Chemical Attack,D.C. Wright.

Report 131 Failure of Polymer Products Due to Thermo-oxidation,D.C. Wright.

Report 132 Stabilisers for Polyolefins, C. Kröhnke and F. Werner,Clariant Huningue SA.

Volume 12

Report 133 Advances in Automation for Plastics InjectionMoulding, J. Mallon, Yushin Inc.

Titles Available in the Current Volume

Infrared and RamanSpectroscopy of Polymers

ISBN: 1-85957-284-7

J. L. Koenig

(Case Western Reserve University)

Infrared and Raman Spectroscopy of Polymers

1

Contents

1. Introduction .............................................................................................................................................. 5

2. Elementary Theory of Vibrational Spectroscopy ................................................................................. 5

2.1 Selection Rules for IR Spectroscopy .............................................................................................. 6

2.2 Selection Rules for Raman Spectroscopy ....................................................................................... 6

3. Basis of Vibrational Spectroscopy as a Structural Tool ....................................................................... 6

3.1 Structural Dependence of Vibrational Frequencies ........................................................................ 6

4. Vibrational Spectroscopic Instrumentation .......................................................................................... 7

4.1 Types of IR Instrumentation ........................................................................................................... 7

4.1.1 Dispersive IR Instrumentation ............................................................................................ 74.1.2 FTIR Instrumentation ......................................................................................................... 74.1.3 Microscopic FTIR Instrumentation .................................................................................... 74.1.4 FTIR Imaging Instrumentation ........................................................................................... 84.1.5 Filter IR Instrumentation .................................................................................................... 84.1.6 Fibre-Optic IR Instrumentation .......................................................................................... 9

4.2 Types of Raman Instrumentation .................................................................................................... 9

4.2.1 Dispersive Raman Instrumentation .................................................................................... 94.2.2 Fourier Transform Raman Instrumentation ........................................................................ 94.2.3 Resonance Raman Instrumentation .................................................................................. 104.2.4 Surface-Enhanced Raman Instrumentation ...................................................................... 104.2.5 Raman Mapping and Imaging Instrumentation................................................................ 114.2.6 Fibre-Optic Raman Instrumentation................................................................................. 11

5. Sampling for Vibrational Spectroscopy ............................................................................................... 11

5.1 IR Sampling .................................................................................................................................. 11

5.1.1 Transmission Spectroscopy .............................................................................................. 125.1.2 Internal Reflection (or Attenuated Total Reflection (ATR)) (a.20) .................................. 125.1.3 External Reflection Spectroscopy .................................................................................... 135.1.4 Diffuse Reflectance FTIR (DRIFT) Spectroscopy........................................................... 135.1.5 Emission Spectroscopy ..................................................................................................... 135.1.6 Microsampling .................................................................................................................. 13

5.2 Sampling for Raman Spectroscopy ................................................................................................... 13

5.2.1 Microscopic Sampling in Raman Spectroscopy and Imaging ......................................... 14

6. Measuring Polymer Orientation with IR and Raman Spectroscopy ............................................... 14

6.1 IR Dichroism................................................................................................................................. 14

6.2 Raman Characterisation of Polymer Orientation ......................................................................... 15

7. IR and Raman Applications to Polymer Characterisation ................................................................ 16

7.1 Material Identification .................................................................................................................. 16

Infrared and Raman Spectroscopy of Polymers

2

7.1.1 Additive Analysis ............................................................................................................. 167.1.2 Chromatographic Separation and Identification .............................................................. 17

7.2 Determination of the Chemical Structure of a Repeating Unit .................................................... 17

7.3 Crystalline and Conformational Structural Order in Polymers .................................................... 18

7.3.1 Introduction ...................................................................................................................... 187.3.2 Crystal Phases of Polymers .............................................................................................. 187.3.3 Complex Formation between Polymers and Complexing Agents ................................... 197.3.4 Conformational Analysis .................................................................................................. 197.3.5 Nematic Ordering in Polymer Dispersed Liquid Crystals ............................................... 19

7.4 Quantitative Analysis .................................................................................................................... 20

7.5 Copolymer Composition and Structure ........................................................................................ 21

7.6 Polymerisation Kinetics and Mechanism in Multicomponent Systems ....................................... 21

7.6.1 Approach .......................................................................................................................... 217.6.2 Examples Using IR Fibre Optics ...................................................................................... 217.6.3 Examples Using Raman Fibre Optics .............................................................................. 227.6.4 Examples Using Rapid Scan FTIR Spectroscopy ............................................................ 22

7.7 Polymer Blends.................................................................................................................................. 23

7.7.1 Utility of Polymer Blends ................................................................................................ 237.7.2 Miscible Blends ................................................................................................................ 23

7.7.2.1 Compatibilised Blends ........................................................................................ 237.7.2.2 Reactive Blends ................................................................................................... 23

7.8 Conducting Polymers .................................................................................................................... 24

7.9 Emulsion Polymers ....................................................................................................................... 24

7.10 Graft Polymers .............................................................................................................................. 25

7.11 Degradation of Polymers .............................................................................................................. 26

7.11.1 Degradation with Ionising Radiation ............................................................................... 267.11.2 Degradation by Photooxidation ........................................................................................ 267.11.3 Degradation by Thermal Oxidation Processes ................................................................. 277.11.4 Degradation by Chemical Exposure ................................................................................. 277.11.5 Analysis of Evolving Gases from Polymers .................................................................... 28

7.12 Orientation of Polymer Chains Due to External Perturbations .................................................... 28

7.12.1 Approach using Vibrational Spectroscopy ....................................................................... 287.12.2 Orientation Functions for Mechanical Deformation ........................................................ 297.12.3 Strain-Induced Crystallisation .......................................................................................... 297.12.4 Deformation-Induced Conformational Changes .............................................................. 307.12.5 Relaxation Processes after Drawing ................................................................................. 307.12.6 Electric Field Induced Reorientation of Polymers ........................................................... 307.12.7 Laser-Induced Orientation ................................................................................................ 30

7.13 Time-Resolved Spectroscopy ....................................................................................................... 30

7.14 Rheooptical FTIR Spectroscopy ................................................................................................... 31

7.15 Two-Dimensional IR (2D-IR) Spectroscopy ................................................................................ 31

7.16 Recycling of Polymers .................................................................................................................. 33

Infrared and Raman Spectroscopy of Polymers

3

The views and opinions expressed by authors in Rapra Review Reports do not necessarily reflect those ofRapra Technology Limited or the editor. The series is published on the basis that no responsibility orliability of any nature shall attach to Rapra Technology Limited arising out of or in connection with anyutilisation in any form of any material contained therein.

7.17 Depth Profiling from Surfaces and Interfaces .............................................................................. 34

7.17.1 Optical Depth Profiling Using ATR-FTIR Spectroscopy................................................. 347.17.2 Depth Profiling Using Photoacoustic IR Spectroscopy ................................................... 347.17.3 Depth Profiling Using Confocal Raman Microspectroscopy .......................................... 35

7.18 FTIR Microspectroscopy .............................................................................................................. 36

7.19 FTIR Imaging ............................................................................................................................... 37

7.20 Raman Microimaging ................................................................................................................... 38

Additional References ................................................................................................................................... 39

Abbreviations ................................................................................................................................................. 41

References from the Rapra Abstracts Database .............................................................................................. 43

Subject Index ...................................................................................................................................................... 129

Infrared and Raman Spectroscopy of Polymers

4

Infrared and Raman Spectroscopy of Polymers

5

1 Introduction

Vibrational spectroscopy represents two physicallydifferent, yet complementary spectroscopictechniques: infrared (IR) and Raman spectroscopy.Vibrational spectroscopy is advantageous as ananalytical tool for polymers, because it provides awealth of information about complex macromoleculeswith respect to composition, structure, conformation,and intermolecular interactions utilising simplesampling techniques. Although both spectroscopicmethods have been successfully utilised for manyyears, recent advances in electronics, computertechnologies and sampling techniques make Fouriertransform IR (FTIR) and laser-excited Ramanspectroscopy powerful and versatile analytical tools.These spectroscopic methods utilise a broad range ofsampling techniques and do not require priorseparation techniques such as solvent extraction andthey do not require high vacuum. Low instrument cost,speed and simplicity make them cost effective forpolymer analysis. Additionally, the techniques aresuitable for quality and process control applications.

IR spectroscopy is one of the most powerfulspectroscopic tools available for the analysis of polymersystems (a.1). IR spectroscopy is molecularly specificwith high sensitivity. It is based on the absorption orattenuation by matter of electromagnetic radiation of aspecified motion of chemical bonds. Through quantumphysics, nature defines the absorption modes, theirlocations in the frequency spectrum and the amount ofenergy absorbed by each molecule. The absorbance at acharacteristic frequency is a measure of the concentrationof the chemical species being probed in the sample.

The Raman effect occurs when a sample is irradiatedby monochromatic light, causing a small fraction ofthe scattered radiation to exhibit shifted frequenciesthat correspond to the sample’s vibrational transitions.Ground-state molecules produce lines shifted toenergies lower than the source, while the slightlyweaker lines at higher frequency are due to moleculesin excited vibrational states. These lines, the result ofthe inelastic scattering of light by the sample, are calledStokes and anti-Stokes lines, respectively. Elasticcollisions result in Rayleigh scattering and appear asthe much more intense, unshifted component of thescattered light. The ratio of the intensities of the Stokesand anti-Stokes lines can be used to determine thetemperature of the sample.

In normal Raman scattering, a molecule is excited to avirtual state, which corresponds to a quantum levelrelating to the electron cloud distortion created by the

electric field of the incident light. A virtual state doesnot correspond to a real eigenstate (vibrational orelectronic energy level) of the molecule, but rather is asum over all eigenstates of the molecule.

Raman spectroscopy is now coming of age as a routineanalytical method. Advances in Raman technology havemeant that robust, user-friendly equipment can bemanufactured at a reasonable cost. Key features of theinstruments include high stability and optical efficiency,large frequency scan ranges, confocal and spatialresolution, mapping capability, rapid imaging, highresolution, and near IR (NIR) excitation to reduceinterfering fluorescence. These advances allow manyapplications of Raman spectroscopy and Ramanmicroscopic systems to polymer analysis.

2 Elementary Theory of VibrationalSpectroscopy

Vibrational spectra including IR and Raman result fromthe interactions of the vibrational motions of a moleculewith electromagnetic radiation (a.2). A simple harmonicoscillator model can describe these vibrationalinteractions. After separating the electroniccontributions, each molecule has an internal vibrationalenergy, U, which can be expressed in terms of thecoordinates and interbond forces between the atomsconstituting the molecule. A nonlinear moleculeconsisting of N atoms has 3N–6 degrees of freedom.Thus, a set of 3N–6 generalised coordinates, Gi, canbe found that completely describes the internal motionsof this nonlinear molecule. The internal energy of themolecule can be written as:

U = U(G1…Gi)

where i = 3N–6.

It can be shown that the internal energy can be written:

U U Qo ii

ii= + ∑1 2 2Λ

where Qi are a set of ith normal coordinates and Λii isa diagonal matrix. Thus, we have a system of weaklycoupled harmonic oscillators. The first term, Uo, is theinternal potential energy of the molecule in theequilibrium state. The second term represents thecontribution to the potential energy from thefundamental collective vibrational bands, while thecubic and higher terms are responsible for combination,difference, and overtone bands.

Infrared and Raman Spectroscopy of Polymers

6

The decomposition of coupled harmonic oscillators intoa collection of independent oscillators is known as anormal mode expansion and the independent oscillatorsare called normal modes. Normal modes are definedas modes of vibration where the respective atomicmotions of the atoms are in ‘harmony’, i.e., they allreach their maximum and minimum displacements atthe same time. These normal modes can be expressedin terms of bond stretches and angle deformation(termed internal coordinates) and can be calculated byusing a procedure called normal coordinate analysis.

2.1 Selection Rules for IR Spectroscopy

A normal vibrational mode in a molecule may give riseto resonant IR absorption (or emission) ofelectromagnetic radiation only when the transition isinduced by the interaction of the electric vector, E, ofthe incident beam with the electric dipole moment, μi,of the molecule. That is, the dynamic dipole momentof the ith normal mode, δμi/δqi or μi, is nonzero. Theintensity of the transition is proportional to the squareof the transition dipole moment, i.e., the matrix elementof the electric dipole moment operator between the twoquantised vibrational levels involved.

2.2 Selection Rules for Raman Spectroscopy

Raman scattering is envisaged as the process ofreradiation of scattered light by dipoles induced (P)in the molecules by the incident light and modulatedby the vibrations of the molecules (a.3). In normalRaman scattering by molecules in isotropic media,the dipoles are simply those that result from the actionof the electric field component, E, of the incident lighton the molecules,

P = αE

where α is the molecular (dipole) polarisability.

The molecule will scatter light at the incident frequency.However, the molecule vibrates with its own uniquefrequencies. If these molecular motions produce changesin the polarisability, α, the molecule will further interactwith the light by superimposing its vibrationalfrequencies on the scattered light at either higher or lowerfrequencies. Raman scattering stems from the oscillatingpolarisability within a molecule as a function of vibrationand not from the permanent dipole of the molecule. Asa result, Raman spectra are less affected by dipoleinteractions and as a result show sharp, stable lines.

3 Basis of Vibrational Spectroscopyas a Structural Tool

Our primary interest is in determining the structureof polymers so we need to understand the molecularbasis of vibrational spectroscopy as a structural tool(a.4). The vibrational energy levels can be calculatedfrom first principles by using a technique callednormal coordinate analysis (a.5), and as a result someof the factors influencing spectra have beendiscovered.

The vibrational frequencies of a molecule depend on:

• Nature of the motion,

• Mass of the atoms,

• Detailed geometric arrangements,

• Nature of the chemical bonding, and

• Chemical and physical environment.

Vibrational techniques are particularly sensitive to thestructure of the macromolecules. A vast literatureexists from which group frequencies have beencorrelated with structural components of themolecules (a.6).

3.1 Structural Dependence ofVibrational Frequencies

A vibrational spectrum either is ordinarily recorded inwavenumbers (cm-1), the number of waves percentimetre. The relationship between ν and thewavelength, λ (μm), is

ν (cm-1) = (104) / λ (μm)

which can also be written

ν (cm-1) = 3 x 1010 Hz

The wavenumber scale is directly proportional to theenergy and the vibrational frequency of the molecule.

In wavenumbers

ΔEvib = h cs ν (cm-1)

where ΔEvib is the vibrational energy level separation,h is Planck’s constant (6.62 x 10-34 J.S), and cs is thespeed of light (3 x 1010 cm/s).

Infrared and Raman Spectroscopy of Polymers

7

The fundamental IR region arbitrarily extends from4,000 cm-1 to approximately 300 cm-1. The far-IRregion extends from 300 to 10 cm-1, and the observedbands are due to molecular torsional motions as wellas lattice and intermolecular modes. The low IR sourceenergy makes this region generally inaccessible exceptwith special instrumentation. The NIR region extendsfrom 14,000 to 4,000 cm-1 (0.7-2.5 μm) and theobserved bands consist of overtones and combinationsof fundamental mid-IR bands (a.7). The NIR isbecoming an important IR method, particularly inquality control.

4 Vibrational SpectroscopicInstrumentation

4.1 Types of IR Instrumentation

IR spectroscopic instrumentation is grouped intomultiplex (Fourier transform) and nonmultiplex(dispersive) methods. These two categories reflect themeans by which the spectra are acquired.

4.1.1 Dispersive IR Instrumentation

A dispersive IR instrument (such as a scanningspectrometer) utilises a grating or prism as awavelength separation device to resolve the IRradiation into individual wavelength components(referred to as spectral resolution elements). A meansis provided in the instrument, such as an exit slit, toisolate specific spectral resolution elements forpassage to the detector. The IR spectrum is obtainedby moving (scanning) the grating over a givenwavenumber region after passing through the sample.The intensity of the spectral resolution element isdetermined by the intensity of the source and thesensitivity of the detector.

Scanning IR spectrometers have a rich history of usebut they have a number of disadvantages arisingprimarily from the ‘step-wise’ nature in which thespectra are acquired. The optical dispersion process andthe entrance and exit slits limit the amount of energyfalling on the detector to a small fraction of the totalIR energy. Additionally, moving the grating or prismimposes strict mechanical tolerances on the opticalcomponents. With scanning spectrometers it is not easyto increase the signal-to-noise ratio (SNR) by multiplescanning, as it is difficult to reproduce precisely theposition of the grating.

4.1.2 FTIR Instrumentation

IR absorbance spectra have traditionally been recordedusing dispersive instruments but, since 1970, FTIRinstruments have been available that are capable ofcollecting high-quality spectra in a fraction of the timepreviously required with enhanced SNR andwavenumber accuracy. The key component of thesespectrometers is a Michelson interferometer, whichoperates on the principle of amplitude division of theincoming light. The mechanism is simple. Theincoming light is split inside an interferometer, onebeam going to an internal fixed mirror and the other tothe moving mirror. After reflection, the beamsrecombine inside the interferometer, undergoingconstructive and destructive interference, producing theinterferogram. The spectral information is containedin the interferogram. After the data are detected andstored, it is necessary to perform a mathematicaltransform operation (a Fourier transform) on the dataset to convert it into a conventional spectrum.

The primary advantage of multiplexing the spectralresolution elements in the IR is the improvement inthe SNR. The improvement arises because the detectorirradiance for each measurement is increased. Becausethe detector noise is constant and independent of thesource, the SNR is improved because the multiplexingdistributes the detector noise over the intensities ofmany spectral resolution elements. This distributionprocess lowers the noise in each spectral resolutionelement more so than if the spectral resolution elementis measured individually by step scanning.

Mid-IR measurements are typically performed usinga linear scan interferometer and appropriate samplingaccessory to guide the light to and from the sampleof interest.

4.1.3 Microscopic FTIR Instrumentation

FTIR microspectroscopy is a microanalyticaltechnique, which interfaces an FTIR spectrometer toan optical microscope. Regions of interest in the sampleare spatially isolated using the microscope’s apertures.It enables the IR spectrum of sampling regions downto about 10 μm resolution to be taken. Consequently,FTIR microscopy is ideal for compositional mappingand analysis of heterogeneous samples whose domainsizes are in the tens of micrometre range.

FTIR microscopes use x15 and x10 condensor lensesof the non-IR absorbing Cassegrainian type. They areconstructed from front surface mirrors and are mounted

Infrared and Raman Spectroscopy of Polymers

8

on-axis so that the path for the visible light is parafocaland colinear with the IR light. The microscope stageis computer controlled with 1 μm steps. The sampleis not physically aperatured since the sample isspatially isolated from the microscope aperatures. ForIR microscopy, two apertures take up positions suchthat their images concide in the sample plane(redundant aperturing). The aperatures are a set ofcrossed knife blades in the form of a rectangle whichis of adjustable size.

The principal problem in IR microscopy is thepresence of scattered light due to diffraction whichlimits the spatial resolution by increasing the noise.Diffraction is significant when the aperturedimensions approach the wavelength of the IRradiation. The main effect of diffraction is that at smallaperature sizes, light spreads outside the specified areainto the surrounding region. As higher spatialresolution is sought, the problem increases, as theapertures are smaller, ultimately leading to loss ofspectral quality and photometric accuracy.

4.1.4 FTIR Imaging Instrumentation

FTIR imaging (as opposed to FTIR mapping) is amethod using two-dimensional array detectors and theimage is obtained in the ‘snap-shot’ mode, i.e., allelements of the field of view of the microscope arerecorded simultaneously. FTIR imaging is anoutstanding new tool for online materials monitoring.A spectroscopic imaging system consists of threecomponents: image capturing, image processing, anda visualisation system.

The spectral data obtained from IR imaging areanalysed to produce a variety of response factors whichare spatially expressed in terms of the individual datagrid coordinates. The data collection associated withthe spectroscopic mapping contains all of theinformation required to deconvolute the contributionsof the different species in the sample. Using a computer,one can analyse the entire spectral range at eachpositional coordinate or, for a given frequency, developa spatial image demonstrating the spatial distributionof an object-specific spectral feature (a.8).

The advantages of FTIR imaging are:

• Micro-spatial (~7 μm) chemical mapping ofheterogeneous complex samples,

• High sensitivity (ppm in many cases),

• High selectivity (IR spectra are fingerprints ofmolecules with many bands available),

• Rapid acquisition of data,

• Sample preparation is simple (optical microscopicmethods are generally useful),

• Experiment can be automated to trigger acquisitionas required and

• Images can be computer-enhanced for visualisationand interpretation.

FTIR imaging with a focal plane array (FPA) detectoris a new state-of-the-art multichannel (a.9) method ofsimultaneously recording the spectral image of asample as shown in Figure 1 (a.10).

The IR chemical imaging system measures chemically-specific IR spectra using a mercury cadmium telluride(HgCdTe) FPA detector which provides broadfrequency response (out to ~ 18 μm), high sensitivity(2 x 1011 cm Hz 1/2/Watt), and an operating temperatureof 40-60 K.

4.1.5 Filter IR Instrumentation

One IR spectroscopic system often used for industrialmonitoring is the ‘selective-wavelength’ spectrometer

Figure 1

Diagram of an FPA camera imaging system(x and y refer to axis)

Infrared and Raman Spectroscopy of Polymers

9

or a ‘filtometer’ (a contraction of the terms ‘filter’ and‘photometer’). These devices consist of a source ofradiation, energy collecting optics, a beam chopper, asample compartment, another set of collection opticsand a radiation detector or detectors. Interference filtersprovide wavelength selection.

The basic function of band-pass optical filters is toefficiently transmit light within a chosen wavelengthband and effectively reject the wavelengths lyingoutside of this band. The ratio of the in-band (desired)transmitted energy to the out-of-band (undesired)transmitted energy is the single most importantparameter to be considered.

The electronics of the filtometer include power suppliesthat operate the source, control temperature and poweramplifiers and related circuits that convert detectorsignals to concentration values. The limitation of thistype of control instrumentation is primarily sensitivityparticularly when remote sensing, via emission, is thesampling method.

Filter IR instruments have found broad applications inprocess control in the past (a.11). By utilising a portableIR spectrometer, the characteristic chemical sensitivityand selectivity of IR measurements can be performedin the field to interrogate the composition of industrialsamples (a.12).

4.1.6 Fibre-Optic IR Instrumentation

IR-transmitting optical fibres are evanescent wavesensors using a mathematical deconvolution techniqueto extract the absorbances and follow theconcentrations of the components as they occur in bothlaboratory scale and process production. The fibre-opticprobe used can be placed at specific locations withinthe samples or at the surface. The specificity of thetechnique, the speed of data acquisition and theportability of equipment make this method ideal as atool to fundamentally probe polymer reactions andprocesses. Chalcogenide optical fibres are used to directIR radiation from an FTIR spectrometer through anattenuated total reflection (ATR) probe immersed in areactor and back to the spectrometer.

4.2 Types of Raman Instrumentation

The evolution of Raman instrumentation has beendramatic. After making difficult measurements withuncertain sources, the laser came along and Raman

became a revitalised field. This was followed by theavailability of computers, two-dimensional detectorsand filter devices to replace monochromaters. Only afew brief remarks will be made here with referencesgiven for the interested reader.

4.2.1 Dispersive Raman Instrumentation

The configuration for a Raman dispersive experimentbasically consists of five parts (laser, sample, dispersingelement, detector and computer) (a.13). Amonochromatic laser beam (excitation radiation) isfocused on the scattering sample. The scattered lightfrom the sample is focused on the entrance slit of amonochromator and dispersed. The dispersion elementdiscriminates between the strong elastic scattering(Rayleigh scattering) and the weak inelasticallyscattered light (Raman scattering) with differentfrequencies. A typical single monochromator providesstray light rejections of 10-5-10-6 (as a fraction of theRayleigh light that enters the spectrometer) limited bythe imperfections on the optical surfaces such asgratings. Double and triple monochromators are oftenrequired to obtain adequate stray light rejection.

The Raman spectrum is given by the detection of theintensity of the scattered, frequency-shifted light by aphotoelectric system. The resulting signal of thedetector is amplified and converted to a formappropriate for plotting as a function of frequency.

4.2.2 Fourier Transform Raman Instrumentation

The basic problem in Raman spectroscopy is theinefficiency of the Raman scattering; roughly only oneout of 108 incident photons is Raman scattered. This,coupled with the fact that most polymeric systems giverise to an interfering fluorescent background, leads toa real problem of detectibility. For example, if a systemcontains one part per million of an interfering systemwhich fluoresces under visible excitation, the sameincident flux of 108 photons will produce 100fluorescent photons which will completely mask theRaman signal. This fluorescence does not occur whenthe excitation frequency is below the electronic energylevels of the molecules. The recent development ofFourier transform Raman (FT-Raman) spectroscopy,using NIR excitation, drastically reduces the problemof fluorescent interference.

FT-Raman also benefits from advantages inherent tointerferometry: high collection efficiency, excellent

Infrared and Raman Spectroscopy of Polymers

10

wavelength precision, easily variable resolution andspectral coverage, software developments in FTIR(a.14). The restrictions of FT-Raman arise from the lowSNR. The SNR is limited by detector noise rather thansignal shot noise. Detectors in the 1 to 2 μm region arenoisy. The result is an SNR comparable to that for asingle-channel dispersive system with equalmeasurement time (a.15).

FT-Raman spectroscopy became possible due to thecommercial availability of the Nd:YAG laser output at9395 cm-1. The Stokes-shifted Raman scattering occursin the 5000-9000 cm-1 spectral range, coincident withthe NIR region. Although the photon energy at 1076 nmis insufficient to cause fluorescence (which canoverwhelm the weak Raman scattering spectrum), theintensity of Raman scattering is diminished by a factorof ~22, in comparison to excitation at 488.0 nm (thelaser frequency of the Ar+ laser); this factor can becompensated for by increasing the excitation power.

To obtain good Raman spectra using the FT-Ramanmethod, the unwanted Rayleigh scattering must beremoved. Because of the nature of the Michelsoninterferometer, both Rayleigh and Raman-scatteredlight enter the system. Since the Rayleigh componentis from 106 to 108 times more intense than the Ramanscattering, it must be removed before it reaches thedetector, because a signal of this intensity drives thedetector into the distributive noise regime, resulting inhigh-frequency noise spread throughout thetransformed spectrum.

4.2.3 Resonance Raman Instrumentation

Resonance Raman spectroscopy occurs when the energyof the exciting beam is close to an electronic energy levelof the molecule and the excitation makes one term inthe sum of eigenstates dominate over all others.Resonance Raman spectroscopy takes place when thefrequency of the exciting line is similar to the absorptionfrequency of a chromophore in the sample. When thisoccurs, the electron cloud surrounding the molecule ismore readily distorted by the electric field of the incidentlight. The transition has a higher probability, and thereis an enhancement of the Raman process. The Ramansignal from the chromophore can be enhanced by sevenor eight orders of magnitude. The vibrational modesenhanced are dominated by vibrational bands that arepart of the chromophore responsible for the resonance.The resonance lines are generally totally symmetric anddistort the molecule along directions of electron densitychanges between the ground and the resonant electronicexcited state.

Ultraviolet Raman resonance (UVRR) spectroscopyprovides for chemical species identification from boththe characteristic vibrational structure and electronicspectra. The resonance enhancement also increases theabsolute sensitivity of detection, making it easier todetect the structures. The advantages of UVRRspectroscopy are high sensitivity, lack of fluorescenceand suitability for use in aqueous solutions.

Resonance Raman spectroscopy combines bothvibrational and electronic spectroscopies. Thevibrational spectrum at a particular excitationwavelength provides the first dimension. Theexcitation spectrum, the intensity of each vibrationalband as a function of the excitation wavelength,provides the second dimension. Since mostmolecules have resonance enhancement in the UV,this approach is quite general, but not universal. Theavailability of a range of excitation frequencies fromthe laser source makes exploitation of this form ofRaman scattering possible.

Detection of UVRR spectra is complicated by a numberof experimental difficulties: the photooxidation andphotodestruction of molecules, distortion of spectralinformation due to optical saturation phenomena andphotoinduced transients, and fluctuations of thescattered light intensity in inhomogeneous samples.

4.2.4 Surface-Enhanced Raman Instrumentation

In surface-enhanced Raman spectroscopy (SERS),increased Raman signals are observed from moleculesattached to metallic clusters ranging in size of the orderof tens of nanometres (a.16). Enhancements as high as1014 have been observed. These enhancement factorscan lead to single-molecule Raman spectroscopy (a.17).Using a Raman microscope the probe volume can beas small as 10 picolitres. Spectra can be measured witha one-second collection time.

In order to achieve large surface Raman signals, it isnecessary that the metal surfaces are specially preparedin one of several ways, which renders them rough orfinely divided on a length scale comparable to opticalwavelengths. Under favourable conditions, SERS-active metals enhance the surface Raman intensity byup to 105-fold, giving strong Raman signals.

The enhancement of Raman scattering at noble metal(gold, platinum, etc.) surfaces can be attributed to twofactors. One is an electromagnetic effect (discussedabove) observed for molecules near roughened noblemetal surfaces, and the second is a chemical interaction

Infrared and Raman Spectroscopy of Polymers

11

between the absorbed molecule and the metal surface.The electromagnetic enhancement observed by SERSarises from the unique optical properties of noble metals.The zero oxidation electronic configurations of thesemetals are d10s1. The single s electron is well shieldedby the inner shell electrons and behaves as a free electron.In the visible region of the spectrum, this free electroncauses the dielectric constant of the metal to have a largenegative real component and a small imaginarycomponent. The large negative component of the realpart means that the electrons react very strongly toincident radiation and their displacement is such thatthe field due to the polarisation of the particles resistsfurther polarisation. The result is a resonance conditionthat absorbs energy from the incident light and creates alocally intense electric field within the metal particle.

When the incident radiation interacts with the surface,it causes the free electrons to oscillate with the incidentelectric field and polarises the noble metal particles.This creates a strong local electric field at the particlesurface known as a surface plasmon. When a moleculeis in close proximity to a noble metal particle themolecule is polarised by the electric field of the noblemetal particle. This leads to an enhancement of theRaman signal because the Raman scattering isproportional to the square of the local electric field.

4.2.5 Raman Mapping and ImagingInstrumentation

The ideal Raman spectrometer would consist of a high-dispersion, low-stray-light (where the scattered lightis low) single monochromator with a multichanneldetector. In the new generation of Raman instruments,a polychromator or spectrograph and a multichanneldetector are used instead of the monochromator andphotomultiplier. The entire spectrum is collectedsimultaneously using an array of detectors in whicheach element of the multichannel detector iscomparable in sensitivity to a single photomultiplier.The assumption is that all light incident on the detectoris correctly positioned with a single wavelengthincident upon each single detector. In this way, the timeneeded to record a spectrum is reduced markedly.Additionally, the simultaneous detection of thespectrum increases the accuracy of intensitymeasurements of different Raman bands and avoidserrors in interpreting accidental changes in thebackground due to laser fluctuations as Raman bands.Furthermore, multichannel detectors offer newpossibilities for investigation of photolabile systems(i.e., systems that degrade by photoirradiation), time-resolved experiments and chemical images.

The wavelength at a particular detector element isdetermined by the position of that element at the focalplane of the monochromator (the grating position). Inanother mode of operation, an acousto-optic tunablefilter (AOTF) is used rather than a monochromater. InRaman applications, the AOTF is used to spectrallyfilter the source (a.18). Under computer control, theAOTF is swept through a wavelength range and, atpredetermined intervals, images are recorded. For morerapid operation, the AOTF may be digitally tuned topredetermined frequencies where single frames maybe collected (a.19).

In practice, the AOTF is placed between the Ramanscatterer and a Si FPA detector yielding a no-movingparts Raman spectroscopic imager. The AOTF replacesthe dispersive monochromator and is operable between400 nm and 1900 nm. At each discrete wavelength acharge collection detector (CCD) frame is collected,digitised and stored. The size, wavelength range,wavelength increment and exposure time for eachimage frame maybe modified under computer control.Potentially, one can record one frame/second.

4.2.6 Fibre-Optic Raman Instrumentation

A dual-fibre optical probe has been developed forRaman spectroscopic monitoring of a number ofpolymer processes. In the dual-fibre configuration theinternal bundles transmit the light to the sample andthe outer fibres carry the signals back to thespectrometer for processing.

5 Sampling for VibrationalSpectroscopy

5.1 IR Sampling

One of the most attractive aspects of FTIR spectroscopyis its ability to deal with a great number of samplingtechniques, making it a versatile method which can beadapted to the study of a wide range of materials.

For IR spectroscopy, sample preparation has been alabour-intensive operation requiring some measure ofskill and experience. Conventional IR spectroscopy ismainly based on transmission measurements except forsamples for which the preparation of a thin layer isproblematic, inadequate, or prohibited. In these casesspecial sample preparation is required as indicated inSection 5.1.1, 5.1.2, etc. The main sampling techniquesmay be seen schematically in Figure 2.

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5.1.1 Transmission Spectroscopy

Transmission spectroscopy is the simplest and mostpopular mode for quantitative analysis. Radiation passesthrough the sample and is absorbed by a length equal tothe thickness of the sample in the direction of IRpropagation. The single beam intensity can be ratioedagainst a background collected without the sample andan absorbance spectrum obtained. The absorbance hasa simple linear relation to the concentration under mostconditions and can be used for quantitative analysis. Ingeneral, it delivers the highest SNR of all samplingtechniques and does not affect the spectral data in anymanner. No special sample handling techniques arerequired and quantitative data processing isstraightforward. However, films usually have to be thin,i.e., 1 to 100 μm. Such films can be prepared by solventcasting or compression moulding.

5.1.2 Internal Reflection (or Attenuated TotalReflection (ATR)) (a.20)

Attenuated reflection may be used for samples with noor low transmission or when sample geometry demands

it. The sample is brought into contact with an IR-transparent crystal of high refractive index. The IRbeam then traverses the length of the crystal whilepenetrating the sample with multiple internal reflectionsat the free crystal surface. Thus, depending on therefractive index and angle of incidence, the region ofthe sample examined is typically a 0.1-10 μm layerclose to the crystal. Spectral data is different from thatobtained in transmission and the signal does not varylinearly with concentration. Hence, calibration isrequired for quantitative studies.

Depth profiling is also a possibility using the ATRtechnique (a.21) and probed depth (i.e., how deep inthe sample the light probes) varies as

dn n

p

o

=−( )

λπ θ2 2 2 2 1 2

sin/ (1)

where dp is the probed depth, no and n are the refractiveindices of the ATR crystal and the sample respectively,θ is the angle of incidence and λ the wavelength ofradiation. Algorithms to extract depth of penetrationindependent of wavenumber have been developed(a.22, a.23).

Figure 2

IR sampling techniques for polymers

Infrared and Raman Spectroscopy of Polymers

13

5.1.3 External Reflection Spectroscopy

Reflection-absorption spectroscopy is an externalreflection technique that utilises an IR beam incident ata grazing angle. This allows for a convenient method tostudy polymers in contact with reflective (e.g., metal)surfaces. When IR light impinges on a metal surface, anelectrical field arises near the surface. The metallicsurface imposes a strict dipole moment selection rule,which demands that the incident light should have acomponent parallel to the plane of incidence (p- orparallel polarisation). The interaction between the sampleand the incident light is strong when the angle ofincidence is between 75° and 89° and approaches amaximum at 88°. For parallel-polarised incidentradiation, only the dipole moments of the surface speciesnormal substrate interact with the electric field. A detaileddiscussion of the technique has been published (a.24,a.25). It has been established that the sensitivity ofreflection absorption IR spectroscopy is greatly improvedwhen using a grazing incidence (65° or more). In theparticular case of thin layers (of organic or inorganicmaterial) deposited on a good reflecting surface such asa metal, a lower detection limit of a few nanometres inthickness can be achieved. The drawbacks include theappearance of asymmetric absorption modes and shiftingof mode frequencies that may be corrected by the use ofthe Kramers-Kronig transformation.

5.1.4 Diffuse Reflectance FTIR (DRIFT)Spectroscopy

Light impinging on a solid or powdered surface isdiffusively scattered in all directions and may bedirected to an IR detector. This technique is particularlyuseful if the sample is strongly scattering and weaklyabsorbing. A general theory for powdered samples wasdeveloped by Kubelka and Munk (a.26) and relates thesample concentration to the scattered radiationintensity. DRIFT spectroscopy requires little samplepreparation, is ideal for particulate substances and hasfast data collection with good SNR. However, someinformation is lost in the highly absorbing regions andthere is small band shape distortion. Quantitativeanalysis should be performed on the same particle size.DRIFT spectroscopy has been used to probe polymerlayers, fibres and polymers on metals (a.27).

5.1.5 Emission Spectroscopy

If collected correctly, emission spectra mirrorabsorbance spectra and can be collected even fromopaque samples. The material must not have thermalgradients, readsorption of emission, or self-adsorption.

5.1.6 Microsampling

As far as microspectroscopy is concerned, onlytransmission and reflection under near-normalincidence are initially implemented. The recent launchof specialised objectives provide the user withadditional techniques such as external reflection undergrazing angle and ATR.

5.2 Sampling for Raman Spectroscopy

The sampling techniques used in Raman spectroscopyare shown in Figure 3. A sample in any state can beexamined without difficulty by using Ramanspectroscopy. The laser beam is narrow, collimated, andunidirectional, so it can be manipulated in a variety ofways depending on the configuration of the sample.

Figure 3

Raman sampling techniques for polymers

Infrared and Raman Spectroscopy of Polymers

14

For liquids, a cylindrical cell of glass or quartz withan optically flat bottom is positioned vertically inthe laser beam. For solids, the particular method useddepends on the transparency of the sample. For clearpellets or samples, right angle scattering is used.With translucent samples, it is helpful to drill a holein the sample pellet. Powdered samples can beanalysed by using front-surface reflection from asample holder consisting of a hole in the surface ofa metal block inclined at 60° with respect to thebeam. Injection moulded pieces, pipes, and tubing,blown films, cast sheets, and monofilaments can beexamined directly. One of the advantages of Ramansampling is that glass containers can be used whichcan be sealed if desired (a.29).

5.2.1 Microscopic Sampling in RamanSpectroscopy and Imaging

The incorporation of high-resolution optics in aRaman spectrometer allows sampling from areas ofless than 1 x 10-6 m in diameter. The addition of aconfocal microscope improves the axial resolution toa couple of microns. Those developments, along withthe introduction of notch filters and holographictransmission gratings, allow the reduction of theacquisition time of Raman spectra from minutes toseconds. The fast data collection combined with thehigh lateral and vertical resolutions makes possiblethe collection of Raman images with several micronspatial resolutions.

6 Measuring Polymer Orientationwith IR and Raman Spectroscopy

Orientation can be defined as the preferential alignment(either uniaxial or biaxial) of polymer chains orsegments when submitted to an external force. Theorientation induces significant changes in the propertiesboth positively and negatively.

A high degree of alignment is the basis of improvedmechanical, optical, and electrical properties in almostall polymers. Many factors influence the orientationbehaviour of polymer chains, including crystallinity,phase separation, free volume, chain rigidity, molecularfriction, interchain interactions and chainentanglements. Consequently, it is necessary tounderstand the correlations among molecular order,material properties, and fabrication procedures.Experimental characterisation of the degree and

direction of alignment is required in order to understandhow molecular design and processing strategies leadto the ultimate state of alignment. There are severalmethods available, including IR dichroism, X-raydiffraction, nuclear magnetic resonance (NMR),birefringence, polarised fluorescence, ultrasonicmeasurements, and polarised vibrational spectroscopies(IR and Raman). Of all these techniques, IR dichroismis one of the most frequently applied, since it isapplicable to many polymer systems, it can be used tomake measurements on the microscopic andmacroscopic scales, and it can specifically measureorientation of different phases (i.e., amorphous orcrystalline) in the same sample.

6.1 IR Dichroism

In general, IR absorption is caused by the interactionbetween the IR electric field vector and the moleculardipole transition moments related to the molecularvibrations. Absorption is at a maximum when theelectric field vector and the dipole transition momentare parallel to each other. In the case of perpendicularorientation, the absorption is zero. Directionalabsorptions are measured using polarised light. Theterms parallel and perpendicular refer to the orientationof the polarised beam with respect to a reference axis.For deformation studies, the reference axis correspondsto the stretching direction.

The IR dichroic ratio may be considered to becharacteristic of the directional orientation of thesegments of the molecule. For a polymer whosemolecular axis is oriented parallel to the spectrometersampling plane, the dichroic ratio, R, is defined as

RA

A=

||

where A|| is the absorbance parallel to the chain axis,and A⊥ is absorbance perpendicular to the chain axis.For highly oriented samples, the dichroic ratio mayapproach either infinity or zero, depending on thealignment of the transition-moment vector withrespect to the molecular chain axis. The alignmentof the chain segments can be determined fromdichroic ratio measurements if the inherentpolarisations are known (a.29). In general, A|| andA⊥ are determined successively by using a polariserthat is aligned parallel and perpendicular to thestretching direction. For samples that have a lowlevel of orientation, the magnitude of the dichroicratio is close to 1. In these cases of minimal

Infrared and Raman Spectroscopy of Polymers

15

orientation, it is better to measure the dichroicdifference A||–A⊥ because it is a more sensitivemeasurement under these conditions.

One of the practical problems in the case of IRdichroism measurements arises from the requirementof low band absorbance (roughly lower than 0.7absorbance units) in order to permit use of the Beer-Lambert law. This condition implies use of very thinfilms in the range of 1 to 200 μm. NIR measurementsalleviate this problem.

6.2 Raman Characterisation of PolymerOrientation

Raman scattering arises from the interaction betweenradiation induced oscillating electric dipoles andmolecular vibrational modes. In general, the inducedpolarisability is not necessarily in the direction of theincident beam, and they are related by a second rangetensor, α, thus:

P = αE

or written in terms of the components:

Px = αxxEx + αxyEy + αxzEz

Py = αyxEx + αyyEy + αyzEz

Pz = αzxEx + αzyEy + αzzEz

where αxx, αyy and αzz are the components of theprincipal axes of the polarisability ellipsoid and αxy,αyz and αxz are the other components. A single crystalcan give up to six different spectra, depending on itsorientation towards the two directions of polarisationof the incident laser light.

Consequently, the Raman scattered light emanatingfrom even a random sample is polarised to a greater orlesser extent. For randomly oriented systems, thepolarisation properties are determined by the two tensorinvariants of the polarisation tensor, i.e., the trace andthe anisotropy. The depolarisation ratio is always lessthan or equal to 3/4. For a specific scattering geometry,this polarisation is dependent upon the symmetry ofthe molecular vibration giving rise to the line.

In solids, the problem of polarisation is morecomplicated, but the results are more rewarding (a.30).In solids, the molecular species are oriented withrespect to each other. Therefore, the molecular

polarisability ellipsoids are also oriented along definitedirections in the solid. Since the electric vector of theincident laser beam is polarised, the directionality inthe crystal can be utilised to excite and obtain Ramandata from each element of the polarisability ellipsoid.With the laser polarisation along z and collection alongz, a spectrum from the αzz component of the tensor isobtained. By rotating the analyser 90°, therebycollecting x polarised light while still exciting along z,αzx is obtained.

In the usual Raman experiment, the observations aremade perpendicular to the direction of the incidentbeam, which is plane polarised. The ‘depolarisationratio’ is defined as the intensity ratio of the twopolarised components of the scattered light which areparallel and perpendicular to the direction of thepropagation of the (polarised) incident light. Thepolarisation of the incident beam is perpendicular tothe plane of propagation and observation. For thisgeometry, the depolarisation ratio is defined as theintensity ratio:

ρ = VH/VV

where, for the right angle scattering experiment, V isperpendicular to the scattering plane and H is in thescattering plane. An alternate notation expressed interms of the laboratory coordinate system is:

A(BC)D

where A is the direction of travel of the incident beam,B and C are the polarisation of the incident and scatteredlight, respectively, and D is the direction in which theRaman scattered light is observed. Generally, theincoming beam is along the x axis, the scattered beamis along the z axis and the y axis is perpendicular to thescattering plane.

One of the major problems is the difficulty ofdetermining that the polarisation is scrambled whetherby scattering inhomogeneities in the sample itself orby the birefringence of the sample itself. Many spectrashow evidence of extensive depolarisation of both theincident and scattered light, and thus each spectrum isan indeterminate mixture of four different polarisations:the intended polarisation, the one resulting fromdepolarisation of the incident light, the one resultingfrom depolarisation of the scattered light, and (to alesser extent) the one resulting from depolarisation ofboth the incident and scattered light. When this occurs,little useful information is available from the individualpolarised spectra.

Infrared and Raman Spectroscopy of Polymers

16

7 IR and Raman Applications toPolymer Characterisation

7.1 Material Identification

IR and Raman spectroscopy are the best methods forthe identification of unknown compounds if the spectraof the reference compounds are known. The ideaunderlying spectroscopic identification is that a patternof frequencies provides a ‘fingerprint’ of a particularmolecule and that this pattern of frequencies can berecognised when a spectral database is searched.Spectral comparison of an unknown sample foridentification is generally done by visual comparison(often with the computer as a tool) or by using cross-correlation techniques. With cross-correlationtechniques, an identification is performed bycalculating a matching score for the spectra of theunknown and an IR spectrum of a known compoundin the database. Additional spectra in the database areranked according to the matching score determined andthe spectroscopist must make a final determinationbased on his knowledge of the properties of theunknown sample relative to the chemicals with highmatching scores.

Independent of the type of scoring system used, thereis always a risk of obtaining a false identification result.Each measured spectra can match the frequencies ofseveral different molecules in addition to the matchwith the molecule actually present in the sample. Falseresults are caused by the accidental matching of thefrequencies of a chemical with no properties similar tothe unknown. An incorrect result is also obtained whenthe score due to random matching cannot be discernedfrom the score match due to matching of the real spectrain the sample. It is therefore useful to include otherinformation when interpreting the quality of the match,such as the chemistry involved in the unknown sample.The likelihood of accidental matches (and hence thelikelihood of false identification) increases if thespectral reproducibility is reduced.

The Sadtler division of Bio-Rad Laboratories (http://www.sadtler.com) has a product on compact disccontaining 175,000 IR and 3,300 Raman spectra. Fora subscription price the user gets the disc and an e-mailed code from Sadtler that opens the disc forsearches on one computer for a year. Once the codeopens the disc, the user may perform unlimited lookupson one computer for one year. A lookup retrievesspectra by names or structures for comparison. Inaddition, the user may perform unlimited searches toidentify or classify unknowns. Other databases for

polymer and additives are also available (166, 357)including one for fibres (376). For Ramanidentification, the databases are smaller because of thelimited history of collection of spectra but attempts arebeing made to bridge the gap (a.31).

7.1.1 Additive Analysis

Polymer additives are materials designed to enhanceor upgrade the performance or capabilities of basepolymers to achieve the optimal properties for a specificapplication (a.32). Plastics would not be able to performtheir diverse functions without the assistance of a verybroad range of plastics additives (a.33). Without them,some plastics would degrade during processing and,over time, the polymers would lose impact strength,discolour, and become statically charged, to list just afew problems. Additives not only overcome these andother limitations, but can also impart improvedperformance properties to the final product.

It is necessary to be able to identify and quantify theadditives in polymers and vibrational spectroscopyis a particularly useful approach to this problem.Compared with traditional chemical analyses,vibrational methods are nondestructive and are time-and cost-effective as well as more precise. A largenumber of examples exist in the literature. Forexample, antistatic agents (polyethylene glycol (PEG)in polyethylene (PE)) can be detected directly usingFTIR sampling (367). An IR spectroscopic techniquefor the analysis of stabilisers (2, 6-di-tert-butyl-4-methylphenol) in PE and ethylene-vinyl acetate (EVA)copolymer has been described (368). It is possible toquantify the amount of external and internal lubricants(stearic acid in polystyrene (PS)) (371). Fillers inpolymers can also be analysed (white rice husk ash(predominantly silica in polypropylene (PP)) (268).Raman spectroscopy has been used to detect residualmonomer in solid polymethyl methacrylate (PMMA)samples (326).

It is also possible to determine multiadditives in thesame sample using FTIR and multivariate analysismethods. For example, the simultaneous determinationof the concentrations of silica, erucamide andbutylhydroxytoluene in PE were measured using IRspectroscopy and suitable calibration models. Theconcentrations were between 20 and 1100 wt/ppm(366). A multiadditive method was developed forcharacterisation of an antiblocking agent (silica) andlubricant (erucamide) in molten low densitypolyethylene (LDPE) samples (324).

Infrared and Raman Spectroscopy of Polymers

17

A method for the determination of vulcanised rubberadditives by FTIR spectroscopy using partial least-squares regression (PLSR) for multivariate calibrationwas developed (264). Interestingly enough,photoacoustic FTIR spectroscopy was used tocharacterise tread lugs sectioned from two worn off-the-road tyres. The tyres had experienced similarservice but displayed significantly differentperformance in that ‘chipping/chunking’ was visiblein one tyre brand. The technique was also used toexamine a variety of rubber compounding ingredients,such as polymers and fillers, and model tyre compoundscontaining different levels of these ingredients (341).A long standing problem in analysing natural rubber(NR) is the determination of attached nitrogenouscompounds. Bands at 3280 and 1540 cm-1 diminishedwhen a fresh field latex was treated with enzymefollowed by washing in the presence of surfactant. Aband at 3320 cm-1 that remained after the treatmentindicated the presence of residual amino acids bondedto the hevea rubber particles (349).

A surface method of measurement of a sizing agent(partly hydrolysed polyvinyl alcohol) on the warp yarnsubstrate (polyester/cotton) using NIR diffusereflectance spectroscopy has been described (337). Apartial least-squares (PLS) modelling procedure useda frequency segment of the NIR spectrum that is mostsensitive to changes in size concentration relative tothe warp yarn.

7.1.2 Chromatographic Separation andIdentification

The combination of chromatography and IRspectroscopy provides a versatile tool for thecharacterisation of additives. High performance liquidchromatography-FTIR (HPLC-FTIR) interface systemsdeposit the output of a chromatograph on an IR opticalmedium, which is then scanned to provide data as atime-ordered set of spectra of the chromatogram (138).A spray-jet interface is used to deposit the effluent froma narrow-bore liquid chromatography (LC) column ona zinc selenide window. The deposited additives areanalysed by FTIR transmission microscopy, yieldingidentification limits in the low-nanogram range (215).Although it is not a real time analysis, it has theadvantages of total solvent removal before IR analysis,analysis of the total LC effluent as opposed toincremental fractions, and the ability to produce IRspectra at high SNR.

A powerful new method of additive extraction has beendeveloped termed supercritical fluid extraction/FTIR

spectroscopy (SFE/FTIR) (303). The SFE/FTIRtechnique has been applied to the analysis of fibrefinishes on fibre/textile matrices. Three different fibrepolymer types were examined (polyurethane (PU),polyamide (PA) and aramid), each requiring a differentfinish. Finishes ranged from a single-componentpolydimethylsiloxane (PDMS) oil to more complexmulticomponent finishes that included varioussurfactants, fatty acid esters and soaps, antioxidantsand oils.

7.2 Determination of the Chemical Structure ofa Repeating Unit

The most common type of structure determination isstructure verification. In this case, enough informationis available (perhaps on the basis of well-knownsynthetic reaction paths) to propose a probablestructure. The structure information which is achievedusing IR and Raman spectroscopy is usually sufficienthere. One of the fundamental problems in polymerscience is the determination of the chemical structureof the repeat unit; this moiety determines all of thechemical properties such as reactivity, stability andweatherability. Vibrational spectroscopic techniques areadvantageous as a method of determining structurebecause the methods are applicable to all polymersregardless of the state of order. The IR and Ramanspectroscopy methods are accurate, faster than chemicalanalysis and reduce exposure to irritating, toxic andcorrosive chemicals.

Bisphenol A phenoxy polymers and bisphenol Apolycarbonates were blended in solution. Chemicalchanges from aromatic to aliphatic carbonate groupswere monitored by FTIR as a function of time andtemperature (348).

The network structure of an epoxy resin system andthe course of reaction of bisphenol A diglycidyl etherwith 1-cyanoguanidine as curing agent dissolved indimethyl formamide in the presence of differentaccelerators were studied. Fractions of reactive groups,such as oxirane rings, primary and secondary hydroxylgroups, imide and nitrile groups, were detected asfunctions of epoxy consumption and reactionconditions. Structural tautomerism of the curing agent,the influence of water, the reaction of nitrile groupsand other structural features of the curing system wereexamined (354).

The compound n-butyllithium was the initiator andcyclohexane the solvent for high-vinyl polybutadienesproduced from anionic polymerisation. Complexing

Infrared and Raman Spectroscopy of Polymers

18

agents were used to change the mode of addition to1,2 or vinyl, 1,2-dipiperidinoethane and diglyme werevery effective, although their effectiveness decreasedwith temperature. The microstructure of the polymerswas characterised by Raman spectroscopy using theRaman active carbon-carbon double bond stretchingbands of cis and trans vinyl structures at 1640, 1650and 1664 cm-1, respectively. The amount of eachcomponent was measured using band areas (369).

An IR method was developed for determining thehydroxyl number in samples of polyesters formed bythe copolymerisation of a hydroxy-functional acrylicoligomer with adipic acid and 1, 6-hexanediol (370).

Oxazolidone-isocyanurate polymers were prepared byreacting five glycidyl ethers with 4, 4´-diisocyanato-diphenylmethane in the presence of 2-ethyl-4-methylimidazole. The degree of cure of the resins wasfollowed by IR spectroscopy by measuring the fractionof the isocyanurate to oxazolidone linkages (377).

7.3 Crystalline and Conformational StructuralOrder in Polymers

7.3.1 Introduction

IR and Raman spectra are particularly sensitive to theconfigurations and conformations of the polymermolecules. The variations in the conformational andconfigurational structures are reflected in specificobservable frequencies. Consequently, it is possible todetect and quantify the amounts of the conformationalisomers whether they be crystalline, liquid crystalline,or disordered (amorphous). The vibrationalspectroscopic approach to structural elucidation inpolymers relies on the comparison of vibrationalspectra of polymers containing specific conformationalstructures (incorporated into the polymer duringpolymerisation or by thermal or chemicalmodification), with spectra of models (polymers andsmall molecules) containing similar structurespresumed to be present in the polymers.

7.3.2 Crystal Phases of Polymers

Structural changes in the orthorhombic-to-hexagonalphase transition of PE crystals were investigated in thecourse of heating to the melting point. The IR andspectral patterns characteristic of the hexagonal phasewere confirmed. In particular, the bands characteristicof the disordered short trans segments (shorter than

five methylene units) and the bands of the kink ordouble gauche linkages were detected. The observationof the trans and gauche bands was confirmed as wellas the existence of conformationally disordered chainsin the hexagonal phase (195).

The defect density of states of the tight (110) fold inPE is calculated. Modes of the (110) fold calculated at1348, 1342 and 1288 cm-1 and are assigned to IR bandsat 1346-1347 cm-1 and 1342-1343 cm-1 and near 1295cm-1. The (110) folds (approximately g′g′ggtg) alsocontribute to the gtg/gtg′ bands at 1368 cm-1, whereg = +60° and g′ = -60° from the plane of the C-Cbackbone and t = trans. In contrast to the (200) fold,the (110) fold does not exhibit a localised gap modenear 700 cm-1. The observed IR bands are assigned tothe defect modes of the (110) fold (373). The (110)folds are folds in the crystal plane and (200) folds liealong the (200) crystal plane.

The phase transition in an ethylene-tetrafluoroethylenealternating copolymer from the orthorhombic to thehexagonal structure is a result of the generation andpropagation of conformational collective defects (182).

Syndiotactic poly-p-methylstyrene (PPMS) exhibitsvarious crystalline forms and clathrate structures. Bandsdue to the syndiotactic stereostructure and bands typicalof the two different chain conformations are observedin the crystalline structures as well as bands sensitiveto intermolecular interactions typical of the differentmodes of chain packing (350).

In polyamide 66, normalised absorbances of thebands at 924 and 1136 cm-1 were plotted againstdensity and the intercept at zero absorbance provideda density of 1.26 g/cm3, which was very close to thecrystalline density. The 924 and 1136 cm-1 bandsare assigned to the conformation in the amorphousphase. The assignments of the bands at 936 and 1200cm-1 to the conformation in the crystalline phasewere confirmed (31).

FTIR analysis provided a direct method for theevaluation of the amount of alpha and beta formcrystalline phases in syndiotactic PS, although bothcontain chains in the same conformation (trans-planar)(186). Syndiotactic PS was found to exhibit two distinctvibrational peaks in the Raman spectrum. The presenceof long all-trans sequences gives rise to a peak at about773 cm-1, whereas trans/gauche conformations resultin a separate peak at 798 cm-1. With increasing levels ofcrystallinity, the integrated intensity of the 773 cm-1

grows at the expense of the 798 cm-1. The relative area

Infrared and Raman Spectroscopy of Polymers

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under the all-trans fundamental band can be directlyrelated to the crystalline volume fraction (173).

Cyclohexa(p-phenylene sulfide) (CHPS) is a precursorof poly(p-phenylene sulfide) (PPS). The FTIR andRaman spectra of CHPS resemble those of amorphousPPS. Specific modes indicative of the crystal structureand band shifts are reported and a crystal structurechange in CHPS which was induced by pressure orheat is identified (84).

7.3.3 Complex Formation between Polymers andComplexing Agents

Interactions between polyvinyl chloride (PVC) andcyclohexanone or n-methyl-2-pyrrolidone generatedthe occurrence of local configurational changes. Theresults suggest that the interaction is restricted to adefinite number of polymer sites although noinformation as to the exact type of these sites can bedrawn. The number of interaction sites is higher forcyclohexanone than for N-methyl-2-pyrrolidone (181).

The IR spectrum of the delta phase of the syndiotacticPS/ethylbenzene complex predominantly involvedbands in the 920 to 960 cm-1 region arising from helicalstructures. The 934 and 943 cm-1 peaks behaved as adoublet, primarily due to the delta phase, with thesplitting increasing on annealing. The 940 cm-1 peakwas solely due to the gamma phase helix. Theseassignments provide the opportunity for using thesebands for further studies of complexation/decomplexation in systems of this type (89).

7.3.4 Conformational Analysis

A study of annealed polycarbonate showed that theheating process was primarily a modification oftrans-trans and trans-cis population of the carbonategroup, leading to a more stable structure with a lowerinternal energy. Ageing proceeded mainly byextremely local rearrangements compatible with adensified structure (177).

The IR characteristic bands at 1230/1250 cm-1 ofstereoregular polyacrylonitrile (PAN) are dependenton not only the configuration, but also on theconformation through the arrangements of theconfigurations on the polymer chain. The effect ofconfiguration and conformation on the IR results wasdetermined to be a function of the film preparationconditions (180).

Isotactic PS samples were shock-cooled andsubsequently freeze-dried from very dilute solutionsin benzene. FTIR studies on these samples indicatedthat there were conformational differences betweenthese samples and a normal isotactic PS. Comparisonof the IR spectra indicated that spectral changesoccurred at the bands near 1261, 1085-1050, 982, 923-906 and 550 cm-1. The changes in intensity of thecrystalline bands showed that the freeze-driedisotactic PS from a very dilute solution exhibited ahigher crystallinity than annealed samples (252).

The conformational structures of polycarbonate werestudied in the solid state and in solution. Based onthe temperature dependences of the IR spectra, bandssensitive to transitions between the trans-trans andtrans-cis conformations of the carbonate group wereidentified (361).

The conformers of the ethylene glycoxy moeity ofPET, have been studied in the amorphous andcrystalline regions. The profiles of the 382 cm-1 bandand the 1020 cm-1 band for a series of specimensannealed at different temperatures. Consistent resultswere obtained from both bands for the compositionsof the three conformers, i.e., the trans conformer inthe crystalline state and both the trans conformer andthe gauche conformer in the amorphous state (365).

Poly(ethylene 2,6-naphthalate) (PEN) filmcontaining alpha, beta and amorphous phases wereprepared, and the amorphous contribution digitallysubtracted to yield the characteristic spectra of theamorphous, alpha, and beta phases. In other words,the amorphous spectrum is determined by meltingthe polymer, so after subtraction, one knows thespectrum of all of them. The alpha crystal formadopts an all-trans conformation, while the betacrystal form adopts a conformation with appreciablegauche character. Conformational changes in PENoccur due to the rotation of the naphthalene ring aswell as rotation of the ethylene glycol units. Thenormalised absorbances of the bands at 824 and 814cm-1 were correlated to polymer density, and can beused to represent the amorphous and alphacrystalline phases, respectively (56).

7.3.5 Nematic Ordering in Polymer DispersedLiquid Crystals

Real-time FTIR was used to study the curing of a UV-curable prepolymer (NOA65) and its mixtures withliquid crystals. Curing reactions were examined as afunction of film thickness, temperature, and liquid

Infrared and Raman Spectroscopy of Polymers

20

crystal content. While there was little dependence ofthe curing behaviour on the thickness of the film, theeffect of temperature was strong. Curing ratesexhibited a maximum around 325 K, whileconversions reached a plateau about 20 K higher.Liquid-crystal addition depressed the conversion.However, compared with the neat matrix, the finalconversion was significantly lower only for phase-separating concentrations. The rate of reactiondecreased, and the induction period for the onset ofpolymerising reactions increased, with increasingliquid-crystal concentration (38).

Nematic ordering can be observed and quantifiedbased on a change in a characteristic band of the liquidcrystal. Moreover, the phase separation and the onsetof nematic ordering can be temporarily resolved. Theconversion at phase separation decreased stronglywith an increase in liquid crystal content, while theconversion required for phase separation increasedwith increasing temperature. The fraction of liquidcrystal present as nematic droplets and total fractionof nematic domains in NOA65 were quantified fromchanges in the vibrational spectrum of the liquidcrystal (E7, which refers to the commercial label forthe liquid crystal) (37).

7.4 Quantitative Analysis

The primary result of IR transmission spectroscopyis the transmittance of the cell plus sample, (It)/(Io),

where Io is the intensity incident on the cell and It isthe intensity which leaves the cell, both measuredoutside the cell (Figure 4).

The absorbance is calculated as -log10 (It)/(Io) and isequated with EmCl, the molar absorption coefficient(Em) multiplied by the concentration (C) multipliedby the pathlength (l) through the liquid. This is theBeer-Lambert law.

The absorbance is a measure of energy lost from theradiation beam solely because of absorption by thesample. The experimental absorbance is a measureof the energy lost because of absorption by thesample, plus the energy lost because of reflectionfrom the interfaces of the cell plus the energy lostbecause of unexplained baseline errors. The energylost because of unexplained baseline errors may bepositive or negative.

Quantification requires knowledge of the beam paththrough the sample. Hence, the sample often needs tobe modified to allow for a known geometry. Spectralsubtraction, least square regression analysis, PLS andspectral deconvolution are some of the spectroscopictechniques widely used to quantify constituents in amulticomponent sample. For almost any type ofspectroscopic analysis, this is usually the first step. Itis especially important for polymers given thevariations in spectra for the same polymer due tomolecular weight, conformation, crystallinity, samplepreparation, age and sampling method.

Figure 4

Transmission IR sampling techniques

Infrared and Raman Spectroscopy of Polymers

21

7.5 Copolymer Composition and Structure

Direct measurement of absorbance of differentfunctional groups, measurement of end groups, analysisof specific interactions and monomer concentration canall be used to monitor quantitative copolymercomposition. Copolymer composition is determined byusing the absorbance intensity ratio of monomerspecific vibrational modes of vibration. A number ofcopolymer systems have been investigated:

Copolymer system item/no.

epichlorohydrin-gylicidyl ethers (28)

ethylene-acrylate (184)

EVA (72)

EVA (141)

ethylene-vinyl alcohol (258)

ethylene-propylene (110)

ethylene-propylene (123)

ethylene-propylene-diene (EPDM) (155)

acrylic/methyl methacrylate (124)

formaldehyde-phenol (127)

2-((phenylamino)carbonyl)-oxyethylmethacrylate (338)

maleic anhydride-styrene (343)

7.6 Polymerisation Kinetics and Mechanism inMulticomponent Systems

7.6.1 Approach

The synthesis of polymeric materials from lowermolecular weight materials usually involves IR orRaman characterisation at some stage. The completespectrum of a reacting species can lead to informationof the concentration of each species involved withoutthe need to stop the reaction or disturb it in any manner.The sample may be easily heated, exposed to UV, orexposed to electrical and magnetic fields or lasers withminor customisation of the sample holder (all in situand for most reactions) in real time. Hence, thesetechniques are used to characterise the polymerisationprocess for many systems.

Real-time chemical processing and analysis yieldsimprovement in product consistency and quality whilemaximising process efficiency. IR and Ramanspectroscopic techniques can be used for the study ofkinetics of copolymerisation and terpolymers. These

techniques are fast and can monitor the conversioncurves in real time. IR and Raman techniques candetermine in the course of the process thepolymerisation and copolymerisation rates in the courseof the process separately for each monomer bymeasuring variations in the intensity of IR and Ramanbands of the reacting groups.

In situ IR and Raman fibre optic probes can be placedat specific locations within the growing polymer totarget the evolution of polymerisation chemistries atthe surface or core of the process. The vibrationaltechniques of IR and Raman spectra permit betteridentification of spectral differences between monomerand polymer. The specificity of the technique, the speedof data acquisition and the portability of equipment allmake this method ideal as a tool to fundamentally probehow the distribution of individual chemical specieschange during the polymerisation. Its utility is inunderstanding the mechanism of a polymerisationincluding modifications including a catalyst or novelformulations and changes in the polymerisationconditions. The kinetic parameters can be evaluatedand the models for the polymerisation mechanismdeveloped. Isothermal experiments can be performedfor a series of reaction temperatures and used todetermine the overall activation energy of thepolymerisation reaction.

7.6.2 Examples Using IR Fibre Optics

Isobutylene polymerisation initiated by 1,2-epoxy-2,4,4-trimethylpentane (TMPO-1)/TiCl4 was studiedusing IR fibre optics. The initiating mechanism involvesthe formation of tertiary carbocations, by both SN1 andSN2 paths. From the linearity of the first-order plots ofmonomer consumption, and the near uniformity of thepolyisobutylene, it was concluded that livingpolymerisation conditions prevailed (i.e., notermination step) (32). The ATR head can monitor verylow concentrations (0.1 mmol/l) (49).

A linear-chained epoxy resin was formulated fromphenyl glycidyl ether and nadic methyl anhydride,catalysed by benzyldimethylamine (248). An IR fibre-optic probe was used to follow the conversion of athermosetting tetrafunctional epoxy resin in which thehardener was an aromatic diamine and a carboxylicdianhydride. A polymerisation system consisting of acycloaliphatic diepoxide, epoxidised natural rubber(ENR), glycidyl methacrylate (GMA) and a cationicphotoinitiator, triphenylsulfonium hexafluoro-antimonate, was studied (75). Multifunctional epoxy/amine formulations (Epon 825 plus 4,4'-methylene-

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22

dianiline) were examined by NIR spectroscopy (276).The polymerisation of bisphenol A diglycidyl ether andtetraglycidyl diaminophenyl methane and amine curingagents, i.e., 4,4'-methylenedianiline and diamino-diphenyl sulfone, were studied using near IR methods(277). Using an embedded silica optical fibre monitoredin situ by evanescent wave spectroscopy, the epoxyring-opening and crosslinking reactions could befollowed in real time (217). IR-transmitting opticalfibres as evanescent wave sensors (59) were used tostudy rigid PU/polyisocyanurate foam formation usingnew catalysts promoting different phases of PU foam.

7.6.3 Examples Using Raman Fibre Optics

Raman fibre optics has been used to study the emulsionhomopolymerisations of styrene and n-butyl acrylate(35). An IR spectroscopic technique for the examinationof radical copolymerisations of acryl and vinylmonomers was developed. A comparative study of thecopolymerisation of model monomer pairs was madeusing monofunctional and polyfunctional compounds.The data established the role of structural-physicaltransformations, involved in the formation ofcrosslinked polymers, on the copolymerisation kineticsand on the nonuniformity of distribution of crosslinksin the copolymers formed (151). Raman fibre optics ofpolymerisation of acrylic terpolymers was also usedto monitor as well as an on-line measurement ofmorphology/composition (66). The high temperature(330 °C) cure reaction of 4-phenoxy-4'-phenyl-ethynylbenzophenone was monitored using amodulated fibre optic FT-Raman spectrometer (80).

The time-dependent evolution of the polymerisationand copolymerisation reactions of styrene/unsaturatedpolyester resin was characterised using opticallevitation with Raman spectroscopy (135). The n-butyllithium-initiated anionic polymerisation of styrenein ethylbenzene was measured using Ramanspectroscopy (214).

Raman experiments were performed on cationicphotopolymerisations of a divinyl ether initiated witha diaryliodonium salt of hexafluoroantimonatephotosensitised by anthracene. Isothermal Ramanexperiments were performed for a series of reactiontemperatures and were used to determine the overallactivation energy of the polymerisation reaction (240).

A Raman spectrophotometer was used to measure insitu the polymerisation rate of acrylamidephotoinitiated by hydrogen chromate anion in aqueoussolution upon irradiation by laser beam (ionised argon)

(363). Changes in the FT-Raman spectrum of 1,4-bis(3-quinolyl)buta-1,3-diyne as a function of gamma-raydosage are used to monitor the degree of monomer topolymer conversion in a solid-state topochemicalpolymerisation reaction (i.e., polymerisation directedby the solid-state structure) (315).

7.6.4 Examples Using Rapid Scan FTIRSpectroscopy

An IR technique can obtain spectra every 5-10 secondsof a reacting PU foam system having a giventemperature profile (360). The real-time IRspectroscopy method was found to be particularlyuseful for analysing high conversion kinetics. Resultswere obtained also for poly(ethylene glycol 200)dimethacrylate and poly(ethylene glycol 600)dimethacrylate (263).

FTIR spectroscopy was applied to the study ofpolymerisation kinetics of simultaneous inter-penetrating polymer networks composed of PU andvinyl ester resin (238). The comparison of vinyl esterresin with or without its pendant hydroxyl groups wasalso made to examine the intercomponent chemicalbinding effect.

The copolymerisation of N-cyclohexylmaleimide(CHMI) and methyl methacrylate (MMA) usingazobisisobutyronitrile as the initiator using rapid scanIR. Using the Mayo-Lewis equation, the reactivityratios of CHMI and MMA were calculated (64).

By measuring the presence of functional groups at finitedepths from the crystal surface by real time ATR-FTIRspectroscopy, the conversion during acrylatepolymerisations was measured. By varying the filmthickness, the reactivity of multiacrylates could bespatially resolved (262). The simultaneous monitoringof vinyl acetate (VA) and erucamide additiveconcentrations in EVA copolymers was undertakenwith NIR spectroscopy using an in-line flow cellattached to an extruder (130).

Monitoring the imidisation of a polyamic acid madefrom 3,3',4,4'-biphenyltetracarboxylic dianhydride(BPDA) and p-phenylenediamine (PDA) wasaccomplished using IR spectroscopy (115).

FTIR spectroscopy was used with a common kineticsprogram to monitor the two separate reactionsoccurring during thermal curing of acetylene-terminated polyisoimide prepolymer (242).

Infrared and Raman Spectroscopy of Polymers

23

By the use of NIR instrumentation designed specificallyfor the process environment, the isocyanate content ofa urethane polymerisation reaction is monitored in real-time (265).

The cure mechanism for curing triglycidyl p-aminophenol with diaminodiphenylsulfone was studied. Theconcentration of primary and secondary amine andepoxide groups were monitored directly as a functionof cure with NIR spectroscopy. In similar fashion,monitoring of the percent conversion of methylmethacrylate to PMMA in situ in a mould used short-wavelength NIR spectroscopy. NIR spectroscopy wasalso used to monitor conversion during conventional,anionic solution polymerisation of styrene and isopreneto homopolymers and block copolymers (314).

FTIR spectroscopy was used to study thepolymerisation of random copolymers of 4-vinylphenolwith n-alkyl methacrylates which were prepared by freeradical copolymerisation of 4-t-butyldimethyl-silyloxystyrene and the corresponding alkylmethacrylates in benzene at 60 °C using azobisiso-butyronitrile (AIBN) as an initiator (321). The thermalreaction of polyphenylene-1,2-dibromoethylene underargon flow was investigated using in situ kinetic IRspectroscopy (345).

Stopped-flow FTIR spectroscopy was used to followgroup transfer polymerisation (GTP) and cyclicoligomeric carbonate formation. The effect of catalyststructure, propagating end stereochemistry and degreeof polymerisation on the rate of monomer addition inGTP was investigated (329).

7.7 Polymer Blends

7.7.1 Utility of Polymer Blends

Many practical benefits can be obtained by blendingpolymers. Blending allows for the beneficial propertiesof two polymers to be combined in one material whileshielding their mutual drawbacks. Deviations in the ruleof mixing can lead to properties of the blend over andabove those of its components. Thus, processibility,chemical and environmental resistance, adhesion, andmechanical properties of polymer blends are superiorto those of their homopolymers.

The attractiveness of blending lies in the property-tailoring possibilities. However, most binary mixturesof polymers are not miscible on the molecular levelbecause the entropy of mixing is not favourable for

high molecular weight polymers. As most polymerpairs are immiscible, they form multiphase systemswith weak physical and chemical interactions acrossthe phase boundaries. As a result, immiscible blendsexhibit poor mechanical properties.

Miscibility in polymer blends results from the Gibbsfree energy of mixing (ΔGm) being a negative value.This term combines the effects of both entropy andenthalpy. It has been well established that the formergenerally has a weak contribution in the case ofpolymers because of their high molecular weight. Thelatter is related to interactions occurring at thesegmental level between polymers and mainlydominates the miscibility of the blends.

7.7.2 Miscible Blends

7.7.2.1 Compatibilised Blends

Compatible blends are two-phase materials withproperties controlled by the properties and geometryof each phase and the nature of the connectivitybetween phases (compatiblilisers modify/improve theinterface). In some cases, the addition of small amountsof an A/B copolymer compatibiliser will result in acompatibilised A-B blend morphology that hasimproved mechanical properties. The compatibiliser isconsidered to be located mainly at the interface betweenthe two immiscible polymers, where it induces localmiscibility. The compatibliser lowers the interfacialtension and allows the dispersion of the incompatibilehomopolymers into small, microscopic domains.

The following blends have been studied:

• PP-LDPE with poly(propylene-g-maleic anhydride)and poly(ethylene-co-vinyl alcohol) as in situreactive compatibilisers (117),

• PET-LDPE compatibilised with diethylmaleategrafted polyethylene (120), and

• EVA copolymer compatibilised with terpene-phenolresins (TPR) (165).

7.7.2.2 Reactive Blends

Reactive blending is an important method for thecompatibilisation of polymer blends. Two or moreimmiscible polymeric components are functionalisedwith chemical units that are coreactive. During melt

Infrared and Raman Spectroscopy of Polymers

24

processing, the polymers chemically react to form acopolymer at the interface between the two phases. Thiscopolymer reduces the interfacial tension between thetwo phases, provides for better dispersion, andpromotes adhesion between the two phases.

A highly crosslinked epoxy resin was modified byreactive blending with bisphenol A polycarbonate. Thebisphenol A polycarbonate was dissolved at hightemperature in the uncured epoxy resin before thecuring process. The physical and chemical interactionsbetween the two components were studied by IR.Isothermal measurements showed that the presence ofpolycarbonate did not affect the overall curingmechanism but decreased both the initial reaction rateand the final conversion of reactants (278).

7.8 Conducting Polymers

The 2000 Nobel Prize in chemistry was awarded toHeeger, MacDiarmid and Shirakawa for turningpolymers which are traditionally insulators intoconductors. They found that by doping polyacetylene,it became conducting. This discovery resulted in theestablishment of new types of organic materials thatcombine the processing and mechanical advantages ofplastics with the electronic and optical properties ofmetals and inorganic semiconductors. Considerableeffort has been directed at determining the structuralbasis of this unusual observation.

The chemical structure of electrically conductingpolypyrrole films doped with p-toluene sulfonate anddodecyl sulfate was studied by FT-Raman spectroscopy.The spectra were compared with those from thecorresponding reduced polymers after dedoping andfound to be consistent with polaron and bipolarondescriptions of the electron transport mechanism inpolypyrrole (331).

Resonance Raman spectroscopy was used to investigatethe products formed upon iodine doping of cis-polyisoprene. Evidence for the production of polyeneswas found and that these are in part responsible for theincreased conductivity of iodine-doped cis-polyisoprene (374).

In situ Raman studies of the conducting and non-conducting poly-n-vinylcarbazole showed that theconducting polymer had a 3,3'-dicarbazyl structureformed by dimerisation at the 3,6 position. Theconducting polymer was also obtained by electrolysisof the nonconducting polymer dissolved in

dichloromethane. The conducting polymer obtained bythis method was found to have a similar structure tothat obtained by direct electrolysis of the monomer.These spectra showed that there were no significantstructural changes occurring in the conducting polymerduring the polymerisation process (292).

7.9 Emulsion Polymers

Emulsion polymerisation is characterised by the factthat a free radical initiator (usually water-soluble) isused to polymerise free radically polymerisablemonomers to give a water-insoluble polymer. The mainingredients of an emulsion polymerisation systeminclude monomer, dispersant, emulsifier and initiator.Water is often used as the dispersant. A water-insolublemonomer can be dispersed in water by means of anoil-in-water emulsifier and polymerised with a water-soluble initiator. Styrene, MMA and VA are systemsfor which emulsion polymerisation are commonly used.

An important characteristic of emulsion polymerisationis that, unlike other polymerisation processes, thepolymerisation rate and molecular weight can beincreased at the same time. This is due to thecompartmentalisation of the system that reduces theprobability of mutual termination of the propagatingradicals. The behaviour of this compartmentalisedsystem depends on the rate of exchange of speciesbetween the elements of the system.

Emulsion polymerisation gives particles in the diameterrange ~50-500 nm, with the ability to accurately controlparticle size. Particle stability is usually achievedthrough the use of surfactants.

The direct analysis of the organic phase of an emulsionpolymerisation is possible. Quantification involves usingthe bending mode peak of water, which makes up thebulk of the reaction medium, as an internal standard.The process is demonstrated for MMA but is generallyapplicable to emulsion polymerisations. It does notrequire the introduction of an extraneous internalstandard component into the reaction mixture (319).

FTIR spectroscopy was used to study hydrogen bondingin films of PU and core shell type polyacrylate-PUmicroemulsions. The effects of hydrogen bonding oncomposition and core shell ratio, and its relationship tocrosslinked structures (Type A and B) was revealed (60).

PS microspheres, produced by microemulsionpolymerisation, generally contain only one or a few

Infrared and Raman Spectroscopy of Polymers

25

polymer chains, and may thus be termed single- orpauci-chain microspheres. Changes in chainconformation on heating were studied using in situFTIR spectroscopy (85).

The phase transition between micellar phases ofpolyethylene oxide-polypropylene oxide-polyethyleneoxide) (PEO-PPO-PEO) triblock copolymer in aqueoussolution was investigated as a function of temperatureusing FTIR spectroscopy. As the temperature increases,PO blocks appear to be stretched conformers withstrong interchain interactions, and the formation of ahydrophobic core in the micellar phase. The EO chainsare found to change to a more disordered structure withlow-chain packing density. Both the EO and PO blocksexhibit dehydration during the phase transition (78).

Using a thermal micro ATR/FTIR spectroscopic system,a quantitative investigation was made of the molecularinteractions in aqueous solutions of poly(N-isopropylacrylamide) (PNIPAAM). The results indicatedthat intermolecular interactions predominate betweenPNIPAAM and water at temperatures below the lowercritical solution temperature (LCST). However, abovethe LCST, PNIPAAM molecules in water are aggregatedbecause of intramolecular interactions and hydrophobicinteractions in the system (93).

The nature of the complexes formed by the interactionsbetween polyacrylic acid (PAA) and polymethacrylicacid (PMAA) with poly(4-vinylpyridine) and poly(2-vinylpyridine) in ethanol/water solution was studiedusing FTIR spectroscopy. The PMAA complexesinvolved hydrogen-bonding interactions, while therewas evidence of ionic interactions in the PAAcomplexes. This difference in the behaviour betweenthe complexes is attributed to the higher acidity of PAAcompared with that of PMAA (140).

The FTIR spectra were acquired as functions of watercontent in the range 2.6-38 wt% and temperatures inthe range 300-373 K for hydrated poly(2-hydroxyethylmethacrylate) (PHEMA). The results suggest two typesof water in the hydrogel polymer system, tightly-boundwater and loosely-bound water. At low concentrations,water was mainly hydrogen-bonded to the polymer(tightly-bound water). At water concentrations greaterthan 18 wt%, however, part of the water existed in adifferent form and behaved as loosely-bound water. Itwas also suggested that some of the water continuedto be hydrogen bonded to the polymer until at least atemperature of 373 K when the bulk water should haveevaporated. FTIR spectroscopy was found to yieldgreater site-specific insight into the local behaviour ofwater in hydrated PHEMA (185).

The partitioning of acrylonitrile between particles andthe aqueous phase of polybutadiene latex was measuredby Raman spectroscopy using rubber latex as substrate.Raman line intensities yielded the partition values inthe two phases (295).

7.10 Graft Polymers

Graft copolymers can be prepared by radical graftingof a polymerisable monomer A onto a reactive polymerbackbone B. As a result of the grafting reaction, acomplex product is obtained comprising the graftcopolymer AB, residual ungrafted polymer backboneB and homopolymer A.

The condensation grafting of polyethylenimine (PEI)onto poly(acrylamide-co-acrylic acid) (PAM-co-AA)was studied by FTIR spectroscopy. The reactionmechanism, which proceeded by a two-step reaction,involved the conversion of AA to acid chloride (AC)using thionyl chloride, followed by the condensationof AC onto PAM and with amine onto PEI to form thegraft copolymer (125).

The grafting of PP films by PAA was demonstrated tostart from the interface between the PP and thepolymerisation solvent. The results suggested that itshould be possible to control the location of graftingboth by the content of antioxidants and by theirextraction (322).

LDPE was functionalised in the bulk through dicumylperoxide-initiated grafting of dibutyl maleate andvinyltrimethoxysilane in the temperature range from140 to 200 °C (327).

The structure of EPDM grafted onto polyamide 66 wasanalysed by FTIR spectroscopy. Evidence indicated thepresence of cyclic imide groups, derived from graftedmaleic anhydride groupings (229).

Polyglycidyl methacrylate and their copolymersobtained by radical graft onto polyvinyl alcohol(PVAL) fibres were studied by IR spectroscopy. Thespectra regions sensitive to the sites of localisation ofthe chains of grafted poly(glycidyl methacrylate) arewithin 3600-3100, 1450-1300, 1120-1000 and 700-500 cm-1, which correspond to the stretching andbending OH vibrations, stretching carbon-oxygenvibrations, and torsional vibrations of the hydroxylgroups, respectively. On this basis, it was establishedthat grafted polyglycidyl methacrylate molecules arelinked to PVAL macromolecules via oxygen atomsof hydroxyl groups (255).

Infrared and Raman Spectroscopy of Polymers

26

The use of an intermediate barrier layer to vary thepenetration depth in an ATR experiment was used inprobing concentration profiles away from the interface,Application of this technique in the study of PMMA/PDMS graft copolymers deposited onto a copper oxidesurface indicated a preferential presence of the siloxanecomponent at the oxide interface; a concentrationgradient was observed to decrease with increasingdistance into the bulk of the sample film (275).

IR spectra of polycaproamide fibre, polyglycidylmethacrylate and polycaproamide fibre grafted withpolyglycidyl methacrylate were recorded. The spectralregions that were sensitive to localisation of the chainsof grafted polyglycidyl methacrylate were identified,i.e., 3500-3100/cm-1 (stretching vibrations of NHgroups), 1700-1500/cm-1 (Amide I and Amide IIabsorption bands), 1030-900/cm-1 (Amide IV) and 720-640/cm-1 (Amide V). It was found that polyglycidylmethacrylate was grafted to the macromolecules ofpolycaproamide via an amide nitrogen (308).

ATR-IR spectroscopy was used to characterise thegrafting of PP films by PAA. It was shown that graftingalways started from the interface between the PP andthe polymerisation solvent. The results suggested thatit should be possible to control the location of graftingboth by the content of antioxidants and by theirextraction (322).

LDPE was functionalised in the bulk through dicumylperoxide-initiated grafting of dibutyl maleate andvinyltrimethoxysilane in the temperature range from140 to 200 °C. The degree of grafting was determinedby IR spectroscopy. The total surface energy increasedwith grafting. The surface energy of the silane-graftedPE was found to be lower than that of dibutyl maleate-grafted PE (327).

7.11 Degradation of Polymers

The lifetime of many polymer products in use is limitedby oxidative degradation. Exposed samples are usuallynon-uniformly oxidised. At the macroscopic level, theheterogeneities can result from oxygen-diffusion-limited effects. If the rate of oxygen consumptionexceeds the rate of oxygen permeation, oxidationoccurs in the surface layers, whereas the core remainspractically unoxidised. The importance of this effectdepends on several parameters. First, intrinsicparameters are linked to material geometry (e.g.,sample thickness) coupled with the oxygenconsumption rate, which depends on the reactivity of

the polymer, the presence of additives, and the oxygenpermeability of the material. Second, extrinsicparameters such as the conditions of accelerated ageingand the oxygen pressure during ageing are important.

Oxidation is accelerated if the temperature is elevated.Exposure to optical and UV radiation can alsoaccelerate the degradation. Additionally, thethermooxidation and photooxidation are accelerated bygenerating chemical effects by the application ofmechanical forces (i.e., mechano-chemicaldegradation). Vibrational spectroscopy is particularlyuseful for studying the degradation processes as themeasurements can be made in real time.

7.11.1 Degradation with Ionising Radiation

IR spectroscopy was used to follow the ageingprocesses of two types of epoxy resins. Resin sampleswere exposed to ionising radiation and the effects atthe molecular level were determined. Aromatic aminecured resins were only slightly affected by the radiation,but those cured by alkyl diamines were more sensitiveand thus absorbed more water molecules (41).

The effect of radiation dose and the hydrolysisconditions on the chemical structure of electronirradiated PTFE was studied. Irradiation produced acidfluoride (COF) groups and, under ambient conditions,these hydrolysed with atmospheric humidity to formfree and associated carboxylic acid (COOH) groups.The concentrations of these groups were different inthe near-surface and bulk regions. The formation ofcarboxylic groups in different states of associationdepended on the hydrolysis conditions (146).

IR spectroscopic analysis showed that the treatment ofPAN films and fibres by gamma-irradiation led tocleavage of the polymer chains forming carbonyl-containing functional groups, the composition of whichdepended on the treatment conditions (330).

7.11.2 Degradation by Photooxidation

The photooxidative degradation of anhydride-curedepoxies was studied. The degradation washeterogeneous, the surface being much more affectedthan the bulk. The disappearance rate of aromaticgroups was dependent only upon their initialconcentration, while the formation kinetics of hydroxylgroups was determined by the diffusion of oxygen intothe material. The formation of hydrophilic products,

Infrared and Raman Spectroscopy of Polymers

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acids, and alcohols was confirmed by chemicaltreatment, and it was concluded that their presence andhigh concentration at the surface could be responsiblefor the degradation of the insulating properties ofepoxies when used as electrical insulators (112).

PS films were exposed to radiation of long wavelength(above 300 nm) and short wavelength (253.7 nm) underatmospheric oxygen. Changes in the FTIR spectra ofthe photooxidised samples were followed. Theabsorption maxima which were found in the carbonyland hydroxyl regions of the IR were assigned, and thecorresponding photoproducts were identified (351).

IR spectroscopy was used to study the microstructureof propylene-ethylene copolymer samples taken fromseats which had degraded during storage or aged duringoutdoor exposure in an Olympic stadium in Barcelonaover a period of 2.5 years. The changes observedincluded increases in aldehyde and ketone groups anddecreases in unsaturation, peroxide, methyl andmethylene groups and isotacticity. The results indicatedthat the main processes taking place werephotooxidation and chain scission (189).

The photooxidation of a nonwoven PE fabric showedhydroperoxide, alcohol, aldehyde, ketone, carboxylicacid, and anhydride groups were formed as the productsof the photooxidation of the PE fabric and the relativeamount of carboxyl increased as the photooxidationprogressed. Distribution of the photooxidation productswas inhomogeneous between the two surfaces of thefabric. The UV radiation at 254 nm causedphotooxidation of PE. No photooxidation was observedin the fabric exposed to the UV radiation at 350 nmunder the same conditions (288).

PEO and polymethyl vinyl ether were UV irradiatedin hydrogen peroxide solutions. Hydroxy andhydroperoxy radicals accelerate the oxidativedegradation of these polymers. Hydroxy and possiblyhydroperoxy radicals can abstract hydrogen frommethylene groups in both polymers. As a result offurther oxidative reactions, different carbonyl, hydroxyand hydroperoxy groups are formed (297).

7.11.3 Degradation by Thermal OxidationProcesses

During thermal degradation of PAN over thetemperature range 150-590 °C, gaseous and volatileproducts were produced with simultaneous stabilisationof the structure of the residual material. The principal

decomposition reaction was linear polymerisation ofthe nitrile group, with cyclisation followed by extendedconjugation being a significant exothermic process.There was no evidence of the formation of oxygen-containing chromophores (113).

The thermooxidative degradation and SiOx filmformation of poly(vinyl imidazole-co-vinyltrimethoxysilane) on copper was investigated. Thermaldegradation of the copolymer was catalysed by copperin the film and at the substrate surface. Copper in thecopolymer film contributed to the formation of acopper-containing SiOx film during thermaldegradation. Copper oxides in the film interacted withthe SiOx film to form a copper-rich phase near the filmdefects and cracks (142).

The thermal degradation (in vacuo, up to 500 °C), of aVA-methacrylic acid copolymer having 65%alternating units, and of the correspondinghomopolymers, was studied. Polyvinyl acetate (PVA)copolymer crosslinks form due to double bondformation through deacetylation. PMAA generateslittle unsaturation, rather crosslinks by intermolecularanhydride formation. It decomposes above 350 °Cwhen the anhydride breaks down with substantial chainscission. In the copolymer, both types of crosslinkingreactions are disturbed by lactone formation betweenalternating VA and methacrylic acid units. The lactoneformation protects the VA units from deacetylation andcompetes strongly with anhydride formation (273).

The thermooxidative degradation of polyphenylenebibenzimidazole (PBI) and a blend of PBI with Ultem1000 polyetherimide was investigated. The FTIRspectra of the blend were analysed by subtractionspectroscopy, allowing the fate of the two blendcomponents to be selectively studied. No chemicalinteraction between the two components wasdetectable by FTIR spectroscopy during thedegradation process (323).

7.11.4 Degradation by Chemical Exposure

The mechanism responsible for the hardening ofhydrogenated nitrile rubber automotive seal compoundson prolonged exposure to automatic transmission fluidsat high temperature was investigated. The increase inhardness was found to result primarily from chemicalattack at the acrylonitrile sites. This chemical attackfirst resulted in the formation of isocyanide or isonitrileions. The proposed mechanism involved crosslinkingat the acrylonitrile sites through the formation ofisonitrile ions and the subsequent formation of imides.

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The isonitrile intermediate formed ionic bondsresulting in the formation of an ionomer once theconcentration became sufficiently high. Ultimatelythese ions crosslinked to form imides in the presenceof oxygen or water. It was proposed that the increasein hardness was due to the formation of the ionomerand the imides (154).

Differences in bands assigned to carbonyl groups andhydroxyl groups in PET films aged in water suggestedformation of different hydrogen-bonded species. Theautocatalytic nature of the hydrolysis in water wasconfirmed and evidence for the so-called‘chemicrystallisation effect’, with crystallinityincreasing with degradation, was observed (50).

7.11.5 Analysis of Evolving Gases from Polymers

A large number of different techniques are used toanalyse fire gases including gas chromatography, massspectrometry, and IR absorption. FTIR spectroscopycan be used for on-line quantification of evolved gasspecies during heating, burning, and smouldering ofthe sample. The use of FTIR spectroscopy enables anumber of the more important gases to be determinedcontinuously. Evolved gas analysis reveals features duemainly to the corresponding monomers or stable,volatile and low relative molecular weight degradationproducts. These gases include those of particularimportance to PU foam containing fires, e.g., hydrogencyanide, nitrogen oxides, hydrogen chloride andhydrogen bromide (from flame retardant additives) aswell as carbon monoxide and carbon dioxide whichare produced from all fires (236). The IR absorptionspectra are used to identify the individual gas specieswithin the fire gas mixture and the intensities of theabsorption bands are used to quantify the gasconcentrations.

Linear-temperature controlled pyrolysis withsubsequent analysis of the pyrolysates (volatiles andresidues) by FTIR spectroscopy can provideinformation on the thermal degradation mechanismsof polymers including aromatic polyesters (325).Thermal analysis of PS, poly-p-methylstyrene andpoly-α-methylstyrene was carried out using evolved-gas IR analysis (302).

On decomposition, the polybutylene terephthalate(PBT) polymers give off mainly water, carbon dioxide,butadiene, tetrahydrofuran (THF) and PBT oligomers.The flame retardants marginally increased the polymerdecomposition temperature (274).

7.12 Orientation of Polymer Chains Due toExternal Perturbations

7.12.1 Approach using Vibrational Spectroscopy

The elucidation of the mechanisms and dynamics ofsegmental mobility in polymers under the influence ofexternal perturbations can contribute to the optimisationof the engineering properties of technically importantpolymeric materials. Application of a uniaxial orbidirectional stretching is a common method of treatinga polymeric material to improve its mechanical end-use properties.

Generally, time-resolved IR spectroscopy has provedan extremely valuable tool to investigate the structuraldetails of molecular changes incurred by a polymerunder the influence of such an external perturbation.The ability to monitor and model such drawing andrelaxation processes would benefit greatly productquality and web efficiency.

FTIR and Raman spectroscopy are two of the fewtechniques providing data on the crystallisation,orientation and conformational changes of a polymerduring and after mechanical treatment.

Front-surface reflection IR spectroscopy is often usedto characterise the structure of drawn samples. Thisapproach provides the complete IR spectrum, includingthe highly absorbing bands that are often saturated intransmission spectra. ATR techniques are used to depthprofile the changes in orientation.

One approach to characterising the molecularorientation in both uniaxially and biaxially orientedsamples of PET makes use of the ratio of theabsorption bands near 1250 and 1725 cm-1, the firstof which shows parallel dichroism and the secondperpendicular dichroism. An equation is developedthat relates this ratio to the molecular orientation withrespect to the direction of measurement. Thus, it ispossible to determine individually the orientationfunctions with respect to the machine and transversedirections (131).

Several sources of error may influence the calculationsof chain orientation carried with the use of data fromIR dichroism experiments. Three specific problems arethe improper treatment of chain conformation, theimperfect polariser behaviour, and the inaccurateassumptions regarding the value of the angle betweena particular IR-active transition moment and thepolymer chain axis (309).

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7.12.2 Orientation Functions for MechanicalDeformation

FTIR spectroscopy was used to monitor orientationphenomena in highly crosslinked epoxy/aminenetworks during uniaxial deformation above their glasstransition temperature (Tg). The resins were preparedfrom the diglycidyl ether of bisphenol A and variouspolyether di- and triamines in order to examine theinfluence of the structure of the network formed. Themolecular orientation was studied in relation to networkdensity and structure. The orientation behaviour wasmainly determined by the flexibility of the polyetherchain and the homogeneity of the network structure.The epoxy resins were also subjected to successiveloading-unloading cycles. The results showed that theorientation of epoxy networks in their rubbery statewas completely reversible and that no significantfatigue due to gradual chain rupture occurred untilsample failure (253).

IR dichroism was used to study the orientationaldevelopment in the high-speed spinning of Nylon 66yarns. A relationship between IR dichroism andorientation factor was developed and a correlationbetween orientation measured by IR and X-raydiffraction demonstrated (372).

The orientation functions and dichroic difference datafor a commercial polyester-urethane from B.F. Goodrichshowed that, in static stretching, the soft domains reachedorientation saturation before the hard domains. On thetimescale of the static experiment, plasticisationdiminished the ability of both domains to reorient, whilethe plasticiser itself did not orient (55).

Micro-Raman spectroscopy was used to study thestructural changes which occur in the cold-drawingof HDPE. The cold-drawn structure was highlyorientated and a large decrease in the Ramanorthorhombic crystallinity was observed. The resultsindicated an ill-defined orthorhombic crystallinestructure with dislocations and disrupted crystalsformed by cold-drawing, possibly resulting frommolecules being pulled through the crystals. Nodisruption was observed in fibrils created duringenvironmental stress crack resistance (ESCR) tests at348 K. Temperature was an important parameter inthe crystalline phase recovery of the orthorhombiccrystallinity and when the cold-drawn HDPE wasannealed, the monoclinic phase disappeared (94). Therole of an ESCR detergent (active environment)during tensile deformation of PE samples was studied.IR spectroscopy indicated that the detergent waspredominantly present within the transition fronts of

the material. The results indicated that theenvironment penetrated the sample during the neckingprocess and stabilised crazing (99).

ATR-IR spectroscopy at various angles of incidencewas used to study ultradrawn films of PE. A gradientof molecular and crystalline structures was found fromthe surface into the core. The skin was highlyorthorhombic. Moving inside the film, both monoclinicand orthorhombic lattices coexisted. A new phase withisolated trans-planar sequences was observed in thecore. Various kinds of collective and oriented or isolatedconformational disorder were identified. A molecularmodel was proposed for the process of orientationduring drawing (346).

7.12.3 Strain-Induced Crystallisation

The morphology of the strain-induced crystallinematerial produced by drawing amorphous PET isdifferent from that of material obtained by thermalcrystallisation. Furthermore, it has been shown thatthermal crystallisation involves two distinct stages.The primary stage starts to become significant around90 °C not far above the Tg, and shows a sigmoidaldependence on log (time). The secondary stagebecomes significant only above about 140 °C andshows a linear dependence on log (time). Significantdifferences between samples with strain-inducedcrystallinity and one that was thermally crystallisedare observed (90).

Specular reflection spectra (spectra obtained usingspecular reflection sampling) was obtained from thesurface of uniaxially drawn PET samples. The overallorientation function and content of trans-conformersis calculated. The results are correlated with mechanicalmodulus and crystallinity values (251). In uniaxiallydrawn PET films the skeletal structures, such as the C-O bond in the ethylene glycol unit and the phenyl ring,are susceptible to deformation by mechanicalstretching, while the dynamic structural changes aroundthe methylene group are small. It was assumed that thebackbone of the polymer is responsible for the changeof the mechanical properties induced by the drawingof the film (158).

The structure of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) fibres exhibit three crystallinestructures: two orthorhombic, and one pseudo-hexagonal. The orthorhombic crystals with the c-axispreferentially orientate perpendicular to the fibre axis,and pseudo-hexagonal crystals are preferentiallyformed in the drawing process (114).

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7.12.4 Deformation-Induced ConformationalChanges

PVC films were stretched to various elongation ratiosand the dichroic behaviour of 615 and 637 cm-1 bandsof the IR spectrum were investigated. The evolution ofthe dichroic ratios and of the relative absorbance ofthe bands in the direction perpendicular to that ofstretching were compared so the occurrence of localchain orientation related to the conformational changefrom gttg-tt to gtgttt which occurs when PVC isstretched (51).

FTIR polarisation spectroscopy was used to study theorientational behaviour of the different constituents ofa liquid crystalline block copolymer (copolyester-imide) during uniaxial elongation at differenttemperatures. Differences in the degree of alignment(as well as in the response to the application of themechanical load) were observed. With increasingtemperature, the level of the applied stress and theinduced degree of orientation decreased, while thedifferences in the orientational behaviour of themesogen and the flexible spacer were retained (243).

7.12.5 Relaxation Processes after Drawing

Epoxy resin films were subject to various successiveloading-unloading cycles including elongation,recovery, annealing and stress relaxation to study thereversibility of the orientation during relaxationprocesses (197).

The relaxation of the segmental orientation and thechain extension in polycarbonate was studied by IRdichroism and heat shrinkage after a step straindeformation to a draw ratio of 1.75. This made itpossible to distinguish between local relaxationmechanisms and large-scale relaxation mechanisms ofthe molecular orientation. It was found that the averagerelaxation time for segmental orientation is shorter andmore temperature-dependent than the averagerelaxation time for the chain extension. The segmentalorientation relaxes almost totally at 170 °C (Tg 148 °C)before the chain extension even starts to relax (201).

7.12.6 Electric Field Induced Reorientation ofPolymers

Dipole reorientation under the influence of an electricfield has been studied in oriented Nylon 11 films withpolarised IR spectroscopy using the amide A (N-H

stretching) and amide I (carbonyl stretching) bands.Butterfly-shaped hysteresis loops were obtained fromgraphs of peak intensity versus applied electric fieldstrength. Time-dependent studies of the absorptionintensities show that both ordered and disorderedspecies switch towards the electric field direction withthe application of electric fields higher than the coercivefield. Upon field removal, only the disordered speciesshow orientation relaxation away from the fielddirection. Below the coercive field, neither speciesaligns with the field (231).

7.12.7 Laser-Induced Orientation

The laser-induced anisotropy in thin films ofcyanoazobenzene side-chain liquid crystallinepolytetradecanedioates, -dodecanedioates, and-adipates selectively deuterated at different positionswas investigated by FTIR. In polyesters with longmain-chain spacing (tetradecanedioates and dodecane-dioates), not only the light-sensitive azo chromophore,but also the main-chain methylene segment and to asmall extent the flexible spacer are preferentiallyoriented perpendicular to the laser light polarisation.The extent of orientation increases with increasingspacer length. Rapid-scan FTIR analysis performed online with laser irradiation reveals that the alignment ofthe aliphatic segments arises simultaneously with thechromophore orientation (143).

7.13 Time-Resolved Spectroscopy

Time-resolved IR spectroscopy is an extremelyvaluable tool to investigate the structural details ofmolecular changes incurred by a polymer under theinfluence of an external perturbation. The elucidationof the transient molecular changes during polymerdeformation is an important issue in polymerprocessing. The ability to monitor and modelmechanical drawing and relaxation processes benefitsproduct quality.

Time-resolved FTIR is used to study the structure anddynamics of ferroelectric liquid crystalline blockcopolymers. From analysis of the dynamic dichroismof the FTIR spectra, it was concluded that thecomponents in the PS microphase are oriented randomlywhile the liquid crystalline groups form an ordered phase.The switching is of an electroclinic type, in which thetilt angle and the mesogenic motion increase withtemperature, especially if the PS block is heated aboveTg. The orientation of the liquid crystalline block after

Infrared and Raman Spectroscopy of Polymers

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heating to the isotropic phase is completely restored dueto the memory effect (i.e., reversible behaviour) of thepolymer microstructure (101).

Time-resolved FTIR spectroscopy measurements wereperformed under isothermal crystallisation conditionsto clarify the origin of the cocrystallisation and phasesegregation phenomena observed for a series of PEblends between the deuterated and hydrogenatedspecies, The degree of undercooling or the temperaturejump depth (i.e., the size of the temperature drop) fromthe molten state to the isothermal crystallisationtemperature was controlled (96).

7.14 Rheooptical FTIR Spectroscopy

IR spectroscopy can be coupled with the polarisationmodulation technique in order to characterise themolecular orientation in polymer films. A computer-controlled variable-temperature stretching machine isused, which allows monitoring of vibrational spectra andstress-strain diagrams during deformation of polymerfilms up to 523 K (355). Polarisation modulationimproves the SNR and minimises errors generated byrepositioning the sample or the polariser for a secondmeasurement. This technique is capable of measuringsmall dichroic effects with high sensitivity, even for verysmall sample draw ratios (291).

Phase-locked electronics are used to record thedynamic IR spectral change in-phase and out of phasewith the applied mechanical field. The methodprovides insight to the response to the external stresson the molecular and submolecular scale. RheoopticalFTIR spectroscopy is one of the few techniquesproviding data on the crystallisation, orientation andconformational changes of a polymer duringmechanical treatment (83). Two dimensionalcorrelation analysis is utilised to enhance theinformation derived from the vibrationalspectroscopic data.

The IR rheooptical technique was applied to study themolecular processes that take place along the stress-straincurve of PET yarns. The results indicate that the firstmodulus maximum marks the breakdown of theamorphous entanglement network and the start ofmolecular uncoiling by gauche-to-trans transitions. Inaddition, stress develops on the crystals and particularlyon tie molecules with a short contour length in theamorphous domains. Ultimately, molecular fracture oftaut-tie molecules (extended chains of polymers betweencrystals) causes the modulus to pass through a second

maximum. The chain ends of broken molecules recoilby trans-to-gauche transitions. Local stress accumulationwill lead eventually to yarn rupture (320).

The molecular orientation of the epoxy networks wasinvestigated using rheooptical FTIR spectroscopy anduniaxial deformation was carried out above and belowthe Tg. The effects of diol chain length and molar ratioon the mechanical properties and orientation parameterwere discussed (79).

For PS/poly(vinyl methyl ether) blends, the additionof poly(vinyl methyl ether) to the blend increases theorientation of the PS chains during the stretching (92).

Rheooptical FTIR spectra of a thermoplastic polyesterurethane and Nylon 6 films were recorded under avarying sinusoidal strain. The large bipolar bands inthe dichroic in-phase spectra, caused by large frequencyshifts of the original monopolar absorption bands, wereascribed to hydrogen bonds (102).

7.15 Two-Dimensional IR (2D-IR) Spectroscopy

The general experimental approach in 2D-spectroscopyinvolves the application of an external perturbation thatcan selectively excite various chemical components ofa given system. The excitation and subsequentrelaxation processes, which are manifested by changesin peak intensities, shifts in spectral frequencies andvariations in band shape, are monitored by a givenspectroscopic probe.

Two-dimensional-IR spectroscopy is a technique wherethe spectral intensity is plotted as a function of twoindependent spectral variables, e.g., frequency. The twoorthogonal axes of independent spectral variablesdefine a 2D spectral plane, and the spectral intensitymay be plotted along the third axis.

This approach can be used for probing the relationshipsbetween the molecular motions in IR spectroscopy.Two-dimensional-IR spectroscopy providesinformation that cannot be obtained by normal IRspectroscopy. Two-dimensional-IR can aid in theinterpretation of complex spectra, especially with thebroad overlapped peaks commonly encountered withpolymers. The advantage of this method is the abilityto separate overlapping bands and investigate the timesequence of certain spectral events (a.34).

The power of the 2D-IR spectroscopy approach resultsprimarily from an enhancement of the spectral

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resolution that has a physical origin. This effect relieson the dissimilarity between the responses of variousfunctionalities absorbing at distinct frequencies. Onecan also make band assignments between IR bands andbands in NIR and Raman spectra.

Two-dimensional-IR spectroscopy requires a series ofperturbation-dependent spectra. The types of physicalperturbations probed with this technique include:mechanical stress, applied potential, temperature,pressure, concentration and composition (a.35).

In 2D-IR spectroscopy, the sample is perturbedexternally to induce time-dependent fluctuations of theIR signal. The external perturbation can be anyperturbation source that can excite chemical species inthe system, including mechanical, optical, electrical,magnetic, chemical, thermal and acoustic perturbations.The reorientation of each functional group in the samplewith a unique rate, extent, and direction producesresolvable fluctuations in the dynamic IR intensities.The changes are recorded in the dynamic spectra inthe form of variation in the intensities, shifts of spectralband positions and changes in the shape of peaks.

Generalised 2D spectroscopy can handle spectralfluctuations as an arbitrary function of time or of anyother physical variables such as temperature, pressure,concentration and composition. Generalised 2D spectraemphasise spectral features not readily observable inconventional 1D spectra. It helps to probe the specificorder of certain spectral events taking place with thedevelopment of a controlling physical variable. Thegeneralised 2D approach is a qualitative method only;one can interpret only positions and signs of correlationpeaks. The absolute magnitude of these peaks cannotbe directly interpreted since they include informationon both the amplitude and phase changes at twodifferent frequencies (a.36).

A 2D experiment can be carried out using aconventional spectrometer by introducing a relativelyslow external perturbation applied to the system ofinterest. In a typical 2D experiment, a series ofperturbation-induced dynamic spectra are collected insome sequential order. Such a set of spectra may bereadily manipulated mathematically, with the use of asimple scheme of correlation analysis to yield thedesired 2D correlation spectra.

Two-dimensional NIR spectroscopy has been used forstudies on the composition-dependent spectral variationsin EVA copolymers. As a result, additional assignmentsof bands were made to ethylene units in amorphous,disordered, and orthorhombic crystalline phases (73).

Polyester-based PU elastomers contain hard and softdomains. It is desirable to characterise the molecularlevel interactions giving rise to the two domains, andto use this information to monitor chemical changes.The 2D correlation method provides a means by whichthe spectral information arising from the two domainscan be resolved using thermal perturbations (95).

Two-dimensional-IR spectra of glassy atactic PS revealthat while the main-chain backbone reorients in thedirection of applied strain, there also exist highlylocalised reorientational motions of phenyl side groupsoccurring independently of the main-chain realignment.This localised submolecular distortion is not observedat temperatures well above the glass transition (107).

Two-dimensional-IR spectra were used to study theorientation and the mobility of a ferroelectric liquidcrystal dimer during switching by an electric field. Thedetailed mutual arrangements of different molecularsegments (poly(siloxane), poly(methylene) chain,polysiloxane chain) in a smectic C phase were derivedfrom the static spectra. Temperature and electric fieldstrength dependencies of the mobility of these segmentswere established (163).

A 2D-IR spectroscopic study on dissociation andhydrogen bonds of Nylon 12 over a temperature rangeof 30-150 °C showed gradual weakening of inter- andintramolecular associative interactions and a decreaseof local order leading to the eventual fusion. (167). Theasynchronous 2D-NIR spectra indicate that the amidegroups with a free carbonyl oxygen appear first, andthen unassociated free amide and amide with free NHfollow as the temperature is increased (174).

Two-dimensional-IR spectroscopy was used to studythe N-H stretching and amide I/amide II region of melt-crystallised Nylon 11 thin films on Teflon substrates.The samples were mechanically oscillated at afrequency of 11 Hz. The dynamic spectra indicated thatthe N-H stretching region splits into two peaks.Analysis of 2D cross plots between the N-H stretchingregion and the amide I/amide II region showed that theprominent peak in the N-H stretching region (about3300 cm-1) was similar in morphological character tothe ordered peak of the amide I region. The amide IIregion resolved into two ordered and one disorderedpeak (254).

Two-dimensional-IR spectroscopy involvingmechanical excitation has been employed to study themechanical relaxation phenomena in an acrylonitrile-butadiene-styrene terpolymer (ABS) sample. The studyrevealed detailed information regarding the molecular

Infrared and Raman Spectroscopy of Polymers

33

segments involved in macroscopic mechanicalrelaxation. From the temperature dependence of thedynamic signals it is corroborated that in the ABSsample the polybutadiene rubber relaxes entirelyindependently from the styrene-acrylonitrile copolymer(SAN) matrix, and thus is present as a separate phasein the material (169).

A 2D-IR spectroscopic analysis on the dynamic spectraindicates that neat LDPE is comprised of three regions:an ordered crystalline region, a disordered liquid-likeregion, and a crystal/amorphous interfacial region. The1468 cm-1 peak in the methylene bending region isassigned to the all-trans structures which primarilyreside in the interfacial region. A variety of LDPEsamples with different additives were used in order todetermine how the additives influence the dynamicmechanical properties of each morphological phaseLPDE. It is found that talc associates with thecrystallites, EVA is distributed in all threemorphological phases of the LDPE, and pyrene isassociated only with the non-crystalline regions (218).

Two-dimensional-IR spectroscopic analysis was usedto monitor the submolecular orientational responses ofthe components of a semicrystalline 50/50 blend ofLDPE with perdeuterated HDPE to a small amplitude,uniaxial, 23.47 Hz, sinusoidal mechanical strain.Analysis of the data indicated that the crystalline partsof the two components reorient at different rates, withthe functional groups of the high density portionreorienting faster, in general, than those of the LDPEin response to the mechanical strain (316).

FT-Raman spectra were determined for atactic PS,poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and theirblends. Composition-dependent spectral variations ofthe blends were analysed using generalised 2-Dcorrelation spectroscopy to study the conformationalchanges and blend interactions. The 2D synchronouscorrelation analysis was able to discriminate betweenthe bands of PS and those of PPE, and was able todetect bands that were not readily identifiable in 1Dspectra. The main chain conformation of PS undergoesa drastic change on blending with PPE (57).

7.16 Recycling of Polymers

One of the main causes of the high costs of recyclingis sorting. It is essential to separate collected post-consumer waste in order to obtain plastics of onesingle type to feed the recycling process. The additionof chemical additives and new granular plastics can

only be done efficiently with the knowledge of allrelevant physical and chemical properties of thecollected basic material.

As physical methods are not sufficient, theidentification method has to monitor structural ormolecular properties of the polymers. The NIR spectralrange (700 to 2500 nm) allows the monitoring ofstructural or molecular properties of the plastic articlesunder investigation for recycling. The reducedabsorption in the NIR allows registration of spectra ofbulky plastics of practical interest in recycling. For fastscanning of the wavelength region of 1000 to 2200 nm,spectrometers based on AOTFs with a scan speed of1000 nm/ms are applied to identify the plastics in massconsumer products and household wastes (206).

On-line spectroscopic imaging requires high-speedsensors and short image processing steps. An opticalinstrument consisting of a high-throughput NIRspectrograph with an indium, gallium, arsenic(InGaAs)-array detector and specially designedcollection optics has been used to record spectra frompost-consumer packages located on an industrialconveyor belt (157). As these imaging systems generatelarge amounts of data, multivariate statistical techniquesare required to extract the important information fromthe multidimensional spectroscopic images (77). Thismeasuring technique is both economic and suitable forindustrial environments, at least for certain wastefractions (household plastics, hollow articles,engineering plastics). The visual distinction betweenthe spectra is demonstrated by aid of principalcomponent analysis (PCA) plots. A fuzzy neuralnetwork further classifies the spectra. The method isassessed to be suitable for on-line identification underindustrial conditions.

A spectroscopic NIR imaging system, using a FPAdetector, has been developed for remote and on-linemeasurements on a macroscopic scale. Multivariatestatistical techniques are required to extract theimportant information from the multidimensionalspectroscopic images. These techniques include PCAand linear discriminant analysis for supervisedclassification of spectroscopic image data (178).

A NIR spectrometer system has been described basedon optical fibres for absorption and reflexionmeasurements, an AOTF and a transputer system. It isable to detect 1,000 spectra per second and to identify20 pieces per second (209). The identification systemwas implemented and tested for a real-world applicationof plastic identification in municipal solid waste.

Infrared and Raman Spectroscopy of Polymers

34

Automated sorting of post-consumer plastic waste wasachieved using a combination of fixed-filter NIR andneural network data analysis. Rapid and reliableidentification of polymers can be made. Theeffectiveness of the method was demonstrated forsorting PET, HDPE, and PVC (261).

The composition of recycled HDPE/virgin PP blendsprepared in a single-screw extruder have beenmonitored in-line at three different points by NIR (247).

The suitability of Raman spectroscopy for computerisedclassification of post-consumer plastics was evaluated.Plastics investigated were PET, PP, PS, PVC, HDPE andLDPE. It was found that Raman spectroscopy could beused to identify both HDPE and LDPE (81).

The composition of a polymeric material is of interestthroughout its useful life from process stream to productfabrication, and finally to post-consumer recycling. Itis desirable to know not only what types of materialsare present, but also their relative concentrations. Inmany cases, Raman spectroscopy can provide a quick,convenient and relatively inexpensive alternativeconventional analytical method for performing thesetypes of determinations (266).

7.17 Depth Profiling from Surfaces andInterfaces

7.17.1 Optical Depth Profiling Using ATR-FTIRSpectroscopy

ATR-FTIR spectroscopy is an optical depth profilingmethod in which a concentration or structural gradientis probed near the surface of a material, such as anadhesive, sealant or coating. Recently, a number ofimprovements have been made in the method (192).

In one method, by varying the thickness of a barrierfilm, different effective penetration depths are achieved(194). ATR-FTIR spectra of a laminate (PMMA/PVAL)were presented at different base layer thicknesses anddifferent angles of incidence on a zinc selenidesubstrate. By varying the thickness of the PMMAbarrier film, different effective penetration depths inthe PVAL were achieved to detect interfacialinteractions (245).

In another method, two internal reflection elements, Geand KRS-5, with an angle of incidence of 45 degrees,were used to obtain the depth profiles of the crystallinityof PP sheets from the surface to the bulk (204).

A metal overlayer ATR-FTIR technique whichmarkedly enhances the SNR of monolayer andsubmonolayer film spectra has been described. Themetals investigated were gold and aluminium, with asubstrate of polyether-urethane elastomer (375). Theuse of silver films under ATR geometry has improvedthe detection limit of the surface layer on polymerfilms. An enhancement factor of 10 and 2 is reportedfor polydimethylsiloxane and polycarbonaterespectively, compared to the conventional ATRtechnique (362).

ATR-FTIR was used to determine the concentration ofa chemical additive (cationic polyacrylamide resin)within a pulp fibre. The depth distribution of theadditive was determined by sputter etching the fibresurface. The obtained profile was comparedqualitatively with that obtained by the variable-angleATR-FTIR depth profiling method. Most of the additivewas located at the surface, with some distributed withinthe fibre (137).

7.17.2 Depth Profiling Using Photoacoustic IRSpectroscopy

Photoacoustic spectroscopy involves the modulationof IR radiation at a frequency in the acoustic range.The radiation strikes a sample and is subsequentlyturned into heat energy by nonradiative deexcitationprocesses (i.e., excitation is loss by thermal motion andnot by the emission of energy). Heat-generated thermalwaves then propagate to the sample surface andfacilitate the rapid expansion and contraction of acarrier gas. A microphone is used to sense the changein pressure in the enclosed cell.

As only photoacoustic spectroscopic (PAS) signalsgenerated within the thermal diffusion length aredetected, the method can be used to discriminate betweenthe surface and underlying layers of solid materials. PASis useful for probing penetration of about 1 x 10-5 m.The depth of detection is dependent on the thermal andoptical properties of the sample. Sampling depth in PASis determined by the mirror velocity of the interferometer.Low optical velocities will result in PAS signals fromdeep within the sample, while high optical velocitieswill allow thermal diffusion from the surface regions.The sampling depth increases (by a factor of about threeacross the wavenumber range 400-4000 cm-1) withdecreasing wavenumber.

In PAS, the time-resolved photoacoustic response tosinusoidally modulated incident source radiation has aphase delay which depends on the depth in the sample

Infrared and Raman Spectroscopy of Polymers

35

from which the photoacoustic response originates.Use of a stepscanning interferometer circumvents thedifficulties arising when a single chopping frequencyis used for all wavelengths (a chopper is used tointerpret the beam at a single frequency). Step-scanphotoacoustic FTIR experiments can be used to collectinformation from selectable and constant depths fromthe sample surface.

FTIR step-scan photoacoustic spectroscopy was usedto study the composition of thermoplastic olefin films,as a function of depth below the surface. Experimentswere completed at various modulation frequencies,enabling a stratification model to be developed. Theuppermost layer (0-3 μm) showed large changes in talcand PP concentration, while the layer below showed asignificant decrease in both the phases. In the third layer(6-9 μm), all three phases showed the maximum values.In the fourth layer (9-12 μm), the talc concentrationreduced, whilst concentrations of elastomericcopolymer of ethylene and propylene (EPR) and PPwere observed, decreasing with depth (44).

FTIR photoacoustic spectroscopy was used for thestudy of the adsorption of poly(n-butyl methacrylate)from cyclohexane, benzene and carbon tetrachlorideonto alumina. The efficiency of adsorption increasedin the order cyclohexane, carbon tetrachloride,benzene, while methanol and tetrahydrofuran showednegative adsorption. Poly(n-butyl methacrylate) hada negative temperature coefficient of adsorption (126).

A step-scan FTIR photoacoustic phase-resolvedtechnique was used to depth profile micrometre-thicklayered plasma polymers (171).

Migration and concentration levels of sodiumdioctylsulfosuccinate (SDOSS) surfactant moleculesin silicone-modified 50%/50% styrene/butyl acrylatelatex were detected at the film-substrate and film-airinterfaces in mono- and double-layered films. TheSDOSS content was shown to be influenced by thepresence of trimethoxysilyl propylmethacrylatesiloxane (202).

Injection-moulded PP plates, with and withouttitanium dioxide pigment, were irradiated in amedium-accelerated photoageing device to theequivalent of 1 year of outdoor exposure.Photoacoustic FTIR spectra of photooxidised sampleswere analysed. The oxidation profiles monitored wereshown to arise from oxygen diffusion limitation andalso from the heterogeneous absorption of light bythe titanium dioxide-pigmented samples (336).

Dimensionally dependent changes are encountered inPVC weathering processes. Changes are observedduring outdoor photodegradation of PVC sidingcapstock (paint without additives such as pigments)formulations, as a function of exposure time andtitanium dioxide level. Profiles through the thicknessdimension were analysed to identify degradationspecies and depth distribution (76).

7.17.3 Depth Profiling Using Confocal RamanMicrospectroscopy

The depth and surface distribution of the PS grafts,crosslinker, and the sulfonation efficiency were studiedusing confocal Raman microspectroscopy. Highlygrafted samples had a homogeneous distribution ofgrafts and homogeneous sulfonation, whereas unevengraft distributions were observed in samples with lowand intermediate degrees of grafting. The crosslinkerconcentration in the interior of the film wasapproximately 50% of the surface concentration (61).

Confocal Raman microscopy was used for theinvestigation of variations in crosslinking with depthin thicknesses of up to 0.5 mm in UV-cured coatings.Variations of curing with depth in pigmentformulations, in thicknesses of up to 30 μm, wereobserved (62).

Confocal Raman spectroscopy was used to examinedepth or lateral profiles of the crosslinking process (e.g.,the reaction progress) in radiation curable coatings witha resolution of approximately 1 μm3. The potential ofconfocal Raman microscopy is demonstrated for theproblems of the inhibition of the radical polymerisationreaction by oxygen, the limited polymerisation reactionin deep layers due to the restricted penetration of UVlight (Lambert-Beer), the reaction in pigmentedcoatings and the distribution of UV stabilisersinteracting with the UV curing process (118).

Confocal Raman microprobe spectroscopy was used tocharacterise polyaniline/poly(N-vinyl carbazole),polypyrrole/poly(N-vinyl carbazole) and polypyrrole/polyaniline films (or reverse order of each pair in thefilms). Two types of film were observed, depending onthe conditions. Either the second polymer wasincorporated into the initially coated layer or a double-layer film with a well-defined interface was formed.Electrolysis of pyrrole and aniline monomer mixturesgave films rich in pyrrole when the pyrrole:aniline molarratios were greater than 0.12. However, polymerisationof N-vinyl carbazole and pyrrole monomer mixtures gaveonly polypyrrole over a wide range of molar ratios (121).

Infrared and Raman Spectroscopy of Polymers

36

Confocal Raman microspectroscopy was used tomeasure local compositions along a direction that wasperpendicular to the original interface. Compositionprofiles generated by interdiffusion in the concentratedregime between polyphenylene oxide-polystyreneblend pairs were determined (128).

Depth profiling was carried out using confocal Ramanmicrospectroscopy to study PAN/PVAL and PAN/PAlaminates. The laminates were annealed at 65, 75 and90 °C. It was demonstrated that the degree of hydrogenbonding interaction between the nitrile and alcoholgroups near the interfacial region changes betweenlaminates annealed at different temperatures. Forcomparison, Raman mapping of a PAN-PVAL blendwas used to study the interactions between the polymersin this (disordered) system (147).

Confocal Raman microspectroscopy was used tocharacterise the chemical composition of clearcoats inpaint systems. Weathered and unweathered samples ofisolated acrylic/melamine and acrylic/urethaneclearcoats, polyester urethane clearcoats in weatheredand unweathered samples of a complete paint systemon plastic, and UV light cured acrylic clearcoats onpolycarbonate substrates were studied (149).

It was demonstrated that confocal Ramanmicrospectroscopy can be successfully used to studythe hydrogen bonding interactions between the esterand alcohol groups near the interfacial region. Variouslaminates have been studied and it is demonstrated thatPMMA layers with lower molecular weight show agreater degree of interpenetration for a given annealingtime (225).

7.18 FTIR Microspectroscopy

FTIR microspectroscopy, coupled with mappingtechniques, is an effective method for evaluatingdimensionally-dependent changes. The method is basedon the specificity of the IR spectrum and thedimensional resolution of the microscope. The keys tothe successful use of FTIR microscopy are experiencein sample preparation, an understanding of lightmicroscopy, and ingenuity in defining solutions.

The fatigue of NR and styrene-butadiene rubber (SBR)is an enormous industrial problem, as importantmechanical properties of these materials deterioratequickly when stressed. Although fatigue may describethe deterioration of certain material properties, it isgenerally believed that the term also describes failure

by cracking. In fact, abrasive wear is due to thecumulative growth of cracks by tearing under repetitiveloading. Therefore, the analysis and characterisationof cracks in NR are crucial to the development ofmaterial with improved fracture resistant properties.Several spectroscopic methods are available forcharacterising the crack tip region of the rubber on themolecular scale; FTIR microspectroscopy has beenused for this purpose (91).

FTIR microspectroscopy was applied for thecharacterisation of compositional heterogeneity of apolymer blend. For a polymer blend prepared by mixingPP and polycarbonate, the spatially specificcompositional heterogeneity could be easily identified(106).

Mapping the phases of PVAL and PVA blends wasaccomplished using FTIR microspectroscopy. Thedimensions, shapes, and distributions of the domainsare dependent on the initial composition of thepolymeric mixtures in solution. Specific interactionsbetween both homopolymers were observed (129).

Polyvinylidene fluoride (PVDF) samples, obtained bycasting from tetrahydrofuran (THF) solutions andsubmitted to various thermal treatments, were examinedby FTIR microspectroscopy. The analysis permittedexamination of microdomains of samples of differentmorphological characteristics and an indication of thepolymorphism of PVDF is obtained (213).

FTIR microspectroscopy was used to investigate thedrying of water-based acrylic polymer coatings on analuminised substrate. Changes in the absorbance peakheights were monitored as an indication of theremaining water content. The effects on drying ofhumidity, solids content, coating thickness and thepresence of coalescing agents were studied. Coalescingagents were found to increase drying time while aidingfilm formation. Drying time decreased with increasingsolids content and increased with increasing coatingthickness. As expected, relative humidity was found tohave an important effect on the drying process (246).

The interphase in PE fibre/epoxy resin matrixcomposites was studied by FTIR microspectroscopyusing a set up for investigation of the matrix as closeto the fibre as a few microns or less. It was shown thatmoisture present on the fibre surface could influencethe polymerisation reaction of the epoxy/anhydridematrix in an irreversible manner (249).

Model composites of Kevlar-49 and D-glass fibre/epoxy systems were analysed using FTIR micro-

Infrared and Raman Spectroscopy of Polymers

37

spectroscopy. The interphase and specific fibre-matrixinteractions of the fibre-reinforced composites werecharacterised. The surfaces of both Kevlar-49 and D-glass fibres were found to affect the curing process incomposite samples significantly. The epoxy was foundto cure at an accelerated rate at the surface of thesefibres indicating strong interaction between the fibresand the matrices. Using FTIR microspectroscopy, theseinteractions were found to be preferential segregationof the epoxy on the Kevlar surface. It was alsodetermined that the amine group of the Kevlar fibreacted to catalyse the curing process (286).

FTIR mapping was used to study vinyl siding.Particular attention was paid to the determination, insingle mapping experiments, of the compositionalchanges associated with capstock to substrate transitionand to evaluation of the degradation species and levelobserved during weathering exposure throughout thethickness of the siding panel (153).

A combination of cryomicrotomy and FTIRmicroscopy was used to investigate chemical changesin unstrained sheets of PU caused by biodegradation(18 month subcutaneous ovine implant).Cryomicrotomy was used to obtain thin sections fromthe surface into the bulk, parallel to the plane of thesurface. FTIR microscopy was then used to detectchemical changes (156).

The effect of mechanical deformation on a UV-curedurethane-acrylate polymer and on a silicon carbide/urethane-acrylate model composite was studied by FTIRmicrospectroscopy. This technique was used for the firsttime to measure the width of the interfacial zone beyondwhich the fibre has no influence on the matrix (161).

FTIR microspectroscopy has proved useful incharacterising contaminants as small as 5 x 10-5 m indiameter in resins and cured films as well ascharacterising cured film surfaces (191).

Glass fibre strand was treated with gamma-methacryloxypropyltrimethoxysilane as a couplingagent and used to reinforce a vinylester resin. Theinterface was studied by FTIR spectroscopy andshowed that the silane was able to migrate into the resinand influence curing at a distance (200 μm) greater thanthe thickness of the interphase (328).

IR microspectroscopy was used to study the cellmembranes of a flexible PU foam and correlations weremade of absorbance values of methyl signals withabsolute thicknesses calculated from the interferencepatterns observed in the spectra (333).

A comparison is made of the polymer and liquid crystaldroplet regions within polymer-dispersed liquid crystalfilms using FTIR microspectroscopy. IR functionalgroup images of a droplet showed characteristictextures corresponding to the visual images of the samedroplet. The textures in the IR images changed withIR polarisation and with an applied electric field.Hysteresis was observed in the IR region as a functionof voltage and temperature (334).

IR microspectroscopy was used to generate functionalgroup images of liquid crystal (E7) droplets dispersedin poly-n-butyl methacrylate (PBMA). The spatialconcentration fluctuations that occurred within thesystem were studied as a function of time. Thisapproach was possible because spectral informationcould be obtained by focusing on regions of the orderof tens of micrometres. The peak intensities were usedas a measure of concentration of the components. Theamount of liquid crystal dissolved in the polymermatrix determined the extent to which the polymerwas plasticised, which in turn affected the shape andsize of the droplets. The growth of the domains atany temperature was also determined by whether thesystem was maintained above or below the Tg of thematrix. It was observed that the growth of the dropletsfollowed temporal power laws (i.e., time raised to apower of ~θn). The spatially resolved spectroscopicimages provided valuable insights into the phaseseparation process and the formation of microdropletsof E7 in PBMA (280).

7.19 FTIR Imaging

FTIR spectroscopic imaging microscopy is a techniquein which instrumentation is designed about an InSbmultichannel IR array detector, FPA detector and avariable-bandpass dielectric filter. The system may beconfigured for either macroscopic or microscopicapplications and high-fidelity, chemically specificimages may be acquired in real time. The functioningof the imaging microscope is demonstrated withsamples including PS microspheres, preparation oflipids and an amino acid embedded in KBr disks, anda tissue sample derived from a coronal slice of amonkey cerebellum (271).

The FTIR imaging method was extended to the real-time acquisition of images from systems varying withtime. Emphasis is given to the monitoring of thediffusion of a low molecular weight liquid crystalpentylcyanobiphenyl into a solid polybutylmethacrylate film (136).

Infrared and Raman Spectroscopy of Polymers

38

An imaging spectrometer made measurements of thevisible and NIR absorption spectra of EVA copolymers.The NIR spectral images obtained clearly indicated thatthe EVA copolymers exhibited a high degree ofchemical inhomogeneity (105).

FTIR imaging is a powerful technique that can be usedto obtain spatially resolved chemical information froma large sample area in a relatively short time. However,temporal resolution of fast FTIR imaging is limited byrapid loss of data quality due to increased noise withfaster image acquisition. The application of theproposed schemes allows for improved SNRcharacteristics in the resulting data. These schemes aretested by monitoring the dissolution of a polymer film(poly (alpha-methyl styrene)) by a low molecularweight solvent (methyl isobutyl ketone (MIBK)). Atotal acquisition time of about 100 s is achieved,allowing the dissolution process to be monitored byusing image acquisitions separated by 3 minutes. Lownoise concentration profiles, linear solvent penetrationrate and polymer dissolution rate are measured. Thisresult represents an order of magnitude improvementover untreated data (47).

The FTIR imaging method was extended to the real-time acquisition of images from systems varying withtime. Emphasis is given to the monitoring of thediffusion of a low molecular weight liquid crystalpentylcyanobiphenyl into a solid polybutylmethacrylate film (136).

Fast FTIR imaging was used to study the distributionof chemical species and the degree of orientation insemi-crystalline systems. The systems investigatedwere PEG and blends of PEG with PEO, PMMA orPVA. The technique was shown to be useful fordetermining the distribution of species with differentmolecular weights and for determining the degree ofsegregation of the different blend components. Usingan IR polariser, the degree of orientation wasdetermined in the systems by generating spatiallyresolved dichroic ratio images (52).

FTIR imaging, combined with statistical methods, wasshown to be a valuable tool for determining phasecomposition in multiphase systems. A method forreducing liquid crystal solubility in production ofpolymer dispersed liquid crystals (PDLC) wasdeveloped which involved cooling a homogeneousliquid crystal/precursor matrix into the two-phaseregime, followed by fast matrix polymerisation. Theproposed procedure was tested by using a well-studiedPDLC system, NOA65 (a UV-curable optical adhesive)and E7 (a mixture of cyanobiphenyls). Liquid crystal

remaining dissolved in the matrix was sharply reducedby this method. Residual solubility of the matrixmaterial in liquid crystal domains was also decreased.While maintaining the same phase composition, themethod also allowed dispersion size to be tailoredaccording to needs as opposed to the invariablecorrelation between droplet size, solubility andpolymerisation rate inherent in the classicalpolymerisation-induced phase separation methods. Thisgeneral methodology could be usefully applied to othersystems (88).

7.20 Raman Microimaging

The incorporation of high-resolution optics in aRaman spectrometer allows sampling from areas ofless than 1 x 10-6 m in diameter. The addition of aconfocal microscope improves the axial resolution to2 x 10-6 m. Those developments, along with theintroduction of notch filters and holographictransmission gratings, allow the reduction of theacquisition time of Raman spectra from minutes toseconds. The fast data collection combined with thehigh lateral and vertical resolutions makes possiblescanning experiments in which the specimen isadvanced in 1 x 10-6 m size steps. Analysis of thespectra provides information on the spatialcomposition of the sample (139). Two alternativemethods of Raman imaging via global illuminationand via point illumination in combination withconfocal light collection can be applied to the studyof heterogeneous polymer systems (205). The effectsof spectrometer slit width, spatial resolution and thenumber of spectral variables of Raman line-imageswere studied. Depth of penetration and SNRconsiderations dominated the proper selection of slitwidth for the sample of PS spheres (10 μm diameter)embedded in an epoxy resin matrix. With the use ofdifferent microscope objectives to analyse the samesample region, the higher-magnification objectivegave better results, probably due merely to the largernumber of spectra processed (222).

Raman microimaging is used to estimate the effect ofthe silica filler on phase separation in binary polymerblends composed of brominated poly(isobutylene-co-para-methyl) styrene (BIMS) and butyl rubber (IIR).The domain sizes, relative concentration of polymercomponents within domains, and distribution ofparticulate silica filler and zinc stearate curative arecharacterised for blends of different compositions andhistory of ageing treatments. The presence of increasedconcentrations of precipitated silica results in better

Infrared and Raman Spectroscopy of Polymers

39

polymer morphology since domain sizes are reduced.Increased temperature treatment also decreases domainsizes up to about 150 °C, but treatment at 200 °Cappears to induce separation of the elastomercomponents. Silica is usually found near the centres ofthe BIMS domains. There is little difference in silicadistribution before and after curing (33).

Using micro-Raman imaging three blends consistingof PP/PE/EPR copolymer, PBT/polycarbonate/LDPE,and SAN copolymer/styrene-maleic anhydridecopolymer/polydimethylphenylene oxide were studiedwith regard to compositional and morphologicalheterogeneities (221).

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a.2 M. Diem, Introduction to Modern VibrationalSpectroscopy, Wiley, New York, NY, USA,1993.

a.3 J.R. Ferraro and K. Nakamoto, IntroductoryRaman Spectroscopy, Academic Press,Orlando, FL, USA, 1994.

a.4 J.L. Koenig, Spectroscopy of Polymers, 2ndEdition, Elsevier, Amsterdam, the Netherlands,1999, 147.

a.5 P.C. Painter, M.M. Coleman and J.L. Koenig,The Theory of Vibrational Spectroscopy andits Application to Polymeric Materials, JohnWiley & Sons, Inc., New York, NY, USA, 1982.

a.6 D. Lin-Vien, N. Colthup, W.G. Fateley and J.G.Grasselli, The Handbook of Infrared andRaman Characteristic Frequencies of OrganicMolecules, Academic Press, San Diego, CA,USA, 1991.

a.7 B.G. Osborne, T. Fearn and P.H. Hindle,Practical NIR Spectroscopy, LongmanScientific and Technical Publishers, Harlow,UK, 1993.

a.8 P.J. Treado and M.D. Morris, AppliedSpectroscopy Review, 1994, 29, 1.

a.9 E.N. Lewis, P.J. Treado, R.C. Reeder, G.M.Story, A.E. Dowrey, C. Marcott and I.W. Levin,Analytical Chemistry, 1995, 67, 3377.

a.10 E.N. Lewis and I.W. Levin, AppliedSpectroscopy, 1995, 49, 672.

a.11 N.C. Crabb and P.W.B. King in MolecularSpectroscopy in Process Analytical Chemistry,Eds., F. McLennan and B.R. Kowalski,Blackie, London, UK, 1995, 40.

a.12 D.C. Hassell and E.M. Bowman, AppliedSpectroscopy, 1998, 52, 18A.

a.13 D.A. Long, Raman Spectroscopy, McGraw-Hill, New York, NY, USA, 1977.

a.14 D.B. Chase and J.F. Rabolt, Ed., FourierTransform Raman Spectroscopy, AcademicPress, Orlando, FL, USA, 1994.

a.15 J. Zhao and R.L. McCreery, AppliedSpectroscopy, 1996, 50, 1209.

a.16 M. Moskvits, Reviews in Modern Physics,1985, 57, 783.

a.17 S. Nie and S. Emory, Science, 1997, 275, 1102.

a.18 P.J. Treado, I.W. Levin and E.N. Lewis, AppliedSpectroscopy, 1992, 46, 1211.

a.19 E.G. Bucher and J.W. Caranhan, AppliedSpectroscopy, 1999, 53, 603.

a.20 N.J. Harrick, Internal Reflection Spectroscopy,Wiley-Interscience, New York, NY, USA,1967.

a.21 M.R. Pereira and J. Yarwood, Journal ofPolymer Science: Polymer Physics Edition,1994, 32, 11, 1881.

a.22 J.B. Huang and M.W. Urban, AppliedSpectroscopy, 1992, 46, 1666.

a.23 J.B. Huang and M.W. Urban, AppliedSpectroscopy, 1993, 47, 973.

a.24 J.D. Swalen and J.F. Rabolt in FourierTransform Infrared Spectroscopy, Applicationsto Chemical Systems, Volume 4, Eds., J.R.Ferraro and L.J. Baslie, Academic Press, NewYork, NY, USA, 1985, 86.

a.25 W.G. Golden in Fourier Transform InfraredSpectroscopy, Applications to ChemicalSystems, Volume 4, Eds., J.R. Ferraro and L.J.Baslie, Academic Press, New York, NY, USA,1985, 140.

a.26 P. Kubelka and Z. Munk, Z. Tech. Physics,1931, 12, 593.

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a.27 S. Bistac, M.F. Vallat and J. Schultz, AppliedSpectroscopy, 1997, 51, 1823.

a.28 D.A.C. Compton and S.V. Compton, AppliedSpectroscopy, 1991, 45, 1587.

a.29 B. Jasse and J.L. Koenig, Journal ofMacromolecular Science: Reviews inMacromolecular Chemistry, 1997, C17, 1, 135.

a.30 D.I. Bower, Journal of Physics B: Atomic andMolecular Physics, 1976, 9, 3275.

a.31 P.J. Hendra and J.L. Agbenyega, The RamanSpectra of Polymers, Wiley, Chichester, UK,1993.

a.32 R. Gachter, H. Muller, Ed., Plastics AdditivesHandbook, 4th Edition, Hanser, Munich,Germany, 1994.

a.33 http://www.polymeradditives.com.

a.34 I. Noda, Applied Spectroscopy, 1993, 47, 1329.

a.35 I. Noda, A.E. Dowrey, C. Marcott and G.M.Story, Applied Spectroscopy, 2000, 54, 236A.

a.36 S. Ekgasit and H. Ishida, Applied Spectroscopy,1995, 49, 1243.

Infrared and Raman Spectroscopy of Polymers

41

ABS Acrylonitrile-butadiene-styreneterpolymer

AC Acid chloride

AIBN Azobisisobutyronitrile

AOTF Acousto-optic tunable filter

ATR Attenuated total reflection

BIMS Brominated poly(isobutylene-co-para methyl) styrene

BPDA 3´,3´,4,4´-biphenyltetracarboxylicdianhydride

CCD Charge collection detector

CHMI N-cyclohexylmaleimide

CHPS Cyclohexa(p-phenylene sulfide)

COF Acid fluoride group

COOH Carboxylic acid group

DRIFT Diffuse reflectance FTIR

ENR Epoxidised natural rubber

EPDM Ethylene-propylene-dieneterpolymer

EPR Ethylene-propylene copolymer

EVA Ethylene-vinyl acetate

FPA Focal plane array

FTIR Fourier transform infrared

GMA Glycidyl methacrylate

GTP Group transfer polymerisation

HDPE High density polyethylene

HPLC-FTIR High performance liquidchromatography - FTIR

IIR Butyl rubber

IR Infrared

LCST Lower critical solution temperature

MIBK Methyl isobutyl ketone

MMA Methyl methacrylate

NIR Near infrared

NMR Nuclear magnetic resonance

NR Natural rubber

PA Polyamide

PAA Polyacrylic acid

PAM-co-AA Poly(acrylamide-co-acrylic acid)

PAN Polyacrylonitrile

PBI Polyphenylene bibenzimidazole

PBMA Poly-n-butyl methacrylate

PBT Polybutylene terephthalate

PCA Principal component analysis

PDA p-phenylene diamine

PDLC Polymer dispersed liquid crystal

PDMS Polydimethyl siloxane

PDPE Low density polyethylene

PE Polyethylene

PEG Polyethylene glycol

PEI Polyethyleneimine

PEN Poly(ethylene naphthalate)

PEO Polyethylene oxide

PET Polyethylene terephthalate

PHEMA Poly(2-hydroxyethyl methacrylate)

PLS Partial least squares

PLSR Partial least squares regression

PMAA Polymethacrylic acid

PMMA Polymethyl methacrylate

PNIPAAM Poly(N-isopropylacrylamide)

PP Polypropylene

PPE Poly(2,6-dimethyl-1,4-phenyleneether)

PPMS Poly-p-methylstyrene

PPO Polypropylene oxide

PPS Poly(p-phenylene sulfide)

PS Polystyrene

PTFE Polytetrafluoroethylene

PU Polyurethane

PVA Polyvinyl alcohol

PVAL Polyvinyl alcohol

PVC Polyvinyl chloride

PVDF Polyvinylidene fluoride

SDOSS Sodium dioctylsulfosuccinate

SERS Surface-enhanced Ramanspectroscopy

SFE/FTIR Supercritical fluid extraction/FTIR

SNR Signal to noise ratio

Tg Glass transition temperature

THF Tetrahydrofuran

TMPO-1 1,2-epoxy-2,4,4-trimethylpentane

TPR Terpene-phenol resins

UVRR Ultraviolet Raman resonance

VA Vinyl acetate

Abbreviations

Infrared and Raman Spectroscopy of Polymers

42

References and Abstracts

© Copyright 2001Rapra Technology Limited 43

References from the Rapra Abstracts Database

Item 1ACS Polymeric Materials Science and Engineering.

Volume 75. Conference Proceedings.

Orlando, FL., Fall 1996, p.106-107.

RAMAN AND FTIR STUDIES OF THE EFFECTSOF DRAW RATIO AND SIDE CHAIN LENGTHON THE MOLECULAR ORIENTATION OFPOLYESTER FILMSVlassopoulos D; Petekidis G; Vogiatzis G; Kamitsos E

I; Yiannopoulos Y; Bruggeman A

Crete,Institute of Electronic Structure & Laser;

Patras,Institute of Chemical Engineering & High

Temperature Processes; Foundation for Research and

Technology Hellas; Athens,National Hellenic Research

Foundation; TNO Plastics & Rubber Research Institute

(ACS,Div.of Polymeric Materials Science & Engng.)

Laser Raman and FTIR spectroscopy measurements were

combined to determine the degree of molecular orientation

in uniaxially oriented polyester films, as a function of the

draw ratio, and so that the effects of side chain length can

be further quantified. The measurement of molecular

orientation in liquid crystalline polymers is of high

importance because of its potential in obtaining ultra-high

modulus materials. A significant degree of molecular

orientation along the stretching direction was identified.

10 refs.

USA

Accession no.806758

Item 2Journal of Sol-Gel Science and Technology

19, Nos.1-3, Dec.2000, p.403-7

STRUCTURE OF HYBRID GELS BY DRIFT ANDNMR SPECTROSCOPIESFidalgo A; Nunes T G; Ilharco L M

Lisbon,Instituto Superior Tecnico

Hybrid inorganic-organic gels were prepared by the sol-

gel process using tetraethoxysilane as precursor, mixed

with a low concentration of polytetrahydrofuran, under

acid catalysis. The hybrid xerogels were characterised

by DRIFTS and solid state proton, carbon-13 and

silicon-29 NMR spectroscopies. The diffuse reflectance

IR (DRIFT) spectra indicated that the polymer was

responsible for decreasing the number of free silanol

groups in comparison with pure silica. Solid state NMR

spectra revealed the types of silicate structures formed

and the conditions for establishing chemical bonds

between the two phases, which were responsible for

the silica network flexibility. It was concluded that it

was possible to design a hybrid gel with tailored

properties, even at very low polymer concentration, by

selecting the appropriate preparation route. 10 refs.

(10th International Workshop on Glass and Ceramics,

Hybrids and Nanocomposites from Gels, ‘Sol-Gel ‘99’,

Yokohama, Japan, Sept.1999)

EUROPEAN COMMUNITY; EUROPEAN UNION; PORTUGAL;

WESTERN EUROPE

Accession no.805107

Item 3ACS Polymeric Materials Science and Engineering.

Volume 75. Conference Proceedings.

Orlando, FL., Fall 1996, p.70-1. 012

ATR FT-IR SPECTROSCOPIC STUDIES OFMICROWAVE PLASMA REACTIONS OFIMIDAZOLE ON POLY(VINYL CHLORIDE)Schmitt B R; Kim H; Urban M W

North Dakota State University

(ACS,Div.of Polymeric Materials Science & Engng.)

This work focuses on imidazole reactions to polyvinyl

chloride (PVC), formation of reactive sites, reaction

mechanisms, and quantitative analysis of the surface

species at various depths. For quantitative surface analysis

ATR FT-IR spectroscopy was used. For hot-pressed PVC,

no imidazole reactions were detected on PVC surfaces

under argon and oxygen microwave plasma conditions.

Under oxygen microwave plasma conditions, however,

newly formed CH2 linkages are detected, resulting from

the C-Cl bond cleavages. In solvent-cast PVC, imidazole

molecules react to PVC through a carbon-carbon double

cleavage of imidazole, and the formation of the ester

linkages between PVC and imidazole molecules.

Quantitative analysis of imidazole reactions to solvent-

cast PVC surfaces at various depths reveals that imidazole

reactions take place within 0.8 microns from the surface.

At surface depths of up to 1.2 microns, surface

concentration of imidazole reacted to PVC declines from

0.37 x 10-6 mole/square centimetre to 0.17 x 10-6 mole/

square centimetre. 8 refs.

USA

Accession no.803055

Item 4ACS Polymeric Materials Science and Engineering.

Volume 75. Conference Proceedings.

Orlando, FL., Fall 1996, p.65-6. 012

POLYOLEFIN CHARACTERIZATION OF FTIRTRANSMISSION SPECTROSCOPYBlitz J P

Eastern Illinois,University

(ACS,Div.of Polymeric Materials Science & Engng.)

FTIR spectroscopy was used to measure polyethylene and

polypropylene isotacticity, specifically to provide data in

the relatively narrow, industrially important high

isotacticity range. The FTIR data reported in this range is

correlated with both NMR and solvent extraction

References and Abstracts

44 © Copyright 2001 Rapra Technology Limited

measurements. The present work demonstrates the

usefulness of ordinary transmission FTIR spectroscopy

in obtaining qualitative and quantitative data concerning

short chain branching in a variety of polyethylenes. It is

possible to obtain quantitative isotacticity values of

polypropylene by transmission FTIR spectroscopy. FTIR

has particular advantages over NMR spectroscopy in

terms of cost and ease of use. In many instances, FTIR

can be utilised more readily than NMR. In other instances,

more detailed structural information can still be provided

by NMR than FTIR. 4 refs.

USA

Accession no.803052

Item 5ACS Polymeric Materials Science and Engineering.

Volume 75. Conference Proceedings.

Orlando, FL., Fall 1996, p.63-4. 012

SPECULAR REFLECTION FT-IR STUDIES OFTHE CONFORMATIONAL BEHAVIOUR OF PETCole K C; Guevremont J; Aiji A; Pellerin E;

Dumoulin M M

Canada,Industrial Materials Institute

(ACS,Div.of Polymeric Materials Science & Engng.)

The use of front surface specular reflection Fourier

infrared spectroscopy was used to obtain information on

molecular conformation and orientation at the surface of

thick samples of drawn poly(ethylene terephthalate)

(PETP). Reflectance spectra measured with polarisation

parallel or perpendicular to the draw direction can be

decomposed into refractive index and absorption index

spectra, by means of the Kramers-Kronig transformation.

The most interesting of the strong bands of PETP is the

carbonyl band. A mechanism for the conformational

changes that take place on drawing PETP is proposed in

which planar states are energetically favoured, the barrier

to rotation is sufficiently low to allow a high probability

of non-planar states. Drawing at 80 degrees Celsius causes

significant conversion of gauche to trans conformers in

the glycol segments, but it does not appear to have an

effect on the terephthalate groups. 12 refs.

USA

Accession no.803051

Item 6ACS Polymeric Materials Science and Engineering.

Volume 75. Conference Proceedings.

Orlando, FL., Fall 1996, p.43. 012

DETERMINING THE ORIENTATIONAL ORDEROF MEMBRANE-BOUND POLYPEPTIDES BYPOLARIZED ATIR-FTIRAxelsen P H; Citra M J

Pennsylvania,University

(ACS,Div.of Polymeric Materials Science & Engng.)

The orientational order of polypeptide helices can be

characterised by polarised attenuated total internal

reflection Fourier transform infrared (PATIR-FTIR)

spectroscopy. This requires an understanding of the

evanescent electric field amplitudes, and these, the

orientation of the vibrational transition moment relative

to the helix axis. A number of expressions used for

calculating evanescent electric field amplitudes in

supported lipid membranes are discussed and their validity

tested by measuring the infrared dichroism of poly-

gamma-benzyl-L-glutamate and poly-beta-benzyl-L-

aspartate under conditions in which their conformation

and molecular order is known. The results suggest that

the aspartyl and glutamyl peptides display differing values

for theta, despite similar amide absorption frequencies

and band shapes. The results also indicate that the

absorption intensities for these polymers in a lipid

membrane are self-consistent only if it assumed the

electric field amplitudes to be determined entirely by the

refractive index of the bulk medium in which the crystal

is immersed.

USA

Accession no.803039

Item 7ACS Polymeric Materials Science and Engineering.

Volume 75. Conference Proceedings.

Orlando, FL., Fall 1996, p.39-40. 012

HIGH-PRESSURE PHOTOACOUSTIC STEP-SCAN FT-IR SPECTROSCOPY OF POLYMERSPennington B D; Urban M W

North Dakota State University

(ACS,Div.of Polymeric Materials Science & Engng.)

The basis for high pressure photoacoustic spectroscopy

and the resulting enhancement of the photoacoustic signal

is described. An experimental setup has been designed

which enhances the photoacoustic signal response, which

is attributed to the more efficient transfer of the

photoacoustic signal from the analysed specimen to the

microphone. In addition, phase analysis results can be

derived from high pressure experiments in step-scan

mode. The high pressure experiments were carried out

using thermoplastic olefin (TPO), silanol terminated

polydimethylsiloxane (PDMS), and polyimide. In all

cases intensity enhancements were detected as pressure

rises. A comparison of the pressure effect on the relative

signal enhancement shows a less pronounced effect in

the liquid polymer (PDMS) than for the solid samples

(TPO or polyimide). This is because the distance from

the sample to the cell window is inversely proportional

to the photoacoustic signal intensity so that a rise in this

distance parameter will result in a decreased photoacoustic

response. As pressure is applied to a specimen, specific

volume and inter-molecular distance change, resulting in

a decrease in the physical dimensions of the sample, which

results in the change in the photoacoustic signal intensity

and the shift of the photoacoustic phase. 15 refs.

USA

Accession no.803035

References and Abstracts

© Copyright 2001Rapra Technology Limited 45

Item 8ACS Polymeric Materials Science and Engineering.

Volume 75. Conference Proceedings.

Orlando, FL., Fall 1996, p.11. 012

QUANTITATIVE ASPECTS OF ATR ANDPHOTOACOUSTIC STEP-SCAN FT-IR ANDINTERFACIAL ANALYSIS OF POLYMERICFILMSUrban M W

North Dakota State University

(ACS,Div.of Polymeric Materials Science & Engng.)

There are significant implications arising from the ability

of stratifying polymer surfaces and interfaces using

attenuated total reflectance and photoacoustic step-scan

Fourier transform infrared (FTIR) spectroscopy.

Theoretical concepts and experimental methods involved

in the stratification approach to polymer films are

discussed. Quantitative analysis of interfacial regions in

multi-layered polymers is given particular emphasis. The

utilisation of ATR and SS PAS, together with the

stratification multi-layer concept, enables depth-profiling

experiments to be carried out on multi-layered polymer

films. It also provides molecular level data relating to

interfacial interactions between the layers.

USA

Accession no.803018

Item 9ACS Polymeric Materials Science and Engineering.

Volume 75. Conference Proceedings.

Orlando, FL., Fall 1996, p.11. 012

SURFACE-ENHANCED AND FOURIER-TRANSFORM RAMAN SPECTROSCOPY OFPOLYMERSBoerio F J; Zhao W W; Tsai Y M

Cincinnati,University

(ACS,Div.of Polymeric Materials Science & Engng.)

In order to determine the interfacial and bulk structure of

polymers surface-enhanced (SERS) and Fourier-

Transform Raman spectroscopy were utilised. Langmuir-

Blodgett monolayers of PMDA/ODA polyimides were

formed by transferring monolayers of the

dimethylhexadecylamine salt of the polyamide acid onto

silver island films. SERS spectra of 1- and 3-layer LB

films of the salts were characterised by bands near 1400

and 1620 cm-1 that were related to carboxylate species

and to a stretching mode of the benzene rings, respectively,

New bands related to isoimide and imide groups appeared

near 1695 and 1800 cm-1 when the films were imidised.

Characterisation of the curing of a model rubber

compound consisting of squalene (instead of natural

rubber), initiators, sulphur, accelerators, adhesion

promoters, anti-oxidants, and carbon black was achieved

by using FT/Raman spectroscopy. Only one band, near

1670 cm-1, was observed between 1500 and 1700 cm-1

for short curing times. For longer curing times, new bands

attributed to conjugated double bonds were observed near

1646, 1640, 1628, 1600 and 1580 cm-1. Also, a new band

related to polysulphidic crosslinks appeared near 210 cm-

1 after reaction for 15 minutes. After about 30 minutes

the intensity of this band reached a maximum. A model

for the curing reaction was developed from these

observations.

USA

Accession no.803017

Item 10ACS Polymeric Materials Science and Engineering.

Volume 75. Conference Proceedings.

Orlando, FL., Fall 1996, p.8. 012

RAMAN SPECTROSCOPY AND CRYSTALLINEPOLYMERS: THE POLYETHYLENESMandelkern L; Rufina G A

Institute of Molecular Biophysics; FAMU-FSU College

of Engineering

(ACS,Div.of Polymeric Materials Science & Engng.)

An overview is given of some of the applications of

Raman spectroscopy that lead to an understanding of

the factors that determine the phase structure of

crystalline, flexible chain polymers. Emphasis is given

to the polyethylenes of different molecular

architectures and their corresponding oligomers, the

n-alkanes. The focus of the spectroscopic data is the

internal mode and LAM spectral regions. In order to

determine the crystallite thickness it is necessary to

establish Young’s modulus and to evaluate the validity

of the basic relation that is involved. This study

illustrates the difficulty in determining the exact

ordered sequence length for polyethylene and for

folded n-alkanes and other oligomers and relates to the

establishing of integral fold periods. For a system of

stacked lamellae, an analysis of both the LAM and

internal modes can give the thickness of the interfacial

region. Data is presented which gives quantitative

agreement of the interfacial thickness, as determined

by either the Raman method or small-angle X-ray

scattering. Studies of n-alkanes and polyethylenes in

the melt and in the crystalline state indicate that the

1060 cm-1 band measures both the long trans sequences

in the crystalline state as well as short sequences in

the interphase and liquid-like regions. The persistence

of this band in the melt precludes its use in quantifying

the level of crystallinity. For a high molecular weight

linear polyethylene it has been found that alpha a

determined from the band around 860 cm-1 was less

than that determined from the 1303 em-1 band. It was

postulated that a fourth element of phase structure was

present. The experimental findings for a large range of

molecular weight polyethylenes have been confirmed,

but an alternate explanation of these results can be

given that is consistent with the three basic elements

of phase structure. 16 refs.

USA

Accession no.803015

References and Abstracts

46 © Copyright 2001 Rapra Technology Limited

Item 11Antec 2000.Conference proceedings.

Orlando, Fl., 7th-11th May, 2000, paper 499

CHARACTERIZATION OF POLYETHYLENEBLENDS BY USING NOVEL TECHNIQUESSUCH AS THE SUCCESSIVE SELF-NUCLEATION AND ANNEALING (SSA) ANDTHE FOURIER SELF-DECONVOLUTION IRSPECTROSCOPY (FSD-IR)Sierra J D; Ospina S; Montoya N; del Pilar Noriega M;

Osswald T A

Instituto de Capacitacion e.Investigacion del Plastico y

del Caucho; Wisconsin-Madison,University

(SPE)

The characterisation of binary and ternary blends of

polyethylenes by successive self-nucleation and annealing

(SSA), and by Fourier self deconvolution infrared

spectroscopy was investigated. The SSA investigation,

which is capable of determining lamellar thickness

distributions, short chain branching, and characterising

grafted polymers, was done using a conventional heat flow

calorimeter. Self deconvolution is a Fourier transform

mathematics technique to enhance the resolution between

adjacent bands, to quantify linear low density

polyethylene. It was concluded that SSA was a low-cost

alternative for the characterisation of novel metallocene

polymers. 7 refs.

COLOMBIA; USA

Accession no.802029

Item 12Colloid & Polymer Science

278, No.10. Oct.2000, p.946-53

TIME-RESOLVED NEAR-INFRARED AND TWO-DIMENSIONAL NEAR-INFRAREDCORRELATION SPECTROSCOPIC STUDIESON POLYMERIZATION OF THE SILANECOUPLING AGENTPERFLUOROOCTYLTRIMETHOXYSILANEOgasawara T; Nara A; Okabayashi H; Nishio E;

O’Connor C J

Nagoya,Institute of Technology; Nicolet Japan Corp.;

Auckland,University

Both two-dimensional near infrared (2D NIR) and time

resolved near infrared (TR NIR) indicate the progress of

the polymerisation process of perfluorooctyl-

trimethoxysilane catalysed by hydrogen chloride in

ethanol. TR NIR was used to monitor the bands associated

with water and ethanolic hydroxyl groups during the

reaction. Consumption and release of water molecules

was observed strongly in the initial reduction, followed

by rapid increase of the band at 5164 reciprocal

centimetres. The band at 4825 reciprocal centimetres

(associated with OH groups) increased throughout the

reaction as a result of the hydrolysis of methoxy groups

and formation of silanols. 2D NIR allowed the observance,

from calculated asynchronous spectral maps, of two

species of silanol groups whose behaviour during the

reaction is considered. 33 refs

JAPAN; NEW ZEALAND

Accession no.796713

Item 13Applied Spectroscopy

54, No.9, Sept.2000, p.1384-90

FT-RAMAN SPECTROSCOPICINVESTIGATIONS ON THE ORGANICCROSSLINKING IN HYBRID POLYMERS. I.MODEL REACTIONS OF SIMPLE EPOXIDESRiegel B; Kiefer W; Hofacher S; Schottner G

Wuerzburg,University; Fraunhofer-Institut fuer

Silicatforschung

Model reactions of epoxypropane and epoxyhexane were

analysed using Fourier Transform-Raman spectroscopy and

Carbon-13 NMR spectroscopy to obtain information on the

possible products of ring opening in epoxy silane-based sol-

gel derived hybrid polymers. A mixture of epoxyalkane,

tetramethoxysilane and aluminium sec-butylate was

employed to investigate behaviour during the sol-gel process.

Raman band and NMR peak assignments for various reaction

products are presented and discussed. 24 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.794693

Item 14Applied Spectroscopy

54, No.8, Aug.2000, p.1192-202

MEASUREMENT OF THE SENSITIVITY ANDPHOTOMETRIC ACCURACY OF FT-IRSPECTROMETERSBowie B T; Griffiths P R

Idaho,University

A method is developed to investigate the sensitivity and

photometric accuracy of a Fourier transform infrared (FT-

IR) spectrometer by statistically analysing a set of spectra

of a 75 mu m thick film of PETP. These tests are applied to

three commercial FT-IR spectrometers. Although the

photometric accuracy of all three instruments is generally

better than 0.1%, small artifacts that cannot be removed

by signal averaging are often observed where strong bands

should have a transmittance of less than 0.01%. Binding

of the moving mirror of one of the spectrometers appears

to degrade its performance. When the standard deviation

of the noise on 100% lines is calculated conventionally,

none of the instruments give efficient signal averaging after

25 scans have been co-added, because of small slopes in

the baseline. By calculation of the noise level by successive

difference, signal averaging is improved, but even with this

approach the noise level on one of the instruments does

not decrease after 100 scans are averaged. 8 refs.

USA

Accession no.789824

References and Abstracts

© Copyright 2001Rapra Technology Limited 47

Item 15Polymer Science Series B

42, Nos.5-6, May-June 2000, p.169-74

IR SPECTROSCOPY STUDY OF POLYMERPOROSITYPakhomov P M; Kruglova E V; Khizhnyak S D

Tver,State University

IR spectroscopic method is developed for evaluating the

porosity (concentration and size of pores) in polymers.

PE and PAN films of various porosity are prepared from

the solutions in liquid and solid paraffins. The

concentration and maximum pore size in the bulk and in

a surface layer of the samples are determined by IR

spectroscopy in the transmission and reflection modes,

respectively. The results obtained are in agreement with

the data of optical and atomic force microscopy. 12 refs.

RUSSIA

Accession no.786845

Item 16Applied Spectroscopy

54, No.7, July 2000, p.968-73

INFRARED RHEO-OPTICS OF BOMBYX MORIFIBROIN FILM BY DYNAMIC STEP-SCAN FT-IR SPECTROSCOPY COMBINED WITHDIGITAL SIGNAL PROCESSINGSonoyama M; Nakano T

Tokyo,University of Agriculture & Technology; Nippon

Bio-Rad Laboratories

Dynamic step-scan FTIR spectroscopy combined with

software-based digital signal processing(DSP) was

applied for IR rheo-optical measurements of isotactic PP

and regenerated Bombyx mori silk fibroin film

undergoing sinusoidal mechanical strain. Comparative

measurements of dynamic IR spectra of PP film using

the DSP-based method and two lock-in amplifiers(LIAs)

indicated that a high signal-to-noise ratio(SNR) advantage

was attained by the DSP method combined with the LIA

method. With the DSP technique, dynamic spectra of

Bombyx mori silk fibroin film with high SNR were

successfully recorded in the whole mid-IR region in only

30 min. The dynamic spectra revealed that stress-induced

dynamic reorientation in fibroin film was mainly localised

in the segment with beta-sheet conformation and was

almost synchronous with the applied mechanical strain.

Two-dimensional correlation analyses of the dynamic

spectra showed that the broad amide I band was resolved

into three components whose positions were dependent

on secondary structures, that the dynamic behaviour of

tyrosine residues was extracted by separation of the

feature due to its aromatic side chains from the broad

envelope of the amide I band in the 2D asynchronous

map and that the dynamic behaviour of the amide A and

B modes was the same as that of the amide II mode, when

the mechanical strain was applied to fibroin film. 36 refs.

JAPAN

Accession no.785947

Item 17Polymer

41, No.24, 2000, p.8659-71

RAMAN MICROSCOPIC STUDIES OF THEDISTRIBUTION OF THE FUNGICIDEFLUORFOLPET IN PLASTICISED PVC FILMSMura C; Yarwood J; Swart R; Hodge D

Sheffield,Hallam University; Avecia Ltd.

Confocal Raman microscopy was used to study the

distribution and redistribution (by leaching) of the

fungicide Fluorfolpet (N-dichlorofluoromethyl-

thiophthalimide, 5%) in PVC films containing various

levels of DOP plasticiser. The distribution of both DOP

and Fluorfolpet was found to be uneven on a micron scale,

but there was no evidence of inhomogeneity of

distribution of either of these on a macroscopic scale.

There was little or no leaching of DOP into water.

Leaching of Fluorfolpet from the films was observed and

the redistribution of Fluorfolpet molecules (measured by

mapping and depth profiling) showed that this leaching

depended strongly on the DOP concentration or the

amount of water penetrating the film. The results were

discussed. 51 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.784928

Item 18ACS Polymeric Materials: Science &

Engineering.Spring Meeting 2000.Volume

82.Conference proceedings.

San Francisco, Ca., 26th-30th March 2000, p.404-5

DEGRADATION OF POLYURETHANES ANDEPOXIES; STEP-SCAN PHOTOACOUSTIC FT-IR AND IR/RAMAN IMAGINGKim H; Urban M W

Cessna Aircraft Co.; Southern Mississippi,University

(ACS,Div.of Polymeric Materials Science & Engng.)

Epoxy and polyurethane films were applied by spraying

to aluminium alloy substrates and exposed to UV light at

60 C to accelerate the effect of UV exposure. The resulting

degradation was studied using step-scan Fourier transform

infrared (FTIR) spectroscopy, FTIR microscopy and

Raman chemical imaging. The epoxy films formed cracks

following 5 weeks exposure, associated with a higher

concentration of primary amine groups, indicating higher

degradation, whilst in the non-cracked areas the intensity

of the N-H deformation band at 1509 /cm increased,

indicating diminished crosslinking reactions. In addition

the C-N bond stretching band at 1296 /cm decreased due

to C-N bond cleavage of tertiary amine groups. The

formation of polyurea was observed in the polyurethane

coating, attributed to crosslinking reactions of urethane

NH groups and NCO from the hexamethylene

diisocyanate used for its synthesis. 10 refs.

USA

Accession no.784762

References and Abstracts

48 © Copyright 2001 Rapra Technology Limited

Item 19ACS Polymeric Materials: Science &

Engineering.Spring Meeting 2000.Volume

82.Conference proceedings.

San Francisco, Ca., 26th-30th March 2000, p.398-9

MAPPING AND IMAGING ORIENTATION,CRYSTALLINITY AND CHEMICALCOMPOSITION IN POLYMER ARTICLESUSING INFRARED AND RAMANMICROSCOPIESEverall N J; Chalmers J M; Kidder L H; Lewis E N;

Schaeberle M; Levin I

ICI plc; Spectral Dimensions Inc.; US,National

Institutes of Health

(ACS,Div.of Polymeric Materials Science & Engng.)

The use of a fibre-coupled confocal Raman microscope

and an infrared microscope for both point mapping and

global imaging in the study of spatial variations in polymer

chemistry and morphology is illustrated by studies of the

curing of the UV-cured acrylate coatings, crystallinity in

drawn polyethylene terephthalate (PET) film, molecular

orientation in PET bottles, and the analysis of a PES/PEES

copolymer blended with epoxy resin and cured at elevated

temperature. 8 refs.

USA

Accession no.784759

Item 20ACS Polymeric Materials: Science &

Engineering.Spring Meeting 2000.Volume

82.Conference proceedings.

San Francisco, Ca., 26th-30th March 2000, p.396-7

INFRARED, RAMAN AND NEAR-INFRAREDSTUDIES ON STRUCTURE-PROPERTIESRELATIONSHIP IN HIGH DENSITY AND LOWDENSITY POLYETHYLENEOzaki Y; Amari T; Sasic S; Sato H; Shimoyama M;

Kamiya T; Ninomiya T

Kwansei-Gakuin,University; Mitsubishi Chemical

Corp.; Hyogo,Prefectural Police Headquarters

(ACS,Div.of Polymeric Materials Science & Engng.)

Infrared, near-infrared, and Raman spectroscopy were

used to study high density, linear low density (LLDPE),

and low density polyethylene. Overlapping spectral

bands were separated using the second derivative,

principal component analysis, and two-dimensional

correlation analysis. A model was developed, using

partial least squares regression, to calculate the density

of LLDPE. 1 ref.

JAPAN

Accession no.784758

Item 21ACS Polymeric Materials: Science &

Engineering.Spring Meeting 2000.Volume

82.Conference proceedings.

San Francisco, Ca., 26th-30th March 2000, p.378-9

STRATIFICATION PROCESSES IN LATEXES;ATR, PHOTOACOUSTIC, AND IR/RAMANIMAGING STUDIESZhao Y; Urban M W

Southern Mississippi,University

(ACS,Div.of Polymeric Materials Science & Engng.)

The surface distribution of sodium dioctyl sulphosuccinate

and sodium dodecylsulphate surfactant molecules in films

formed from poly(styrene-co-n-butyl acrylate-co-

methacrylic acid) latex was investigated using Fourier

transform infrared (FTIR) and Fourier transform Raman

spectroscopies, and surface morphology and depth profiling

were investigated using attenuated total reflectance FTIR.

It was concluded that these techniques were effective for

the study of surfactant stratification during the latex film

formation. The concentration of surfactant aggregates was

significantly higher at the film/air interface than at the film/

substrate interface, with surfactant hydrophilic groups

exhibiting preferential parallel orientation, and hydrophobic

groups preferential perpendicular orientation to the latex

film surface, the degree of orientation being surfactant

structure related. 21 refs.

USA

Accession no.784750

Item 22Journal of Polymer Science: Polymer Physics Edition

38, No.13, 1st July 2000, p.1773-87

DIFFUSION MEASUREMENTS USING ATR-FTIR SPECTROSCOPY: ACETONE DIFFUSIONIN POLYPROPYLENE - USE OF PENETRANTFLUID PRESSURE TO IMPROVE SAMPLE-IRECONTACTYi X; Portnoy J; Pellegrino J

US,National Inst.of Standards & Technology

A simple method for improving the sample film to crystal

contact during measurement of the diffusion of liquids

into polymer thin films is described using attenuated total

reflectance (ATR)-FTIR. The method is based on

controlling the penetrant fluid pressure above a threshold

value (greater than 230 kilo Pascal) in the ATR flow cell.

Using acetone in a commercial polypropylene film, the

calculated diffusion time constant was found to be

constant at pressures above this threshold value. It was

concluded that the apparent good fit between experimental

data and a model does not justify complete confidence in

the accuracy of the calculated diffusion time constant. A

reasonable measure of consistency between experimental

conditions and the mass transfer and optical absorbance

model assumptions was obtained by monitoring the

absorbance of the non-overlap polymer absorbance bands.

This indicated whether the required intimate contact

between the sample film and crystal was reached and

maintained. 16 refs.

USA

Accession no.784616

References and Abstracts

© Copyright 2001Rapra Technology Limited 49

Item 23Journal of Macromolecular Science B

B39, No.3, 2000, p.387-95

FTIR ANALYSIS OF NANOPARTICLES OFSYNDIOTACTIC POLYSTYRENE CONTAININGSINGLE AND/OR MULTIPLE CHAINSChen M; Fan Z; Bu H

Fudan,University

Samples of nanoparticles containing single and/or

multiple chains are prepared by precipitation from dilute

solutions of syndiotactic PS (s-PS). Vibrational spectra

of the nanoparticles are determined at room temperature

and are compared with bulk s-PS. Significant changes in

line shape and line width are observed in the spectra of

the nanoparticles. Infrared analysis of the nanoparticles

also indicates a faster crystallisation rate and higher

crystallinity than for the bulk sample. 12 refs.

CHINA

Accession no.784110

Item 24China Synthetic Rubber Industry

23, No.4, July 2000, p.219-21

Chinese

CURING KINETICS OF PU ELASTOMERS BYFTIRZaifeng L; Zhenqin X; Caifeng D; Zhaolian G; Dehe L;

Guanghua Y

Qingdao,Institute of Chemical Technology;

Beijing,University of Petroleum

The kinetics of curing reaction of PU elastomers is

analysed by in situ quantitative FTIR. The reactions,

uncatalysed and catalysed by dibutyltin dilaurate

(DBTDL), follow second-order kinetics at low

conversion. At high conversion, however, the second-

order rate constants decrease with the increase of reaction

extent, due to the influence of diffusion control. The

reaction kinetics parameters are given and the possible

reaction mechanism is further offered. DBTDL is an

effective positive catalyst for the reaction of -NCO with -

OH. 8 refs.

CHINA

Accession no.783773

Item 25Analytical Chemistry

72, No.12, 15th June 2000, p.71R-9R

INFRARED SPECTROSCOPYGillie J K; Hochlowski J; Arbuckle-Keil G A

Applied Extrusion Technologies Inc.; Abbott

Laboratories; Rutgers,University

This review on IR spectroscopy highlights three areas in

which it has become increasingly important during the

last two years. These areas are two-dimensional infrared

(2D IR) spectroscopy, combinatorial chemistry and human

health. This trend is quite evident in the abstracts

examined. The review is focused on articles published

during 1998 and 1999, but occasionally includes articles

from earlier work if they provide additional information.

148 refs.

USA

Accession no.783746

Item 26Journal of Applied Polymer Science

77, No.4, 25th July 2000, p.764-75.

IN SITU FTIR MEASUREMENT OF CARBONDIOXIDE SORPTION INTO POLY(ETHYLENETEREPHTHALATE) AT ELEVATED PRESSURESBrantley N H; Kazarian S G; Eckert C A

Georgia,Institute of Technology

Using poly(ethylene terephthalate) near-IR spectroscopy

was used to investigate the sorption rate and solubility of

carbon dioxide in the polymer at elevated pressures. The

effects of carbon dioxide processing on the crystallinity

of the poly(ethylene terephthalate) was also studied. 40

refs.

USA

Accession no.782739

Item 27Polymer

41, No.18, 2000, p.6965-8

INVESTIGATION OF GLASS FORMATION ANDPHYSICAL AGEING IN POLY(ETHYLENETEREPHTHALATE) BY FT-IR SPECTROSCOPYAtkinson J R; Biddlestone F; Hay J N

Birmingham,University

The changes in chain conformation of PETP which occur

during glass formation and physical ageing were studied

using FTIR spectroscopy. On cooling and on physical

ageing, a change from the trans to the gauche

conformations of the ethylene units in PETP was found

to occur. This was at variance with the results of a

previously reported investigation. 12 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.782252

Item 28Polymer Testing

19, No.4, 2000, p.415-7

CHARACTERIZATION OFPOLYEPICHLOROHYDRIN ANDCOPOLYMERS OF EPICHLOROHYDRIN-GYLICIDYL ETHERS BY IR SPECTROSCOPYGlavcheev I; Sirashki G; Mateva R

Sofia,University of Chemical Technology &

Metallurgy; Svistov,D.Tsenov Economic University

A study of the possibilities of using infra red spectra for

the characterisation of H-bonds formed as the result of

macromolecular interactions and the most suitable

References and Abstracts

50 © Copyright 2001 Rapra Technology Limited

absorbencies to be used for qualitative and quantitative

calculation used epichlorohydrin, phenylglycidyl ether

and butylglycidyl ether as its basis. A good agreement

between chemical structure, oxygen atom content and

calculated H-bonds was found using IR spectra. 7 refs.

BULGARIA; EASTERN EUROPE

Accession no.779577

Item 29Polymer Bulletin

44, No.3, April 2000, p.293-300

DETERMINATION OF SMALL INTERACTIONSIN POLYMER COMPOSITES BY MEANS OFFTIR AND DSCCanavate J; Pages P; Saurina J; Colom X; Carrasco F

Catalunya,Universitat Politecnica; Girona,Universidad

A series of composites of polystyrene (PS) and block

poly(styrene-butadiene) (SBS) prepared by extrusion

blending in the injection screw and injection moulding

were studied by Fourier transform infrared (FTIR)

analysis. Moulded samples were then dissolved and cast

as a film and again studied using FTIR, with higher levels

of miscibility noted than on the original moulding. SBS

content of the samples was between 20 and 80 percent,

with studies also completed on the pure polymers.

Differences observed from simulated spectra of the

polymer composites were explained by interactions

between the two polymers due to partial miscibility.

Corroboration of results was provided by calorimetry

studies. 16 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;

WESTERN EUROPE

Accession no.779461

Item 30Macromolecules

33, No.9, 2nd May 2000, p.3431-40

FOURIER TRANSFORM INFRAREDSPECTROSCOPY OFPERFLUOROCARBOXYLATE POLYMERSPerusich S A

Auburn,University

Perfluorocarboxylate polymers in the carboxylic methyl

ester, potassium salt and carboxylic acid forms were

analysed by FTIR transmission and ATR spectroscopies.

Band assignments were made for most of the dominant

peaks. An absorbance band ratio, comparing the 555/cm

C-F band to the 982/cm C-O-C ether band, was found to

be a direct measure of the equivalent weight of the

polymers. In addition, the transition from the methyl ester

form to the acid form was determined by examining the

2969/cm methyl ester band versus the broad 3200/cm band.

Quantitative expressions were presented for use in the

computation of equivalent weight and acid content based

on the FTIR thin film absorbance measurements. The

technique used provided a direct measure of the trade-off

between high anionic selectivity (high equivalent weight)

and good conductivity (low equivalent weight). 7 refs.

USA

Accession no.778456

Item 31Macromolecular Rapid Communications

21, No.7, 12th May 2000, p.354-7

IN SITU FTIR SPECTROSCOPIC STUDY OFTHE REGULARITY BANDS AND PARTIAL-ORDER MELTS OF ISOTACTICPOLY(PROPYLENE)Xinyuan Zhu; Deyue Yan; Hongxi Yao; Pingfang Zhu

Shanghai,Jiao Tong University

An experimental method was developed for the

determination of the order of the regularity bands of

isotactic polypropylene, using fast heating Fourier

transform infrared spectroscopy, which resulted in the bands

being arranged in terms of the order degree, from high to

low: 940, 1220, 1167, 1303, 1350, 841, 998, 900, 808, 1100

and 973 /cm. Partially ordered melt was formed when the

crystalline polymer melted, with the crystalline peak

shifting to lower temperatures and the exothermic enthalpy

increasing, with decreasing degree of order. 23 refs.

CHINA

Accession no.778334

Item 32Macromolecules

33, No.10, 16th May 2000, p.3518-24

REAL-TIME MID-IR MONITORING OF THEINITIATION AND PROPAGATION IN EPOXI-INITIATED LIVING ISOBUTYLENEPOLYMERIZATIONSMichel A J; Puskas J E; Brister L B

Western Ontario,University

The initiation and propagation of the polymerisation of

isobutylene (IB), initiated by 1,2-epoxy-2,4,4-

trimethylpentane (TMPO-1)/TiCl4, was monitored in-situ

using a fibre optic transmission mid-infrared probe.

Polyether formation, the isomerisation of TMPO-1 into

2,4,4-trimethylpentanal, and its complexation by TiCl4

occurred simultaneously with the initiation of the

polymerisation. It is proposed that the initiating mechanism

involves the formation of tertiary carbocations, by both

SN1 and SN2 paths. From the linearity of the first-order

plots of monomer consumption, and the near uniformity

of the polyisobutylene, it was concluded that living

polymerisation conditions prevailed. 16 refs.

CANADA

Accession no.778280

Item 33157th ACS Rubber Division Meeting - Spring 2000.

Conference preprints.

References and Abstracts

© Copyright 2001Rapra Technology Limited 51

Dallas, Tx., 4th-6th April 2000, paper XVIII

RAMAN MICRO IMAGING OF POLYMERBLENDSAppel R; Zerda T W; Waddell W H

Texas,Christian University; ExxonMobil Chemical Co.

(ACS,Rubber Div.)

Raman microimaging is used to estimate the effect of the

silica filler on phase separation in binary polymer blends

composed of BIMS and BR. The domain sizes, relative

concentration of polymer components within domains,

and distribution of particulate silica filler and zinc stearate

curative are characterised for blends of different

compositions and history of ageing treatments. The

presence of increased concentrations of precipitated silica

results in better polymer morphology since domain sizes

are reduced. Increased temperature treatment also

decreases domain sizes up to about 150 deg.C, but

treatment at 200 deg.C appears to induce separation of

the elastomer components. Silica is usually found near

the centres of the BIMS domains. There is little difference

in silica distribution before and after curing. 6 refs.

USA

Accession no.778124

Item 34Polymer News

25, No.5, May 2000, p.172-5

FT-IR DEVICE FOR ON-LINE MONITORING OFCURE REACTIONS UNDER PRESSURECarotenuto G; Del Nobile A M; Nicolais L

Italy,National Research Council; Naples,University

A special device is designed to study the effect of pressure

on the kinetic behaviour of a commercial phenolic resin

by IR spectroscopy (FTIR). Accurate and reproducible

spectra are generated, the characteristic IR peaks assigned

and the reaction kinetics evaluated by monitoring the rates

of peak disappearance. The pressure has the effect to

increase both reaction rate and maximum conversion

value. 6 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;

WESTERN EUROPE

Accession no.778119

Item 35Macromolecular Symposia

Vol.150, Feb.2000, p.121-6

EMULSION (CO)POLYMERISATION OFSTYRENE AND BUTYL ACRYLATEMONITORED BY ON-LINE RAMANSPECTROSCOPYvan den Brink M; Pepers M; van Herk A M; German A L

Eindhoven,University of Technology

On-line, in-situ Raman spectroscopy was used to monitor

the solution homopolymerisations of styrene and n-butyl

acrylate. The results obtained were then applied to the

study of the emulsion homopolymerisations of both

monomers. The data from the emulsions

homopolymerisations were then employed to calculate

monomer concentrations during the emulsion

copolymerisation of styrene and butyl acrylate. 15 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; WESTERN EUROPE

Accession no.777405

Item 36Macromolecular Symposia

Vol.143, Aug.1999, p.323-36

DIFFUSION OF ALCOHOLS AND WATER INPOLYAMIDE 11: A STUDY BY FOURIER-TRANSFORM NEAR-INFRAREDSPECTROSCOPYWu P; Siesler H W

Essen,University

The diffusion of different deuterium-labelled (OD) low

molecular weight alcohols and deuterium oxide in

polyamide 11 (PA11) was investigated by monitoring the

NH/ND exchange in the polymer by Fourier transform

near-infrared spectroscopy (FTNIR). The results

demonstrate that the diffusion process of the different

penetrants is strongly controlled by their molecular

structure and geometry. To characterise this phenomenon

quantitatively, the diffusion coefficients for the different

deuteration agents were determined for PA11.

Furthermore, it was shown that with this technique the

less ordered regions of the polymer could be separated

spectroscopically from the crystalline domains, which are

not accessible for the isotopically labelled diffusants. 27

refs. (World Polymer Congress, 37th International

Symposium on Macromolecules, Gold Coast, Australia,

12-17 July 1998)

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.770951

Item 37Macromolecules

32, No.26, 28th Dec.1999, p.8989-95

STUDYING POLY-DISPERSED LIQUID-CRYSTAL FORMATION BY FTIRSPECTROSCOPY. II. PHASE SEPARATION ANDORDERINGBhargava R; Shi-Qing Wang; Koenig J L

Case Western Reserve University

It is shown that rapid scan FTIR is a powerful tool for

monitoring physical changes (phase separation and

nematic ordering). Phase separation was observed during

the curing process by a scattering-induced change in the

absorbance spectrum of the sample. Nematic ordering

could be observed and quantified based on a change in a

characteristic band of the liquid crystal. Moreover, the

phase separation and the onset of nematic ordering were

temporarily resolved. The conversion at phase separation

decreased strongly with an increase in liquid crystal

References and Abstracts

52 © Copyright 2001 Rapra Technology Limited

content, while the conversion required for phase

separation increased with increasing temperature. The

fraction of liquid crystal present as nematic droplets and

total fraction of nematic domains in the polymer dispersed

liquid crystal were quantified from changes in the

vibrational spectrum of the liquid crystal (E7). On the

basis of mass balance applied to the closed process, the

phase diagram of the system could be determined as a

function of curing temperature. Solubility limits obtained

by this method agree well with results obtained by other

researchers. The concept of a spectroscopic composite

plot that completely describes the formation process in a

polymer dispersed liquid crystal is proposed. 36 refs. (Part

1, previous paper, this journal, p.8982-8)

USA

Accession no.766636

Item 38Macromolecules

32, No.26, 28th Dec.1999, p.8982-8

STUDYING POLYMER-DISPERSED LIQUID-CRYSTAL FORMATION BY FTIRSPECTROSCOPY. I. MONITORING CURINGREACTIONSBhargava R; Shi-Qing Wang; Koenig J L

Case Western Reserve University

Real-time FTIR was used to study the curing of a UV-

curable prepolymer (NOA65) and its mixtures with liquid

crystals. Curing reactions were examined as a function

of film thickness, temperature, and liquid crystal content.

While there was little dependence of the curing behaviour

on the thickness of the film, the effect of temperature was

strong. Curing rates exhibited a maximum around 325K,

while conversions reached a plateau about 20K higher.

Liquid-crystal addition depressed the conversion.

However, compared with the neat matrix, the final

conversion was significantly lower only for phase-

separating concentrations. The rate of reaction decreased,

and the induction period for the onset of polymerising

reactions increased, with increasing liquid-crystal

concentration. It is concluded that real-time FTIR is a

useful tool for monitoring polymer-dispersed liquid

crystal formation and optimising curing conditions.

NOA65 (from Norland Products Inc.) is a thiolene-

chemistry curable prepolymer mixture of trimethylol-

propane diallyl ether, trimethylolpropane tris(thiol),

isophorone diisocyanate ester, and a benzophenone

photoinitiator. 34 refs.

USA

Accession no.766635

Item 39Polymer

41, No.8, 2000, p.2961-70

FT-IR STUDIES OF SIDE CHAIN LIQUIDCRYSTALLINE THERMOPLASTIC ELASTOMERS

Nair B R; Gregoriou V G; Hammond P T

Massachusetts Institute of Technology

The response of a PU with liquid crystals pendant to the

soft segments to an applied strain was studied using FTIR

linear dichroism. It was found that this complex material

followed the trend established in the literature for both

side chain liquid crystalline homopolymers and

segmented PUs. At low strains, the soft segments aligned

with strain, inducing an orientation in ‘lone’ hard

segments. Up to strains of 40%, the liquid crystalline

mesogens aligned with the strain field and the hard

segments in hydrogen bonded domains aligned

perpendicular to the field. At strains above 40%, a

rearrangement of the ordering was found that resulted in

smectic layers and the hard segments aligning parallel to

the field. A model was proposed to represent these findings

and the cooperative movement of the different

macromolecular components of the PU was considered.

37 refs.

USA

Accession no.766050

Item 40Journal of Biomaterials Science: Polymer Edition

10, No.12, 1999, p.1289-302

FTIR SPECTROSCOPIC INVESTIGATION ANDMODELLING OF SOLUTE/POLYMERINTERACTIONS IN THE HYDRATED STATEAm Ende M T; Peppas N A

Purdue University

Attenuated total reflectance infrared spectroscopy is used

to investigate possible interactions during transport of

oxyprenolol.HCL bovine scrum albumin, alpha-

chymotrypsin and fibrinogen through polyacrylic acid and

its random copolymeric gels. Carbonyl and carboxylate

ion peak shifts are used to identify drug/gel binding due

to electrostatic and hydrogen bond interactions between

the polymer carrier and the drugs tested. These findings

are used to interpret the decrease in calculated diffusion

coefficients of drugs diffusing through these gels and the

associated hindering of drug transport. A model is

developed to analyse this transport process as a function

of the binding heat of the drug with the polymer. 16 refs.

USA

Accession no.765134

Item 41Journal of Polymer Science: Polymer Physics Edition

38, No.2, 15th Jan.2000, p.329-40

EPOXY-AMINE RETICULATES OBSERVED BYINFRARED SPECTROMETRY. II.MODIFICATIONS OF STRUCTURE AND OFHYDRATION ABILITIES AFTER IRRADIATIONIN A DRY ATMOSPHERENgono Y; Marechal Y

CEA/Grenoble

References and Abstracts

© Copyright 2001Rapra Technology Limited 53

Infrared spectroscopy was used to follow the ageing

processes of two epoxy resins. Resin samples were

exposed to ionising radiation and the effects at the

molecular level, and how the resins modified their

hydration mechanisms was discussed. Aromatic amine

cured resins are only slightly affected by the radiation,

but those cured by alkyl diamines are more sensitive and

thus absorb more water.molecules. 14 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.763885

Item 42Macromolecular Rapid Communications

20, No.12, Dec.1999, p.607-11

POLYELECTROLYTE COMPLEX LAYERS: APROMISING CONCEPT FOR ANTI-FOULINGCOATINGS VERIFIED BY IN-SITU ATR-FTIRSPECTROSCOPYMueller M; Rieser T; Lunkwitz K; Meier-Haack J

Dresden,Institute of Polymer Research

In-situ ATR FTIR spectroscopy was used to study the

interaction between the differently charged model proteins

human serum albumin, lysozyme, immunoglobulin G and

multilayer assemblies, which were deposited by

alternating adsorption of polyethyleneimine and

polyacrylic acid onto silicon crystals. Low adsorbed

protein amounts were observed if the top polyelectrolyte

layer and the protein were equally charged, whereas

enhanced protein adsorption occurred for electrostatic

attraction between protein and top polyelectrolyte layer.

18 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.761294

Item 43Macromolecules

32, No.24, 30th Nov.1999, p.8161-6

VIBRATION MODE INTERACTION IN THERAMAN SPECTRA OF POLY(1,6-BIS(N-CARBAZOLYL)-2,4-HEXADIYNE)Bloor D; Fehn T

Durham,University; Bayreuth,University

The Raman spectrum of the above polydiacetylene was

re-examined and analysed in terms of the resonant

interaction of backbone and side-group vibration modes.

FTIR Raman spectra were recorded for partially and fully

polymerised samples. These data complemented earlier

studies of the resonance-Raman spectra of partially

polymerised crystals conducted at low temps. The

multipeaked spectrum, which was observed in the vicinity

of the stretching vibration of the backbone carbon double

bond, was analysed using these results. A model that

incorporated the resonant interaction of the carbon double-

bond mode with three vibrational modes of the carbazolyl

side groups was shown to provide a good fit to the

available experimental data. 29 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

UK; WESTERN EUROPE

Accession no.760880

Item 44Polymer

41, No.4, 2000, p.1597-606

DISTRIBUTION OF INDIVIDUALCOMPONENTS IN THERMOPLASTICOLEFINS: STEP-SCAN FT-IRPHOTOACOUSTIC PHASE ANALYSISKiland B R; Urban M W; Ryntz R A

North Dakota State University; Visteon Automotive

Systems

Fourier transform infrared step-scan photoacoustic

spectroscopy was developed to study the composition of

thermoplastic olefin films, as a function of depth below

the surface. Infrared bands associated with talc,

polypropylene (PP), and ethylene-propylene rubber (EPR)

were used as depth-profiling probes to identify

photoacoustic signals. Experiments were done at various

modulation frequencies, enabling a stratification model

to be developed. The uppermost layer (0-3 micrometre)

showed large changes in talc and PP concentration, whilst

the layer below showed a significant decrease in both the

phases. In the third layer (6-9 micrometre), all three phases

showed the maximum values. In the fourth layer (9-12

micrometre), the talc concentration reduced, whilst

concentrations of EPR and PP were observed, decreasing

with depth. 32 refs.

USA

Accession no.760721

Item 45Applied Spectroscopy

53, No.11, Nov.1999, p.1412-8

IN-LINE NEAR-INFRARED MONITORING OFPOLYMER PROCESSING. I. PROCESS/MONITOR INTERFACE DEVELOPMENTReshadat R; Desa S; Joseph S; Mehra M; Stoev N;

Balke S T

Toronto,University

Near-infrared inline monitoring of polymer processing

means using an optical fibre-assisted spectrometer to obtain

spectra of the polymer melt flowing through commonly

used processing equipment (an extruder). Conditions in

the extruder are typically 200 deg.C and 20 MPa. The

design of interfaces between the spectrometer and the

molten polymer is shown. Three designs are shown, each

permitting monitoring at a different location in the process:

a melt-at-die interface, a melt-in-barrel interface and a

strand interface. These designs are for monitoring just

before the extruder exit, in the main barrel of the extruder

and after the product exits from the extruder as a strand,

References and Abstracts

54 © Copyright 2001 Rapra Technology Limited

respectively. All these interfaces protect the inserted optical

fibre probe from the harsh environment within the extruder

while permitting easy replacement or a probe without

interrupting the process. This latter characteristic is very

important because it permits easy probe repair as well as

the use of other types of probes (for monitoring colour or

particles, for example) to be used during a run. Examples

of near-infrared spectra obtained with each of the interfaces

used with an immiscible blend of PE and PP are shown.

Large differences in the spectra demonstrate that the design

of the interface will affect multivariate analysis directed at

composition prediction. Subsequent papers are directed at

using the melt-at-die interface for composition prediction

and accounting for nonlinear relationships between

absorbance and concentration. 6 refs.

CANADA

Accession no.760231

Item 46Applied Spectroscopy

53, No.11, Nov.1999, p.1398-402

PLASTIC DEFORMATION OF POLYETHYLENESTUDIED BY INFRARED DICHROISMElkoun S; Seguela R; Depecker C

Lille,Universite des Sciences et Technologies; URA

CNRS

IR dichroism measurements are carried out to investigate

the plastic deformation mechanisms of homogeneous and

heterogeneous ethylene copolymers issued from the

metallocene and the Ziegler-Natta catalyses, respectively.

The two copolymers having the same density display

significantly different plastic behaviour that should result

from different mechanisms of crystal slip. Such

mechanisms are analysed on the basis of the main crystal

slip systems (100)(001) and (010)(001) having the higher

shear compliances. Attention is focused on the Schmid

factor, S, of the slip planes, which is the ratio of the shear

stress acting on each slip plane to the applied tensile stress.

From the orientation functions of the three crystallographic

axes of the orthorhombic unit cell, the Schmid factor of

the two slip systems is determined as a function of plastic

strain. The heterogeneous copolymer exhibits somewhat

higher data for the (010)(001) slip, which suggests a

preferred activation of this system during the yielding stage.

In contrast, the homogeneous copolymer displays close

values for the two slip systems, indicating that plastic flow

is more likely governed by a combined activation of the

two slip systems and with eventual cross slip owing to the

common (001) slip direction. 17 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.760229

Item 47Applied Spectroscopy

53, No.11, Nov.1999, p.1313-22

TOWARDS FASTER FT-IR IMAGING BYREDUCING NOISEBhargava R; Ribar T; Koenig J L

Case Western Reserve University

Fourier transform infrared (FT-IR) imaging is a

powerful technique that can be used to obtain spatially

resolved chemical information from a large sample area

in a relatively short time. However, temporal resolution

of fast FT-IR imaging is limited by rapid of data quality

due to increased noise) with faster image acquisition.

Various coaddition schemes to reduce noise and

improve the quality of images acquired from such

systems are presented. The application of the proposed

schemes allows for improved signal-to-noise ratio

(SNR) characteristics in the resulting data. These

schemes are tested by monitoring the dissolution of a

polymer film (poly alpha-methyl styrene) by a low-

molecular-weight solvent (methyl isobutyl ketone

(MIBK)). Pseudo coaddition improves the SNR by

approximately 45%, while the SNR for sampling

coaddition is found to scale as aproximately N0.5,

where N is the number of coadded pixels. A total

acquisition time of about 100 s is achieved, allowing

the dissolution process to be monitored by using image

acquisit ions separated by 3 min. Low noise

concentration profiles, linear solvent penetration rate

and polymer dissolution rate are measured. Detection

limits of approximately 5% and quantification limits

of ~20% are achieved using optimal coaddition

strategies. This result represents an order of magnitude

improvement over untreated data. 25 refs.

USA

Accession no.760228

Item 48156th ACS Rubber Division Meeting - Fall 1999.

Conference preprints.

Orlando, Fl., 21st-23rd Sept.1999, paper 122

RAMAN STUDY OF KINETICS OFGRAPHITISATION OF CARBON BLACKSZerda T W; Gruber T

Texas,Christian University

(ACS,Rubber Div.)

Raman spectra of laser heated carbon blacks provide

information on the dynamics of graphitisation process.

Continuous wave and pulsed-laser heating is used. It

is shown that two ordering mechanisms of distinctly

different reaction rates are present during the heat

treatment. The mechanism dominating during the initial

stages of graphitisation is characterised by a very fast

rate. The rate during the later stages of the process,

after the initial first couple of seconds is orders of

magnitude slower. 8 refs.

USA

Accession no.759712

References and Abstracts

© Copyright 2001Rapra Technology Limited 55

Item 49156th ACS Rubber Division Meeting - Fall 1999.

Conference preprints.

Orlando, Fl., 21st-23rd Sept.1999, paper 160

REAL-TIME MONITORING OFPOLYMERISATION PROCESSES USING A MID-IR FIBREOPTIC PROBEPuskas J E; Michel A J; Brister L B

Western Ontario,University

(ACS,Rubber Div.)

A novel fibreoptic mid-IR probe is developed for the real-

time monitoring of polymerisation processes. The probe

is equipped with two interchangeable heads: one is an

attenuated total reflectance (ATR) head and the other one

is a transmission (TR) head. The TR head can monitor

very low concentrations (0.1 mmol/L). The ATR probe is

used to monitor both homogeneous and heterogeneous

isobutylene (IB) polymerisations by the disappearance

of the C=C double bond stretch at 1655 cm -1 and of the

C-H stretch in the CH3- group at 1375 cm -1. Polymer

formation is monitored by the appearance of the following

signals characteristic of polyisobutylene (PIB): the 1230

cm -1 band identified as the vibrations of the distorted

carbon tetrahedrons (-C(CH3)2- groups); the 1364/1391

cm -1 asymmetrical doublet representing the C-H bending

of the t-butyl groups; and the 1470 cm-1 methylene

‘scissoring’ vibration. The TR probe is used to monitor

the initiation step in a living IB polymerisation initiated

by 2-(2,2-dimethyl-propyl)-2-methyl-oxirane (TMPO-1)/

TiCl4. The appearance of bands characteristic of aldehyde/

ketone isomerisation products and polyethers at 1635,

1665 and 1100 cm-1, respectively, is observed in real-

time. The disappearance of the C-O-C stretching at 1260

cm-1 can only be monitored in the absence of IB because

of overlapping with the 1230 cm-1 band. Due to the

sensitivity of the TR probe the 1655 cm-1 band is saturated

at the beginning of the polymerisation, so IB consumption

is followed by monitoring the 2nd overtone of the =CH2

bending at 1780 cm-1. The results demonstrate the

versatility and powerfulness of this new method. 8 refs.

CANADA

Accession no.759419

Item 50Polymer Degradation and Stability

67, No.1, 2000, p.149-58

FTIR STUDY OF THE EFFECT OFHYDROLYTIC DEGRADATION ON THESTRUCTURE OF THIN PETP FILMSSammon C; Yarwood J; Everall N

Sheffield,Hallam University; ICI Research &

Technology Centre

Thin films (about 100 nanometres) were prepared by spin

casting. They were treated with pure water or 1%

potassium hydroxide at 90C for up to 8 days. Changes in

chemistry and morphology were followed using FTIR and

Reflection Absorption Infrared Spectroscopy. Dramatic

changes in the intensity of the characteristic carbon-

hydrogen band were noted as a function of degradation

of the samples degraded by both the water and the alkali.

This was interpreted as resulting from a change in the

environment of the aliphatic methyl groups and

subsequent extensive hydrogen bonding, due to an

increase in the numbers of hydrophilic end groups.

Differences in bands assigned to carbonyl groups and

hydroxyl groups suggested formation of different

hydrogen bonded species in the two systems. The

autocatalytic nature of the hydrolysis in pure water was

confirmed and evidence for the so-called

‘chemicrystallisation effect’, with crystallinity increasing

with degradation, was observed. The thin nature of the

films allowed a spectroscopic insight into the morphology

of the degrading films as a function of treatment time. 26

refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.758436

Item 51Polymer International

48, No.11, Nov.1999, p.1108-12

IRREVERSIBILITY OF STRETCHING-INDUCED LOCAL CONFORMATIONALCHANGES AS VERIFIED THROUGH AN FTIRDICHROISM STUDY FOR PVCGuarrotxena N; Millan J-L

Madrid,Instituto de Ciencia y Tec.de Polim.

Polyvinyl chloride (PVC) films were stretched to various

elongation ratios and the dichroic behaviour of 615 and

637 /cm bands of the infrared spectrum was investigated.

The evolution of the dichroic ratios and of the relative

absorbance of the bands in the direction perpendicular to

that of stretching were compared so that the occurrence of

local chain orientation related to the conformational change

GTTG-TT to GTGTTT at mmr isotactic tetrads could be

differentiating from the normal orientation of syndiotactic

sequences, to confirm that this conformational change

occurs when stretching PVC. 19 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;

WESTERN EUROPE

Accession no.757990

Item 52Journal of Polymer Science: Polymer Physics Edition

37, No.17, 1st Sept.1999, p.2353-9

FAST FTIR IMAGING: A NEW TOOL FOR THESTUDY OF SEMICRYSTALLINE POLYMERMORPHOLOGYSnively C M; Koenig J L

Case Western Reserve University

Fast FTIR imaging was used to study the distribution

of chemical species and the degree of orientation in

semi-crystalline systems. The systems investigated

were pure poly(ethylene glycol) (PEG) and blends of

References and Abstracts

56 © Copyright 2001 Rapra Technology Limited

PEG with PEO, PMMA or PVAC. The technique was

shown to be useful for determining the distribution of

species with different molecular weights and for

determining the degree of segregation of the different

blend components. Using an IR polariser, the degree

of orientation was determined in the systems by

generating spatially-resolved dichroic ratio images.

20 refs.

USA

Accession no.757179

Item 53Journal of Polymer Science: Polymer Physics Edition

37, No.16, 15th Aug.1999, p.2261-8

STUDYING ANOMALOUS DIFFUSION IN ALIQUID CRYSTAL/POLYMER SYSTEM USINGFAST FTIR IMAGINGSnively C M; Koenig J L

Case Western Reserve University

Fast FTIR imaging showed that the diffusion of liquid

crystal 4-n-pentyl-4'-cyanobiphenyl into a poly(butyl

methacrylate) matrix exhibited anomalous diffusion

behaviour. A fit to several models was attempted, but

no single model described the observed diffusion

behaviour adequately. A simple mass uptake analysis

would have indicated that diffusion occurred according

to Fick’s second law, whereas fast FTIR correctly

identified the process as anomalous. 20 refs.

USA

Accession no.757170

Item 54Macromolecules

32, No.20, 5th Oct.1999, p.6807-12

IN SITU SPECTROELECTROCHEMICALRAMAN STUDIES OF POLY(3,4-ETHYLENEDIOXYTHIOPHENE) (PEDT)Garreau S; Louarn G; Buisson J P; Froyer G; Lefrant S

Nantes,Institut des Materiaux

The results are reported of a spectroelectrochemical

study of the oxidative doping of PEDT carried out using

UV-vis-NIR optical absorption spectroscopy and

resonance Raman scattering spectroscopy with two

excitation lines, namely green (514 nm) and infrared

(1064 nm). Changes in the Raman spectra during

doping are interpreted in terms of modification of

electronic distribution along the chain. Results of

vibrational calculations, determined using a

symmetrised dynamical matrix model, are compared

with experimental data and a coherent set of force

constants related to the assignment of the Raman bands

and estimation of the polymer chain modification

during doping is proposed. 17 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.756395

Item 55Macromolecules

32, No.21, 19th Oct.1999, p.7147-55

STATIC AND DYNAMIC FT-IR LINEARDICHROISM STUDIES OF PLASTICIZATIONEFFECTS IN A POLYURETHANE ELASTOMERGraff D K; Haochuan Wang; Palmer R A;

Schoonover J R

Los Alamos National Laboratory; Duke,University

The physical role of plasticisation was assessed by

combining FTIR data for plasticised Estane 5703 (a

polyester-urethane from B.F.Goodrich) subjected to

mechanical deformation with spectral differences as a

function of added plasticiser. The orientation functions

and dichroic difference data for Estane showed that, in

static stretching, the soft domains reached orientation

saturation before the hard domains. With added plasticiser,

hydrogen bonding to the hard segments was disrupted

and the Tg of the soft domain decreased, indicating that

plasticiser remained solubilised in the soft domain. On

the time scale of the static experiment, plasticisation

diminished the ability of both domains to reorient, while

the plasticiser itself did not orient. With added plasticiser,

neither domain reached orientation saturation during the

pre-stretching process and dynamic distortion resulted in

a similar response from both domains. Bimodal bands in

the dynamic data indicated that the strain applied on a

rapid time scale (20 Hz) allowed resolution of the

components of differently oriented bands. 34 refs.

GOODRICH B.F.USA

Accession no.756264

Item 56Macromolecules

32, No.19, 21st Sept.1999, p.6319-25

STRUCTURAL AND CONFORMATIONALCHARACTERIZATION OF POLY(ETHYLENE2,6-NAPHTHALATE) BY INFRAREDSPECTROSCOPYVasanthan N; Salem D R

TRI/Princeton

X-ray diffraction analysis showed that poly(ethylene 2,6-

naphthalate) (PEN) film, annealed from 160 to 260 C

crystallised in the alpha-crystal form, whilst crystallisation

directly from the melt yielded the beta-crystal form when

the crystallisation temperature (Tc) was greater than 200

C, and in the alpha form at lower Tc. Infrared spectra

from PEN samples containing alpha, beta, and amorphous

phases were determined, and the amorphous contribution

digitally subtracted to yield characteristic spectra of the

amorphous, alpha, and beta phases. It is proposed that

the alpha crystal form adopts an all-trans conformation,

whilst the beta crystal form adopts a conformation with

appreciable gauche character. Conformational changes in

PEN occurred due to the rotation of the naphthalene ring

as well as rotation of the ethylene glycol units. The

References and Abstracts

© Copyright 2001Rapra Technology Limited 57

normalised absorbances of the bands at 824 and 814 /cm

were correlated to polymer density, and could be used to

represent the amorphous and alpha crystalline phases,

respectively. Using drawn PEN film, the assignment of

the amorphous 1338 /cm band to the trans conformation

was studied. 32 refs.

USA

Accession no.756087

Item 57Macromolecules

32, No.19, 21st Sept.1999, p.6307-18

TWO-DIMENSIONAL FOURIER TRANSFORMRAMAN CORRELATION SPECTROSCOPYSTUDIES OF POLYMER BLENDS:CONFORMATIONAL CHANGES AND SPECIFICINTERACTIONS IN BLENDS OF ATACTICPOLYSTYRENE AND POLY(2,6-DIMETHYL-1,4-PHENYLENE ETHER)Ren Y; Murakami T; Nishioka T; Nakashima K; Noda I;

Ozaki Y

Kwansei-Gakuin,University; Idemitsu Petrochemical

Co.Ltd.; Saga,University; Procter & Gamble Co.

Fourier transform Raman spectra were determined for

atactic polystyrene (PS), poly(2,6-dimethyl-1,4-

phenylene ether) (PPE) and their blends, composition-

dependent spectral variations of the blends being analysed

using generalised two-dimensional correlation

spectroscopy to study the conformational changes and

blend-interactions. The two-dimensional synchronous

correlation analysis was able to discriminate between the

bands of PS and those of PPE, and was able to detect

bands which were not readily identifiable in one-

dimensional spectra. The main chain conformation of PS

underwent a drastic change on blending with PPE.

Abnormal behaviour of bands at 1448 and 1329 /cm was

attributed to backbone methylene vibrations, and of the

band at 1070 /cm to C-C stretching vibration. Numerous

out-of-phase band variations were observed. It was

concluded that not only the phenyl ring of PS and PPE,

but also the CH3 groups of PPE played an important role

in the formation of the blends. 41 refs.

JAPAN; USA

Accession no.756086

Item 58Journal of Applied Polymer Science

74, No.11, 9th Dec.1999, p.2703-15

KINETIC STUDY OF PHENOLIC RESIN CUREBY IR SPECTROSCOPYCarotenuto G; Nicolais L

Naples,University

Fourier transform infra red spectroscopy was used to study

the cure reaction and reaction kinetics of a commercial

phenolic resin, using IR spectra in the absorbance mode.

It was found that below 140 deg. centigrade that the

kinetics of the reaction followed the Jander kinetic model

and that a diffusive mechanism was in control. Above

140 deg.C a homogenous first order reaction model best

described the reaction, as indicated by analysis using

integral methods on the isothermal data. Other models

tested, including diffusion controlled reactions, nucleation

and growth kinetics and phase boundary movement did

not fit the observed data as well as the first order

homogenous model. A proposal for a mechanistic model

for the resol cure at temperatures greater than 140 deg.C

is made. 34 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;

WESTERN EUROPE

Accession no.756012

Item 59Polyurethanes Expo ’99. Conference proceedings.

Orlando, Fl., 12th-15th Sept.1999, p.303-11

FIBRE OPTIC FTIR: A NOVEL PUR/PIRCATALYST DEVELOPMENT TOOLMcDaniel P L; Johnson G L; Kniss J G; Sabram K A

Air Products & Chemicals Inc.

(American Plastics Council,Alliance for the

Polyurethanes Industry)

Development of new catalysts promoting different

phases of PU foam formation (blowing, gelling,

crosslinking) is typically done using a series of physical

and handmix generated reactivity profile properties.

The ability to understand the evolution of chemical

species associated with rigid PU/polyisocyanurate

(PUR/PIR) foam formation has been historically only

inferred based on their final distribution in the fully

cured foam using FTIR or solid state carbon-13 NMR.

Neither technique gives insight into the reactions as

they occur. Recently, the use of IR transmitting optical

fibres as evanescent wave sensors and a mathematical

deconvolution technique (iterative target

transformation factor analysis) to extract and follow

the isocyanate, urea, urethane and trimer concentrations

as they occur in both lab scale and machine scale foam

production have been refined. The fibre optic probe

used can be placed at specific locations within the

growing foam to target the evolution of isocyanate

chemistries at the surface or core of the foam. The

specificity of the technique, speed of data acquisition

and portability of equipment all make this method ideal

as a tool to fundamentally probe how catalysts alter

the distribution of individual chemical species during

the initial moments in foam formation. Its utility in

understanding the mechanism whereby a novel new

catalyst, Polycat 48, improves dimensional stability in

a HCFC-141b blown appliance formulation, is

demonstrated. The fibre optic FTIR results for Polycat

48 are contrasted to a control catalyst blend of Polycat

5 and Polycat 41 in the same formulation. 10 refs.

USA

Accession no.755697

References and Abstracts

58 © Copyright 2001 Rapra Technology Limited

Item 60Journal of Polymer Science: Polymer Physics Edition

37, No.19, 15th Sept. 1999, p.2642-50

IR SPECTRA STUDIES OF CORE-SHELL TYPEWATERBOURNE POLYACRYLATE-POLYURETHANE MICROEMULSIONSDong A; Wan T; Feng S; Sun D

Edited by: Tianjin,University

FTIR spectroscopy was used to study hydrogen bonding

in films of polyurethane and core shell type polyacrylate-

polyurethane microemulsions. The effects of hydrogen

bonding on composition, core shell ratio and its

relationship to crosslinked structures (Type A and B) was

revealed. Shifts of the -NH and C=O stretching bands to

higher frequencies and the -NH bending bands to lower

frequencies, with increase in acetone C=O number in the

core reveals that the hydrogen bonds are broken between

the soft and hard segments and those in the short range

order in the hard segment phase. 24 Refs.

CHINA

Accession no.755231

Item 61Journal of Polymer Science: Polymer Chemistry

Edition

37, No.16, 15th Aug.1999, p.3317-27

MICRO-RAMAN INVESTIGATIONS OF PVDF-BASED PROTON-CONDUCTING MEMBRANESMattsson B; Ericson H; Torell L M; Sundholm F

Chalmers University of Technology

Proton-conducting membranes were prepared by grafting

poly(vinylidene fluoride) (PVDF) with styrene followed

by sulphonation. The depth and surface distribution of

the polystyrene grafts and crosslinker, and the

sulphonation efficiency were studied using confocal

Raman microspectroscopy. Highly grafted samples had a

homogeneous distribution of grafts and homogeneous

sulphonation, whereas uneven graft distributions were

observed in samples with low and intermediate degrees

of grafting. The crosslinker concentration in the interior

of the film was approximately 50% of the surface

concentration. Sulphonation efficiencies were poor at low

graft levels, and were further inhibited by the presence of

divinyl benzene crosslinker. At degrees of grafting in

excess of 60%, the sulphonation efficiency was not

affected by the crosslinker. The matrix polymer structure

was largely retained after irradiation, grafting, and

sulphonation. 32 refs.

SCANDINAVIA; SWEDEN; WESTERN EUROPE

Accession no.753415

Item 62Progress in Organic Coatings

35, No.1-4, Aug.1999, p.197-204

DEPTH PROFILING OF UV CURED COATINGSCONTAINING PHOTOSTABILIZERS BY

CONFOCAL RAMAN MICROSCOPYSchrof W; Beck E; Koniger R; Reich W; Schwalm R

BASF AG

Confocal Raman microscopy combines chemical

information from vibrational spectroscopy with the spatial

resolution of confocal microscopy. Examples of its use are

given, including: the investigation of variation of

crosslinking with depth in thicknesses of up to 0.5 mm in

UV-cured coatings; variations of curing with depth in

pigment formulations, in thicknesses of up to 30

micrometre; and studies of the effect of UV light stabilisers

on the UV curing of coating formulations. 11 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.752449

Item 63Journal of Applied Polymer Science

74,No.3, 17th Oct.1999, p.532-40

TETRAFUNCTIONAL EPOXYRESINS:MODELING THE CURING KINETICSBASED ON FTIR SPECTROSCOPY DATAMusto P; Martuscelli E; Ragosta G; Russo P; Villano P

Italy,National Research Council

The curing kinetics of two thermosetting systems based

on a tetrafunctional epoxy resin are investigated by

Fourier transform infrared spectroscopy. Two

formulations are studied, in which the hardener is anaromatic diamine and a carboxylic dianhydride,

respectively. The quantitative evaluation of the epoxy

conversion is based on spectra collected in the near-

infrared range (8000-4000 cm -1) as well as in the medium

IR range (4000-400 cm -1). The kinetic parameters

evaluated in the above frequency intervals are

significantly different. The reasons for such a discrepancy

are critically discussed. Several kinetic models, based on

the widely employed Kamal approach, are applied to

verify their predictive capability. Satisfactory results are

obtained for the amine-cured system, particularly with a

modified equation taking into account the autocatalytic

nature of the process as well as a limiting diffusional

effect. Less accurate results are achieved for the

anhydride-cured system. 23 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;

WESTERN EUROPE

Accession no.752308

Item 64Journal of Applied Polymer Science

74,No.3, 17th Oct.1999, p.516-22

REACTIVITY RATIOS OF N-CYCLOHEXYLMALEIMIDE ANDMETHYLMETHACRYLATE BY INFRAREDSPECTROSCOPYDong S; Wei Y; Zhang Z

Harbin,Institute of Technology

References and Abstracts

© Copyright 2001Rapra Technology Limited 59

The copolymerisation of N-cyclohexylmaleimide

(CHMI) and methyl methacrylate (MMA) with

azobisisobutyronitrile as the initiator is investigated.

IR spectroscopy is applied to determine the copolymer

compositions of the copolymers synthesised at 60, 70,

80 and 90 deg.C while the conversions of the

copolymerisations are controlled to be below 10%.

According to the Mayo-Lewis equation, the reactivity

ratios of N-cyclohexylmaleimide and methyl

methacrylate are calculated. It is proved that N-

cyclohexylmaleimide is less reactive, and the optimum

temperature of the copolymerisation is 80 deg C. 8 refs.

CHINA

Accession no.752306

Item 65Macromolecules

32, No.17, 24th Aug.1999, p.5552-60

RAMAN SPECTROSCOPICCHARACTERISATION OF ASSOCIATION ANDTHERMOREVERSIBLE GELATION INAQUEOUS SYSTEMS OF POLY(N-ACETAMIDOACRYLAMIDE)Ostrovskii D; Jacobsson P; Nystrom B; Marstokk O;

Kopperud H B M

Chalmers University of Technology; Oslo,University;

Jotun AS

A study was made of self-association and

thermoreversible gelation in aqueous solutions of

poly(N-acetamidoacrylamide) using Raman

spectroscopy. The presence of polymer-polymer

coordination was observed even at low concentrations,

indicating polymer cluster formation. The influence of

sodium thiocyanate, as denaturant, on intermolecular

and intramolecular interactions was also examined and

the effects of polymer concentration, level of

denaturant addition and type of solvent, on gel

formation evaluated. 41 refs.

NORWAY; SCANDINAVIA; SWEDEN; WESTERN EUROPE

Accession no.752236

Item 66Macromolecular Symposia

Vol.141, 1999, p.103-16

RAMAN SPECTROSCOPY FOR POLYMERCHARACTERISATION IN AN INDUSTRIALENVIRONMENTEverall N; King B

ICI Wilton Research Centre

The versatility of Raman spectroscopy for the on-line

analysis of polymers both in the laboratory and also in-

situ on the production line is demonstrated and the benefits

and disadvantages of the technique as an on-line method

are considered. Application of the technique to an analysis

of acrylic terpolymers, monitoring of polymerisation and

on-line measurement of morphology/composition is

considered and difficult on-line sampling situations are

briefly discussed. 14 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.752092

Item 67Computational and Theoretical Polymer Science

9, No.3/4, 1999, p.327-33

CONFORMATIONAL DEPENDENCE OFRAMAN FREQUENCIES AND INTENSITIES INALKANES AND POLYETHYLENEKoglin E; Meier R J

Julich,Institute of Applied Physical Chemistry; DSM

Research

Raman vibrational frequencies and intensities of octane,

dodecane and hexadecane conformers were calculated

using quantum mechanical ab initio methods. The results

agreed with various trends observed in the experimental

spectra of alkanes, as well as several observations from

the experimental Raman spectra of PEs. The data obtained

indicated that ab initio calculated Raman data on alkanes

provided valuable information regarding the interpretation

of polymer Raman spectra, in particular information

concerning issues where interpretation based on

experimental verification was not possible. 23 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

NETHERLANDS; WESTERN EUROPE

Accession no.750357

Item 68Antec ’99. Volume II. Conference proceedings.

New York City, 2nd-6th May 1999, p.2502-6. 012

MEASURING THE DIFFUSIVITY OFADDITIVES IN POLYMER FILMS USING INSITU FTIR-ATR SPECTROSCOPYGaghardi C A.; Muire L B; Hirt D E

Clemson,University

(SPE)

In many polymer-film applications, additives migrate from

the bulk of a film to the film surfaces. For these cases, it is

more realistic to measure the additive diffusivity in a

diffusion-out mode rather than using a mass-sorption

(diffusion-in) experiment. This is particularly true for

additives that are solids at the testing temperature. This

research focuses on the evaluation of additive diffusivity

in a diffusion-out mode via in situ FTIR-ATR spectroscopy,

which has the advantage of requiring only small samples

of thin films. The technique is described, including methods

to obtain reproducible contacting pressure between a film

sample and an ATR crystal and to perform in situ

experiments at elevated temperatures. Diffusivity results

are presented for the migration of an erucamide slip agent

in LLDPE films. 11 refs.

USA

Accession no.749605

References and Abstracts

60 © Copyright 2001 Rapra Technology Limited

Item 69Antec ’99. Volume II. Conference proceedings.

New York City, 2nd-6th May 1999, p.2429-32. 012

INFRARED CHARACTERISATION OF VINYLCINNAMATE COPOLYMER BLENDS BEFOREAND AFTER UV EXPOSUREColeman M; Hu Y; Painter P C

Pennsylvania,State University

(SPE)

During the past three years or so, chain connectivity and

its effect on the free energy of mixing and phase behaviour

of (co)polymer blends has been studied. IR spectroscopy

has been the primary tool because in carefully chosen

mixtures it is possible to measure the fraction of hydrogen

bonded groups present as a function of composition and

temperature. Attention is now turned to the effect of

crosslinking one or both of the (co)polymers in the blend

and the results of recent FTIR spectroscopic studies are

presented.

USA

Accession no.749591

Item 70Antec ’99. Volume II. Conference proceedings.

New York City, 2nd-6th May 1999, p.2424-8. 012

MOLECULAR ANALYSIS OF POLYMERS BYFTIR PHOTOACOUSTIC SPECTROSCOPYMcClelland J F; Jones R; Bajic S

MTEC Photoacoustics Inc.; Iowa State University

(SPE)

FTIR photoacoustic spectroscopy (PAS) has advantages

relative to conventional IR techniques (transmission,

reflection and emission) because it is non-destructive,

does not involve sample preparation and can probe

samples with compositional gradients and layers. The

theory, instrumentation, methods and applications of

FTIR-PAS are discussed and results are presented on

several polymer analyses based on FTIR-PAS. 4 refs.

USA

Accession no.749590

Item 71Antec ’99. Volume II. Conference proceedings.

New York City, 2nd-6th May 1999, p.1937-41. 012

IN-LINE MONITORING OF MULTIPLEADDITIVES IN POLYETHYLENE MELT USINGFIBRE-OPTIC SPECTROSCOPYLi J; Hansen M G

Tennessee,University

(SPE)

The feasibility of simultaneous in-line monitoring of

additives Irganox 1076, Irgafos 168, Tinuvin 622,

erucamide and Armostat 310 is studied in molten LDPE.

The near IR (NIR) and UV spectroscopic systems used

for the determination of additives are described. Based

on Partial Least Square (PLS) multivariate regression

analysis, calibration models are built for predicting the

concentrations of additives. It is found that some additives

can be predicted reliably. 7 refs.

USA

Accession no.748748

Item 72Polymer Testing

18, No.7, 1999, p.551-7

DIRECT DETERMINATION OF VINYLACETATE CONTENT OF ETHYLENE-VINYLACETATE COPOLYMERS IN THICK FILMS BYINFRARED SPECTROSCOPYMeszlenyi G; Kortvelyessy G

Szeviki Organic Chemistry Research Institute

An IR spectroscopic method was developed for the

determination of vinyl acetate content in thick (about 100

micrometres) films of EVAs. The A3460/A3610 ratio was

used for the quantitative analysis, the function of this ratio

plotted against vinyl acetate content of the EVA films

being a convex hyperbola. The technique was simple and

rapid and did not require a complicated sample preparation

procedure. 11 refs.

EASTERN EUROPE; HUNGARY

Accession no.748436

Item 73Applied Spectroscopy

53, No.8, Aug.1999, p.919-26

TWO-DIMENSIONAL NEAR-INFRAREDCORRELATION SPECTROSCOPY STUDIES ONCOMPOSITION-DEPENDENT SPECTRALVARIATIONS IN ETHYLENE/VINYL ACETATECOPOLYMERS: ASSIGNMENTS OF BANDS DUETO ETHYLENE UNITS IN AMORPHOUS,DISORDERED, AND ORTHORHOMBICCRYSTALLINE PHASESYanzhi Ren; Shimoyama M; Ninomiya T; Matsukawa

K; Inoue H; Noda I; Osaki Y

Kwansei-Gakuin,University; Hyogo,Prefectural Police

Headquarters; Osaka Municipal Technical Research

Institute; Procter & Gamble Co.

Results of the above studies are presented and discussed

in relation to the potential of three powerful techniques,

i.e. two-dimensional correlation analysis, the calculation

of the second derivatives and calculation of regression

coefficients in chemometrics, in examining the rather

complex near-IR spectra. 22 refs.

JAPAN; USA

Accession no.748410

Item 74Journal of Applied Polymer Science

73, No.14, 29th Sept.1999, p.2837-47

References and Abstracts

© Copyright 2001Rapra Technology Limited 61

FTIR QUANTITATIVE CHARACTERIZATIONOF CHEMICALLY MODIFIEDPOLYPROPYLENES CONTAINING SUCCINICGRAFTED GROUPSGarcia-Martinez J M; Laguna O; Areso S; Collar E P

Instituto de Ciencia y Tecnologia de Polimeros

The grafting of succinic anhydride onto PPs was evaluated

quantitatively by FTIR spectroscopy. The relative

absorbance values obtained from the IR spectra were

correlated with grafting levels of the sample as determined

by an improved traditional hot titration method. The

results obtained appeared to be valid for either atactic or

isotactic modified PPs and suggested that a careful review

should be conducted of the use of this technique in the

quantification of polar groups grafted onto polyolefins.

37 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;

WESTERN EUROPE

Accession no.747390

Item 75Journal of Applied Polymer Science

73, No.8, 22nd Aug.1999, p1569-77

UV CURING OF SURFACE COATING SYSTEMCONSISTING OF CYCLOALIPHATICDIEPOXIDE-ENR-GLYCIDYL METHACRYLATEBY CATIONIC PHOTOINITIATORS-CHARACTERIZATION OF THE CURED FILMBY FTIR SPECTROSCOPYKumar R N; Woo C K; Abusamah A

Malaysia,Science University

Films were cast from a system consisting of a

cycloaliphatic diepoxide, epoxidised natural rubber

(ENR), glycidyl methacrylate (GMA) and a cationic

photoinitiator, triphenylsulphonium hexafluoro-

antimonate. The films were cured by UV radiation, and

characterised using Fourier transform infrared

spectroscopy. It was determined that the acrylic double

bonds, the epoxy groups of GMA, the isoprene double

bonds, the epoxy groups of ENR, and the epoxy groups

of the cycloaliphatic epoxide resin all participated in

the photoinitiated polymerisation and crosslinking

reactions resulting in an interpenetrating polymer

network. 21 refs.

MALAYSIA

Accession no.744182

Item 76Journal of Vinyl and Additive Technology

5, No.2, June 1999, p.81-6

FOURIER TRANSFORM INFRARED MICROSPECTROSCOPY MAPPING STUDIES OFWEATHERED PVC CAPSTOCK TYPEFORMULATIONS. II. OUTDOOR WEATHERINGIN PENNSYLVANIAGarcia D; Black J

Elf Atochem NA

FTIR micro spectroscopy, coupled with mapping

techniques, was shown to be an effective method for

evaluating dimensionally-dependent changes such as

those encountered in PVC weathering processes. The

method was based on the complexity and specificity of

the IR spectrum and the dimensional resolution of the

microscope. A systematic FTIR study was conducted of

changes observed during outdoor photodegradation of

PVC siding capstock formulations, as a function of

exposure time and titanium dioxide level. The results were

compared with previously-obtained accelerated QUV

data. Profiles through the thickness dimension were

analysed to identify degradation species and depth

distribution. 14 refs.

USA

Accession no.743282

Item 77Polymer Recycling

3, No.4, 1997/1998, p.287-93

QUALITATIVE AND QUANTITATIVECHARACTERISATION OF MIXED POLYMERSUSING NEAR-INFRARED-SPECTROSCOPY(NIR)Michaeli W; Plessmann K W; Andrassy B; Breyer K;

Laufens P

IKV; Aachen,University of Technology

Details are given of an experimental technique, (the PLS2

method), which has been developed to determine the

composition of mixed polymers using the NIR technique

as a tool for the quality control of recycled plastics. PP/

polystyrene blends were quantitively analysed, and the

effects of aluminium and paper contaminants were

evaluated. 9 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.742800

Item 78ACS Polymeric Materials Science &

Engineering.Volume 80.Conference proceedings.

Anaheim, Ca., Spring 1999, p.556-7

IN-SITU FTIR INVESTIGATION ON CHAINCONFORMATION CHANGE UPON HEATINGFOR PAUCI-CHAIN POLYSTYRENEMICROSPHERE MADE BY MICROEMULSIONPOLYMERIZATIONWeihua Ming; Yiqiang Zhao; Jun Zhao; Shoukuan Fu;

Jones F N

Fudan,University; Eastern Michigan,University

(ACS,Div.of Polymeric Materials Science & Engng.)

Polystyrene microspheres, produced by microemulsion

polymerisation, generally contain only one or a few

polymer chains, and may thus be termed single- or pauci-

References and Abstracts

62 © Copyright 2001 Rapra Technology Limited

chain microspheres. Changes in chain conformation on

heating were studied using in-situ Fourier transform

infrared spectroscopy. Discontinuities in the relationship

between peak height and temperature were attributed to

the glass transition and changes in the phenyl ring stretch

mode due to the formation of phenyl ring stacking. 12

refs.

CHINA; USA

Accession no.742138

Item 79Polymer Bulletin

42, No.5, May 1999, p.579-86

RHEO-OPTICAL FOURIER TRANSFORMINFRARED SPECTROSCOPY OF DIOL-MODIFIED DIGLYCIDYL ETHER OFBISPHENOL-A EPOXY RESINSScherzer T

Leipzig,Institut fuer Oberflachenmodifizierung

Diol-modified epoxy resins were prepared from bisphenol

A diglycidyl ether modified with alpha,omega-diols of

different chain lengths and at different molar ratios. the

molecular orientation of the epoxy networks was

investigated using rheooptical FTIR spectroscopy and

uniaxial deformation was carried out above and below

the glass transition temperature. The effects of diol chain

length and molar ratio on the mechanical properties and

orientation parameter were discussed. 17 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.741938

Item 80Applied Spectroscopy

53, No.6, June 1999, p.682-6

IN SITU ANALYSIS OF A HIGH TEMPERATURECURE REACTION IN REAL TIME USINGMODULATED FIBRE-OPTIC FT-RAMANSPECTROSCOPYAust J F; Cooper J B; Wise K L; Jensen B J

Old Dominion University; US,NASA,Langley

Research Center

The high temperature (330C) cure reaction of 4-phenoxy-

4'-phenylethynylbenzophenone was monitored using a

modulated fibre-optic Fourier transform-Raman

spectrometer. Spectral evidence for two different reaction

pathways (cyclisation and chain extension) is provided.

The formation of a conjugated double bond system of

varying chain lengths is indicated. 19 refs.

USA

Accession no.741261

Item 81Applied Spectroscopy

53, No.6, June 1999, p.672-81

POST-CONSUMER PLASTIC IDENTIFICATIONUSING RAMAN SPECTROSCOPYAllen V; Kalivas J H; Rodriguez R G

Idaho,State University

The suitability of Raman spectroscopy, when used with

K-nearest neighbours, library searching or cyclic subspace

regression, for computerised classification of post-

consumer plastics was evaluated. Plastics investigated

were PETP, PP, PS, PVC, HDPE AND LDPE.

Modifications were made to the original cyclic subspace

regression algorithm for modelling multiple sample

properties and the adapted algorithm employed to directly

compare the mechanisms of principal component

regression and the PLS2 form of partial least-squares. It

was found that Raman spectroscopy could be used to

identify both HDPE and LDPE. 33 refs.

USA

Accession no.741260

Item 82Applied Spectroscopy

53, No.5, May 1999, p.557-64

COMPARISON OF NEAR-INFRARED ANDRAMAN SPECTROSCOPY FOR THEDETERMINATION OF CHEMICAL ANDPHYSICAL PROPERTIES OF NAPHTHAMin-Sik Ku; Hoeil Chung

SK Corp.

Near-infrared and FTIR Raman spectroscopy were

compared and evaluated for the quantitative analysis of

naphtha using partial least-squares regression. 19 refs.

SOUTH KOREA

Accession no.740339

Item 83ACS, Polymeric Materials Science and Engineering.

Vol.76. Conference proceedings.

San Francisco, Ca., Spring 1997, p.191-2. 012

TOWARDS A BETTER UNDERSTANDING OFSEGMENTAL MOBILITY IN POLYMERSUNDER EXTERNAL PERTURBATIONS: TIME-RESOLVED FTIR-STUDIESAmeri A; Ekgasit S; Hendann C; Michel S; Wu P;

Okretic S; Pfeifer F; Zebger I; Siesler H W

Essen,University

(ACS,Div.of Polymeric Materials Science & Engng.)

The elucidation of the mechanisms and dynamics of

segmental mobility in polymers under the influence of

external perturbations can tremendously contribute to the

improvement of certain manufacturing processes or to the

optimisation of the engineering properties of technically

important polymeric materials. Application of a uniaxial

or bidirectional elongation, on the other hand, is a

common pretreatment of a polymeric material to improve

its mechanical end-use properties. Generally, time-

References and Abstracts

© Copyright 2001Rapra Technology Limited 63

resolved IR spectroscopy has proved an extremely

valuable tool to investigate the structural details of

molecular changes incurred by a polymer under the

influence of such an external perturbation. The elucidation

of the transient molecular changes during polymer

deformation is an important issue in polymer processing.

In the film forming process, an amorphous sheet is cast

from the melt onto a cooled drum, followed by sequential

forward and sideways drawing at different temperatures

and heat setting in ovens. The ability to monitor and model

such drawing and relaxation processes would benefit

greatly product quality and web efficiency. Rheo-optical

FTIR spectroscopy is one of the few techniques providing

data on the crystallisation, orientation and conformational

changes of a polymer during mechanical treatment. To

emphasise the potential of the technique, selected

examples of rheo-optical measurements on industrially

relevant thermoplastic and elastomeric polymers are

presented and interpreted in terms of their deformation,

recovery and relaxation mechanisms. Where applicable,

2D-correlation analysis is utilised to enhance the

information derived from the vibrational spectroscopic

data. 3 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.737971

Item 84Polymer

40, No.17, 1999, p.4723-31

INFRARED AND RAMAN SPECTROSCOPY OFCYCLOHEXA(P-PHENYLENE SULPHIDE) ANDTHE POLYMER OBTAINED THEREFROMZimmerman D A; Koenig J L; Ishida H

Case Western Reserve University

Cyclohexa(p-phenylene sulphide) (CHPS) was studied as

a precursor of poly(p-phenylene sulphide) (PPS). The

FTIR and Raman spectra of CHPS were found to resemble

those of amorphous PPS closely. Specific modes

indicative of the crystal structure and band shifts were

reported. A crystal structure change in CHPS which was

induced by pressure or heat was identified. Polymerisation

of CHPS was carried out and the polymerised CHPS

showed a slightly higher crystallinity than that of

commericial low molecular weight PPS with minimal

branching. 23 refs.

USA

Accession no.737357

Item 85Colloid & Polymer Science

277, No.4, April 1999, p.376-81

FOURIER TRANSFORM INFRARED STUDY OFTHE PHASE TRANSITION IN AQUEOUSSOLUTIONS OF ETHYLENE OXIDE-PROPYLENE OXIDE TRIBLOCK COPOLYMER

Guo C; Liu H Z; Chen J Y

Chinese Academy of Sciences

The phase transition between unimer and micellar phases

of polyethylene oxide-polypropylene oxide-polyethylene

oxide) (PEO-PPO-PEO) triblock copolymer Pluronic

P105 in aqueous solution is investigated as a function of

temperature using Fourier transform infrared

spectroscopy. The transition of 8 wt.% Pluronic P105 in

aqueous solution is found to occur at 25 deg.C. As the

temperature increases, PO blocks appear to be stretched

conformers with strong interchain interaction, and the

formation of a hydrophobic core in the micellar phase.

The EO chains are found to change to a more disordered

structure with low-chain packing density from the unimer

phase to the micellar phase. Both the EO and PO blocks

exhibit dehydration during the phase transition. 20 refs.

CHINA

Accession no.732300

Item 86Coloring Technology for Plastics.

New York, N.Y., Plastics Design Library, 1999, p.197-

207. 52

MEASURING STABILISERS IN PIGMENTEDPLASTICS WITH NEAR-INFRAREDSPECTROSCOPYSolera P; Nirsberger M; Castillo N

Ciba Specialty Chemicals Corp.

Edited by: Harris R M

Near-infrared (NIR) spectroscopy has become a

commonplace analytical tool in the plastics industry. NIR

techniques have made quantification of many organic

components in polymer processing easy and quick. The

work presented outlines the methodology for using NIR

to measure stabiliser levels in colour concentrates and

natural polymer formulations. Advantages and limitations

are considered as well as particle size and product form.

4 refs.

USA

Accession no.732217

Item 87Coloring Technology for Plastics.

New York, N.Y., Plastics Design Library, 1999, p.191-

5. 52

PRACTICAL ANALYSIS TECHNIQUES OFPOLYMER FILLERS BY FOURIERTRANSFORM INFRARED SPECTROSCOPY(FTIR)Coles B J; Hall C J

Hauser Inc.

Edited by: Harris R M

The identification of polymers by FTIR is often complicated

by the presence of fillers. However, for kaolin clay, FTIR

analysis should be able to identify the filler and predict its

References and Abstracts

64 © Copyright 2001 Rapra Technology Limited

concentration using a standard curve. The resulting

percentage is more reliable than a simple ash, which may

change the chemical composition of the filler. 2 refs.

USA

Accession no.732216

Item 88Macromolecules

32, No.8, 20th April 1999, p.2748-60

FTIR IMAGING STUDIES OF A NEW TWO-STEPPROCESS TO PRODUCE POLYMERDISPERSED LIQUID CRYSTALSBhargava R; Shi-Qing Wang; Koenig J L

Case Western Reserve University

A method for reducing liquid crystal solubility in

production of polymer dispersed liquid crystals(PDLCs)

was developed which involved cooling a homogeneous

liquid crystal/precursor matrix into the two-phase regime,

followed by fast matrix polymerisation. The proposed

procedure was tested by using a well-studied PDLC

system, NOA65 (a UV-curable optical adhesive) and E7

(a mixture of cyanobiphenyls). Liquid crystal remaining

dissolved in the matrix was sharply reduced by this

method. Residual solubility of the matrix material in liquid

crystal domains was also decreased. While maintaining

the same phase composition, the method also allowed

tailoring dispersion size according to needs as opposed

to the invariable correlation between droplet size,

solubility and polymerisation rate inherent in the classical

polymerisation-induced phase separation methods. This

general methodology could be usefully applied to other

systems. FTIR imaging, combined with statistical

methods, was shown to be a valuable tool for determining

phase composition in multiphase systems. 49 refs.

USA

Accession no.731938

Item 89Macromolecules

32, No.8, 20th April 1999, p.2684-9

CONFORMATIONALLY SENSITIVE INFRAREDVIBRATIONS OF THE SYNDIOTACTICPOLYSTYRENE/ETHYLBENZENE COMPLEXMoyses S; Spells S J

Sheffield,Hallam University

The 920 to 960/cm region of the IR spectrum of the delta

phase syndiotactic PS/ethylbenzene predominantly

involved bands arising from helical structures and was

studied as a function of heating temp. Curve fitting and

deconvolution showed the necessity, for annealing temps.

above 120C, of adding a third component at 940/cm to

peaks at 934 and 943/cm. The 934 and 943/cm peaks

behaved as a doublet, primarily due to the delta phase, with

the splitting increasing on annealing. The 940/cm peak was

solely due to the gamma phase helix. These assignments

provided the opportunity for using these bands for further

studies of complexation/decomplexation in such systems.

The reduction in absorbance of 934 and 943/cm peaks

occurred at a lower temp. than the rise in the 940/cm

absorbance and this was attributed to disordering of the

delta phase helices prior to reformation as gamma phase

helices. Similar measurements using deuterated

syndiotactic PS also showed helix and zigzag bands, but

without a predominantly delta phase helix peak. Solvent

peaks in the deuterated syndiotactic PS/ethylbenzene

system were used to monitor the delta to gamma phase

transition. In combination with DSC and TGA data, the

m.p. of the alpha phase was found to be depressed by 7C

for the deuterated polymer, while the delta to gamma phase

temp. was shown to be about 24C higher. 26 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.731930

Item 90Polymer Preprints. Volume 40. Number 1. March 1999.

Conference proceedings.

Boston, Ma., March 1999, p.627-8. 012

ELUCIDATION OF CRYSTALLINE STRUCTUREIN POLYETHYLENE TEREPHTHALATE BYEXTERNAL REFLECTION INFRAREDSPECTROSCOPYCole K C; Ajji A; Pellerin E

Canada,National Research Council

(ACS,Div.of Polymer Chemistry)

Despite countless studies of the microstructure of PETP

and its relationship to process conditions and properties,

the complex behaviour of this polymer is not fully

understood. While it is clear that it cannot be described in

terms of a simple two-phase (amorphous-crystalline)

model, the nature of the third or intermediate phase is not

easy to define. The morphology of the ‘strain-induced

crystalline’ material produced by drawing amorphous PETP

is different from that of material obtained by thermal

crystallisation. Furthermore, it has been shown that thermal

crystallisation involves two distinct stages. The primary

stage starts to become significant around 90 deg.C not far

above the glass transition temperature, and shows a

sigmoidal dependence on log (time). The secondary stage

becomes significant only above about 140 deg.C and shows

a linear dependence on log (time). Front-surface reflection

IR spectroscopy is used to characterise the structure of

drawn samples. This approach is particularly interesting

because it provides the complete IR spectrum, including

the highly absorbing bands that are often saturated in

transmission spectra. Significant differences between

samples with strain-induced crystallinity and one that was

thermally crystallised are observed. The study is extended

to samples thermally crystallised over a wider range of

conditions, in order to better understand the phenomena

that govern the crystallisation of PETP. 4 refs.

CANADA

Accession no.730486

References and Abstracts

© Copyright 2001Rapra Technology Limited 65

Item 91ACS Polymeric Materials Science & Engineering.

Volume 74. Conference proceedings.

New Orleans, La., Spring 1996, p.266-7. 012

CRACK ANALYSIS OF UNFILLED NATURALRUBBER USING INFRAREDMICROSPECTROSCOPYNeumeister L A; Koenig J L

Case Western Reserve University

(ACS,Div.of Polymeric Materials Science & Engng.)

The fatigue of natural and styrene-butadiene rubbers is

an enormous industrial problem, as important mechanical

properties of these materials deteriorate quickly when

stressed. Although fatigue may describe the deterioration

of certain material properties, it is generally believed that

the term also describes failure by cracking. In fact,

abrasive wear is due to the cumulative growth of cracks

by tearing under repetitive loading. Therefore, the analysis

and characterisation of cracks in NR are crucial to the

development of material with improved fracture resistant

properties. Several spectroscopic methods are available

for characterising the crack tip region of the rubber on

the molecular scale. Attenuated total reflectance or ATR-

IR has been used to characterise the structure of many

different polymers. For example, it has been used to

characterise the structure of 1,2-polybutadiene as well as

to study the reactions of polymers. Transmission has also

been well established as a viable technique for the

molecular characterisation of transparent materials

including thin films of unfilled NR. Again the spectra

can be used for quantitative and qualitative

experimentation and analysis. 7 refs.

USA

Accession no.724898

Item 92International Symposium on Orientation of Polymers:

Application to Films and Fibres. Retec proceedings.

Boucherville, Qc., 23rd-25th Sept.1998, p.573-74.

8(11)32

MOLECULAR ORIENTATION ANDRELAXATION STUDIES OF POLYMERS USINGPOLARISATION MODULATION INFRAREDSPECTROSCOPYPellerin C; Vrabie D G; Duchesne C; Bazuin C G;

Brisson J; Pezolet M; Prud’homme R E

Quebec,Universite Laval

(SPE; NRC/IMI)

The apparatus is described and details given of its use

with PETP homopolymer, PS/poly(vinyl methyl ether)

miscible blend and styrene-styrenesulphonic acid

copolymer/ethyl acrylate-4-vinylpyridine copolymer

ionomer blend with ionic interactions. Orientation and

relaxation curves were obtained for all three samples. It

is concluded that the technique is very efficient for

obtaining curves with high precision. For these three

systems, the relaxation rate increases with temperature.

For PETP, a reorientation as a function of time was

observed. This phenomenon is dependent on temperature

and draw ratio, and is probably due to the crystallisation

of the sample. For the PS/poly(vinyl methyl ether) blend,

the addition of poly(vinyl methyl ether) to the blend

increased the orientation of the PS chains during the

stretching. For the ionomer blends, the orientation of both

types of chain was higher when the ionic content

increased. 4 refs.

CANADA

Accession no.724352

Item 93Polymer

40, No.10, 1999, p.2619-24

THERMAL MICRO ATR/FT-IRSPECTROSCOPIC SYSTEM FORQUANTITATIVE STUDY OF THE MOLECULARSTRUCTURE OF POLY(N-ISOPROPYLACRYLAMIDE) IN WATERShan-Yang Lin; Ko-Shao Chen; Liang Run-Chu

Taipei,Veterans General Hospital; Tatung,Institute of

Technology

A newly developed thermal micro attenuated total

reflection (ATR)/FTIR spectroscopic system with curve

fitting program was used for the quantitative investigation

of molecular interactions in aqueous solutions of poly(N-

isopropylacrylamide) (PNIPAAM). The lower critical

solution temperature (LCST) in water of the PNIPAAM

studied was found to be about 33C by cloud point

measurement, DSC and the thermal micro ATR/FTIR

spectroscopic system. The results from the new

spectroscopic system with curve fitting program indicated

that intermolecular interactions might predominate

between PNIPAAM and water at temperatures below the

LCST but above the LCST, PNIPAAM molecules in water

were aggregated because of intramolecular interactions

within the PNIPAAM molecules and the hydrophobic

interactions in the system. 35 refs.

TAIWAN

Accession no.724062

Item 94Polymer

40, No.10, 1999, p.2569-86

MORPHOLOGICAL CHARACTERISATION OFTHE CRYSTALLINE STRUCTURE OF COLD-DRAWN HDPE USED AS A MODEL MATERIALFOR THE ENVIRONMENTAL STRESSCRACKING (ESC) PHENOMENONLagaron J M; Dixon N M; Reed W; Pator J M; Kip B J

DSM Research; BP Chemicals; Valladolid,Universidad

Micro-Raman spectroscopy was used in conjunction

with mechanical deformation to study the structural

changes which occur in the cold drawing of HDPE. The

cold drawn structure was highly orientated and a large

References and Abstracts

66 © Copyright 2001 Rapra Technology Limited

decrease in the Raman orthorhombic crystallinity was

seen. The results indicated an ill-defined orthorhombic

crystalline structure with dislocations and disrupted

crystals formed by cold drawing, possibly resulting from

molecules being pulled through the crystals. In-situ

Raman straining experiments, carried out on cold drawn

HDPE at 240K, showed that further orthorhombic

crystalline disruption occurred with strain. No disruption

was observed in fibrils created during environmental

stress crack resistance tests at 348K. Temperature was

an important parameter in the crystalline phase recovery

of the orthorhombic crystallinity and when the cold

drawn HDPE was annealed, the monoclinic phase

disappeared. 47 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; SPAIN; UK; WESTERN EUROPE

Accession no.724059

Item 95ACS Polymeric Materials Science & Engineering,

Spring Meeting 1998. Volume 78. Conference

proceedings.

Dallas, Tx., Spring 1998, p.24. 012

ANALYSIS OF A POLYURETHANEELASTOMER USING THERMAL 2D FT-IRGraff D K; Wrobleski D A; Marsh A L; Kober E M;

Smith M E; Schnoover J R

Los Alamos National Laboratory

(ACS,Div.of Polymeric Materials Science & Engng.)

PU-polyester elastomers contain hard and soft domains

which give these materials unique structural and elastic

properties and lead to their use in various applications. It

is desirable to characterise the molecular level interactions

giving rise to the two domains, and to use this information

to monitor chemical changes which take place in the

polymer as a function of exposure to agents known to

effect structural changes. IR spectroscopy has been used

to study polymeric structures, including PU elastomers,

as the vibrational absorption bands characteristic of

different functional groups are sensitive to changes in their

chemical environment. One difficulty in the application

of IR spectroscopy to complex chemical systems has been

the ambiguity of interpretation due to the limitations of

different deconvolution techniques. The development of

a 2D correlation method has provided a means by which

convoluted spectral information, such as that arising from

the two domains of estane, can be resolved as a function

of some perturbation. A thermal 2D FT-IR study of estane

is presented. 2 refs.

USA

Accession no.719142

Item 96ACS Polymeric Materials Science & Engineering,

Spring Meeting 1998. Volume 78. Conference

proceedings.

Dallas, Tx., Spring 1998, p.22-3. 012

DYNAMIC OPTO-RHEOLOGICAL STUDY OFESTANE COPOLYMERS USING STEP-SCANFTIR SPECTROSCOPYWang H; Palmer R A; Graff D K; Schoonover J R

Duke,University; Los Alamos National Laboratory

(ACS,Div.of Polymeric Materials Science & Engng.)

Urethane copolymers generally consist of linear segments

of PU and polyester (or polyether). At room temperature,

these polymers undergo a microphase separation, in which

the PU segments form hard domains while the polyester

segments form relatively soft domains that act as the

crosslinks between the hard cores. This morphology

provides such copolymers distinctive thermal and

mechanical properties which have led to an extensive

range of applications. A wide variety of techniques has

been utilised to characterise the microscopic (molecular)

structure of polymeric materials, including those of PUs

and urethane copolymers, since the knowledge of the

microscopic structure of these polymers is critical to the

understanding of their macroscopic properties. Recently,

a dynamic infrared opto-rheological method has been

developed which involves the combination of dynamic

mechanical analysis and time-resolved IR spectroscopy

to study the real time IR spectral changes in polymer films

under sinusoidal (or impulse) tensile stress of small

amplitude. Phase-locked electronics are used to record

the dynamic infrared spectral change in-phase and in-

quadrature with the applied mechanical field. The result

provides insight to the response to the external stress on

the molecular and submolecular scale. While for relatively

narrow spectral ranges this experiment is efficiently

carried out by use of a dispersive spectrometer, for

measurements over broader spectral windows, the use of

step-scan Fourier transform IR (S2FT-IR) has proved to

be more effective. Dynamic opto-rheology using S2FT-

IR spectroscopy is applied to the urethane-ester copolymer

Estane 5703. Dynamic in-phase and quadrature spectra

in the mid-IR region at two orthogonal polarisations are

collected, and dynamic dichroic spectra calculated and

interpreted. 18 refs.

USA

Accession no.719141

Item 97ACS Polymeric Materials Science & Engineering,

Spring Meeting 1998. Volume 78. Conference

proceedings.

Dallas, Tx., Spring 1998, p.20-1. 012

STEP SCAN PHOTOACOUSTIC FT-IRSPECTROSCOPY AND STRATIFICATIONPROCESSES IN THERMOPLASTIC OLEFINS(TPO)Stegge J M; Urban M W

North Dakota State University

(ACS,Div.of Polymeric Materials Science & Engng.)

The majority of methods used for analysis of complex

systems such as thermoplastic olefins (TPO) are

References and Abstracts

© Copyright 2001Rapra Technology Limited 67

destructive. The technique that offers non-destructive

features and allows probing surfaces on a molecular level

for interactions is step-scan photoacoustic FT-IR (S2 PAS

FTIR) spectroscopy. Although step-scan photoacoustic

FTIR experiments can be used to collect information from

selectable and constant depths from the sample surface,

a possible limitation arising from this experiment is the

contamination of the signal from sample areas above the

sampling depth. In order for a signal to be produced the

heat generated must travel completely through the sample

from the depth of origin to the sample surface. In an effort

to overcome this limitation it is beneficial to spread the

spectral information out over another dimension. This can

be accomplished by introducing a time dependence to the

signal detection, and monitoring the sample response to

a perturbation. While various external perturbations,

including mechanical, thermal and magnetic field

variation, have been employed or suggested to induce time

dependence into a system, internal perturbations such as

the photothermal effect have been mostly neglected or

unrecognised. Through the use of this type of perturbation

a two-dimensional correlation analysis can be used to gain

increased spectral resolution or investigate component

interaction. 12 refs.

USA

Accession no.719140

Item 98ACS Polymeric Materials Science & Engineering,

Spring Meeting 1998. Volume 78. Conference

proceedings.

Dallas, Tx., Spring 1998, p.18-9. 012

MULTI-DIMENSIONAL SURFACE ANDINTERFACIAL ANALYSIS OF POLYMERS ANDCOATINGS; ATR, STEP-SCANPHOTOACOUSTIC, FT-IR/FT-RAMANIMAGINGUrban M W

North Dakota State University

(ACS,Div.of Polymeric Materials Science & Engng.)

Vibrational spectroscopy represents two physically

different, yet complementary spectroscopic techniques:

IR and Raman spectroscopy. Although both methods have

been utilised for many years, recent advances in

electronics, computer technologies and sampling made

Fourier transform infrared (FTIR) and Raman (FT-

Raman) one of the most powerful and versatile analytical

tools. Enhanced sensitivity and surface selectivity allows

non-invasive, no-vacuum molecular level analysis of

surface and interfaces. Emphasis is placed on recent

advances in attenuated total reflectance (ATR), step-scan

photoacoustic (SS-PA), Fourier transform infrared (FT-

IR) and FT-Raman microscopies, as utilised to the analysis

of polymeric surfaces and interfaces. A combination of

these probes allows detection of molecular level changes

responsible for macroscopic changes in three dimensions

from various depths. 7 refs.

USA

Accession no.719139

Item 99Polymer

40, No.7, 1999, p.1629-36

ROLE OF AN ACTIVE ENVIRONMENT OF USEIN AN ENVIRONMENTAL STRESS CRACKRESISTANCE (ESCR) TEST IN STRETCHEDPOLYETHYLENE: A VIBRATIONALSPECTROSCOPY AND SEM STUDYLagaron J M; Pastor J M; Kip B J

DSM Research; Valladolid,Universidad

The role of an environmental stress crack resistance

(ESCR) detergent (active environment) during tensile

deformation of PE samples was studied using Raman and

IR spectroscopy. Raman spectroscopy was found not to

be suitable for detecting this environment inside the

sample, but IR spectroscopy indicated that the

environment was predominantly present within the

transition fronts of the material. A stress-induced

environment diffusion mechanism was suggested. SEM

showed differences in the deformation process between

drawing in air or in detergent. The results indicated that

the environment penetrated the sample during the necking

process and stabilised crazing. The molecular mechanisms

were discussed. 14 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; SPAIN; WESTERN EUROPE

Accession no.714041

Item 100ACS Polymeric Materials Science and Engineering.

Fall Meeting 1998. Volume 79. Conference

proceedings.

Boston, Mas., 23rd-27th Aug.1998, p.506-7. 012

INFRARED SPECTROSCOPIC STUDY OFOXIDATION IN POLYURETHANE HARDSEGMENTSSkorich S R; Benz M E

Medtronic Inc.

Previous studies have indicated that in vivo oxidation of

polyether urethanes (PEUs) has involved depletion of the

soft segment of the material . The use of an attenuated

total reflectance (ATR) objective on the infrared (FTIR)

microscope has allowed analysis of much smaller areas

on PU tubing samples removed from in vivo implantation.

By means of the micro ATR, the differences between the

IR spectra of clear vs. fissured areas of PEUs are

enhanced, and IR peaks typical of fissured areas are

observed. Similar peaks were observed on fissured areas

of a polycarbonate urethane (PCU) which shares the same

hard segment with the PEUs. It became clear that the hard

segment was involved in the fissuring process as well as

the soft segment. Hard segments in both these materials

were based on 4,4'-methylene bis diisocyanate (MDI) and

References and Abstracts

68 © Copyright 2001 Rapra Technology Limited

1,4-butanediol (BDO). Two model diethyl carbamate

(urethane) compounds are synthesised from 4,4'-

methylene dianiline and 4,4'-diaminobenzophenone. The

spectra of these materials show the same sort of spectral

differences as between the clear and fissured materials

above. These compounds closely model the hard segment

of the above materials, and differ only in the oxidation to

a carbonyl group of the central methylene group in the

molecule. This implies that the same process is occurring

in the PU hard segments, in addition to any soft segment

reactions. 6 refs.

USA

Accession no.713291

Item 101Macromolecules

31, No.25, 15th Dec.1998, p.9008-12

MOLECULAR ORIENTATION AND DYNAMICSIN FERROELECTRIC DIBLOCK COPOLYMERSMONITORED BY FTIR SPECTROSCOPYMerenga A; Shilov S V; Kremer F; Mao G; Ober Ch K;

Brehmer M

Leipzig,University; St.Petersburg,Institute of

Macromol.Compounds; Cornell University;

Wuppertal,Bergische Universitaet

In ferroelectric liquid crystalline block copolymers the

properties of ferroelectric liquid crystals are combined

with those of diblock copolymers. Hence, one observes

in these materials a microphase separation between the

amorphous polymer (PS) and the ferroelectric liquid

crystal segment (a side chain containing oxybiphenylene

nitrooxybenzoate groups). The latter group can be

switched by applying an external electric field. Time

resolved FTIR was used to study structure and dynamics

of these systems. From analysis of the dichroism of the

FTIR spectra, it was concluded that the components in

the PS microphase are oriented randomly while the liquid

crystalline groups form an ordered phase. Time-resolved

measurements of the switching of the liquid crystalline

block were performed during the application of an external

electric field. It may be shown that switching is of an

electroclinic type and that the tilt angle and the mesogenic

motion increase with temperature, especially if the PS

block is heated above Tg. The orientation of the liquid

crystalline block after heating to the isotropic phase is

completely restored due to the memory effect of the

polymer microstructure. 12 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

RUSSIA; USA; WESTERN EUROPE

Accession no.711651

Item 102European Polymer Journal

34, No.11, Nov.1998, p.1571-7

DYNAMIC INFRARED SPECTROSCOPY, ATOOL TO DETECT HYDROGEN BONDS INPOLYMERS?

Kischel M; Kisters D; Strohe G; Veeman W S

Gerhard-Mercator Universitat

Dynamic infrared linear polarised spectra of

thermoplastic polyester urethane and nylon-6 films were

recorded under a varying sinusoidal strain. Dichroic

spectra were calculated from the dynamic polarised

spectra. The large bipolar bands in the dichroic in-phase

spectra, caused by large frequency shifts of the original

monopolar absorption bands, were ascribed to hydrogen

bonds. 29 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.709540

Item 103Polymer

40, No.5, March 1999, p.1131-7

POLYMERIZATION OF HYDROXYALKYLMETHACRYLATES CHARACTERIZED BYCOMBINATION OF FT-RAMAN AND STEP-SCAN FT-I.R. PHOTOACOUSTICSPECTROSCOPYKammer S; Albimsky K; Sandner B; Wartewig S

Halle,Martin-Luther-Universitat

The free radical polymerisation of 2-hydroxyethyl

methacrylate was studied by FT-Raman spectroscopy and

that of bisphenol-A-bis(2-hydroxypropyl methacrylate)

was studied by this technique and also by FTIRphotoacoustic spectroscopy. Raman spectroscopy was

used to determine the conversion of C=C double bonds

of the monomers exactly. 18 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.707124

Item 104Polymer Degradation and Stability

62, No.2, 1998, p.395-401

OXIDATION OF RUBBERS ANALYSED BYHORIZONTAL ATR/IR SPECTROSCOPYDelor F; Barrois-Oudin N; Duteurtre X; Cardinet C;

Lemaire J; Lacoste J

Blaise Pascal,Universite; Renault; Hutchinson

The analysis of rubbers containing large amounts of

carbon black by IR spectroscopy is difficult ,

particularly studies of their chemical evolution upon

ageing. The use of a horizontal ATR accessory equipped

with a germanium crystal is described. Horizontal

ATR(Ge)/FTIR analysis of both thermal- and

photooxidations of EPDM, polychloroprene and NBR

were first validated by conventional transmission

spectroscopy in the absence of carbon black. Horizontal

ATR(Ge) was then used with fully formulated rubbers

with the aim of studying their long-term behaviour. The

effects of temp., UV exposure, carbon black or stress

as well as the oxidation profile across the materials on

References and Abstracts

© Copyright 2001Rapra Technology Limited 69

the identification of carboxylic acid/carboxylate groups

were examined. 8 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.706569

Item 105Analytical Chemistry

70, No.22, 15th Nov.1998, p.4701-8

SIMULTANEOUS MULTISPECTRAL IMAGINGIN THE VISIBLE AND NEAR-INFRAREDREGION: APPLICATIONS IN DOCUMENTAUTHENTICATION AND DETERMINATION OFCHEMICAL INHOMOGENEITY OFCOPOLYMERSTran C D; Yan Cui; Smirnov S

Marquette,University

A multispectral imaging spectrometer capable of

simultaneously recording spectral images in the visible

and near-IR was developed. In this instrument, an

acoustooptic tunable filter was used to diffract beams with

orthogonal polarisation, one of them being detected by a

silicon camera for the visible region, while the other beam

was detected in the near-IR region with a near-IR camera.

Preliminary applications of the imaging spectrometer

included measurements of the visible and near-IR

absorption spectra of ink used to print U.S. currency and

studies of EVA copolymers. The near-IR spectral images

obtained clearly indicated that the EVA copolymers

exhibited a high degree of chemical inhomogeneity. 22

refs.

USA

Accession no.704919

Item 106Polymer Analysis and Characterization. V. Applied

Polymer Symposium proceedings.

Inuyama, 1st-4th June 1992, p.251-9. 91T

CHARACTERISATION OF COATEDINTERFACES AND POLYMER BLENDS USINGFOURIER TRANSFORM INFRAREDMICROSPECTROSCOPYNishioka T; Teramae N

Idemitsu Petrochemical Co.Ltd.

(ISPAC)

Applied Polymer Symposium 52

Fourier transform infrared microspectroscopy is applied

for the characterisation of a coated interface and a polymer

blend. The coated sample investigated is prepared by

coating a urethane paint on an ethylene-ethyl acrylate

copolymer whose ethyl-ester group is partially hydrolysed

(EAA/EEA). It is demonstrated that a mixed phase is

formed along the coated interface between the paint and

the EAA/EEA. Interaction between molecules of the

urethane paint and the EAA/EEA is observed. For a

polymer blend prepared by mixing PP and polycarbonate,

the spatially specific compositional heterogeneity could

be easily identified. 18 refs.

JAPAN

Accession no.704051

Item 107Polymer Analysis and Characterization. V. Applied

Polymer Symposium proceedings.

Inuyama, 1st-4th June 1992, p.55-62. 91T

TWO-DIMENSIONAL INFRARED STUDIES OFSUBMOLECULAR LEVEL DYNAMICS OFPOLYMERSNoda I; Dowrey A E; Marcott C

Procter & Gamble Co.

(ISPAC)

Applied Polymer Symposium 52

Two-dimensional infrared (2D IR) spectroscopy is used to

elucidate the submolecular-level dynamics of an amorphous

polymer under a dynamic deformation. In 2D IR, a polymer

sample is perturbed by a small-amplitude oscillatory strain,

and the resulting dynamic fluctuation of IR signals is used

to construct a set of 2D correlation maps. These 2D maps

are especially suited for obtaining detailed information about

local dynamics of submolecular constituents of the system.

2D IR spectra of glassy atactic PS reveal that while the main-

chain backbone reorients in the direction of applied strain,

there also exist highly localised reorientational motions of

phenyl side groups occurring independently of the main-

chain realignment. This localised submolecular distortion is

not strongly observed at temperatures well above the glass-

to-rubber transition. 6 refs.

USA

Accession no.704035

Item 108Synthetic Metals

96, No.1, 15th July 1998, p.63-70

SERS SPECTRA OF POLYANILINE THIN FILMSDEPOSITED ON ROUGH AG, AU AND CU.POLYMER FILM THICKNESS ANDROUGHNESS PARAMETER DEPENDENCE OFSERS SPECTRABaibarac M; Cochet M; Lapkowski M; Mihut L;

Lefrant S; Baltog I

Rumania,National Institute of Material Physics;

Nantes,Institut des Materiaux; Silesian Technical

University

SERS spectra under 1064 nm excitation were studied for

two forms of polyaniline, one of the emeraldine base type

and the other of the emeraldine salt type to identify the

chemical effects at the polymer/metal interface that are

involved in the specific modifications of the SERS

spectra. 19 refs.

EASTERN EUROPE; EUROPEAN COMMUNITY; EUROPEAN

UNION; FRANCE; POLAND; RUMANIA; WESTERN EUROPE

Accession no.703351

References and Abstracts

70 © Copyright 2001 Rapra Technology Limited

Item 109International Composites Expo ’98. Conference

proceedings.

Nashville,Tn., 19th-21st Jan.1998, Session 21-D. 627

UTILISING FOURIER TRANSFER NEARINFRARED (FT-NIR) TO MONITOR KEYCHEMICAL CHARACTERISTICS IN THEMANUFACTURE OF THERMOSET PLASTICSLandis L P; Cameron D G

Premix Inc.; DHC Analysis Inc.

(SPI,Composites Institute)

Thermoset plastic companies manufacture a variety of

products that utilise a complex array of ingredients and

process environments. In a typical thermoset plastic,

there could be over ten ingredients including resins,

inorganic fillers, glass fibre, inhibitors, initiators, low

profile additives, flame retardants, pigments and other

special additives. To help monitor and control the

manufacture of thermoset plastics near IR methods and

protocols have been developed which are at least ten

times more precise than the wet chemical methods.

Premix has been using Fourier Transform Near Infrared

(FT-Near IR) in the quality assurance laboratory since

1995 to measure key quality characteristics of some raw

materials as well as resultant pastes. Wet chemical

techniques (e.g. Karl Fischer Titration) for certain

samples have been replaced by FT-Near IR. It is a non-

destructive method that can be applied on, at or in-line.

It allows companies to reduce the use of costly and

dangerous chemicals which are often needed in many

test methods, and realise significant savings through

improved process control, product quality and waste

reduction. 2 refs.

USA

Accession no.702072

Item 110Applied Spectroscopy

52, No.9, Sept.1998, p.1248-52

APPLICATION OF SAPPHIRE FIBERS TO AN IRFIBER-OPTIC SENSOR FOR THEINVESTIGATION OF POLYMERS ATELEVATED TEMPERATUREGoetz R; Mizaikoff B; Kellner R

Vienna,University of Technology

The determination of the composition of ethylene-

propylene copolymers at a temp. of 200C by means of an

IR fibre-optic sensor based on sapphire fibres was studied.

LDPE and PP were also investigated. Data are presented

on spectra of LDPE and PP at 200C obtained using the

sensor, CH3/CH2 ratio after curve fitting versus C2

content, ratio of absorbance at 2950 and 2852/cm versus

C2 content and calibration graph of multivariate

calibration. 31 refs.

AUSTRIA; WESTERN EUROPE

Accession no.700291

Item 111Applied Spectroscopy

52, No.9, Sept.1998, p.1141-4

NEAR-FIELD RAMAN SPECTRALMEASUREMENT OF POLYDIACETYLENENarita Y; Tadokoro T; Ikeda T; Saiki T; Mononobe S;

Ohtsu M

JASCO Corp.; Kanagawa,Academy of Science &

Technology

Two-dimensional near-field Raman spectra and

topographic images of the polydiacetylene surface were

measured simultaneously by using a near-field Raman

spectrometer. The spectra (located 100 nm apart) had

different spectral features. The peak intensity ratio of two

C:C peaks at 1520 and 1457/cm did not correlate with

the topographic image and showed differences in the

subwavelength scale. These differences could be

interpreted as spatial differences in the number of

successive bonds on the polydiacetylene surface. In

contrast, the near-field Raman intensity of the C:C bond

at 1457/cm correlated strongly with the topographic

image. This phenomenon could be interpreted as a change

in the efficiency of collecting Raman scattering light. 26

refs.

JAPAN

Accession no.700289

Item 112Journal of Applied Polymer Science

70, No.6, 7th Nov.1998, p.1221-37

PHOTOOXIDATION OF ANHYDRIDE-CUREDEPOXIES: FTIR STUDY OF THEMODIFICATIONS OF THE CHEMICALSTRUCTUREOllier-Dureault; Gosse B

Schneider Electric; CNRS-LEMD

The photooxidative degradation of anhydride-cured

epoxies was studied using transmission Fourier transform

infrared and attenuated total reflection spectroscopy. The

degradation was heterogeneous, the surface being much

more affected from the bulk. Epoxies containing

flexibilisers, which were rich in ester groups but

containing fewer phenyl groups, degraded much more

rapidly during the first hours of exposure than those

without flexibilisers. After 40 hours of irradiation, the

disappearance rate of aromatic groups was dependent only

upon their initial concentration, whilst the formation

kinetics of hydroxyl groups was determined by the

diffusion of oxygen into the material. The formation of

hydrophilic products, acids, and alcohols was confirmed

by chemical treatment, and it was concluded that their

presence and high concentration at the surface could be

responsible for the degradation of the insulating properties

of epoxies when used as electrical insulators. 20 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.700202

References and Abstracts

© Copyright 2001Rapra Technology Limited 71

Item 113Journal of Polymer Science : Polymer Chemistry

Edition

36, No.14, Oct.1998, p.2503-12

SPECTROSCOPIC INVESTIGATIONS OFPOLYACRYLONITRILE THERMALDEGRADATIONSurianarayanan M; Vijayaraghavan R; Raghavan K V

India,Central Leather Research Institute; Indian

Institute of Chemical Technology

The thermal degradation of polyacrylonitrile was

investigated using Fourier transform infrared

spectroscopy, high-resolution solid-state nuclear

magnetic resonance spectroscopy, pyrolysis gas

chromatography, and elemental analysis. Over the

temperature range 150-590C, gaseous and volatile

products were produced with simultaneous stabilisation

of the structure of the residual material. The principle

decomposition reaction was linear polymerisation of

the nitrile group, with cyclisation followed by extended

conjugation being a significant exothermic process.

There was no evidence of the formation of oxygen-

containing chromophores. 29 refs.

INDIA

Accession no.699986

Item 114Journal of Polymer Science : Polymer Physics Edition

36, No.14, Oct.1998, p.2471-82

STRUCTURAL ANALYSIS OF POLY(3-HYDROXYBUTYRATE-CO-3-HYDROXYVALERATE) FIBERS PREPARED BYDRAWING AND ANNEALING PROCESSESFuruhashi Y; Ito H; Kikutani T; Yamamoto T; Kimizu

M; Cakmak M

Tokyo,Institute of Technology; Ishikawa,Industrial

Research Institute; Akron,University

Wide-angle X-ray diffraction, density, infrared

dichroism and birefringence measurements were used

to characterise the structure of poly(3-hydroxybutyrate-

co-3-hydroxyvalerate) fibres which had been prepared

by drawing and annealing. Three crystalline structures

were present: two orthorhombic, and the third was

pseudo-hexagonal. Both negative and positive values of

birefringence were observed, being dependent upon the

drawing and annealing temperatures. The birefringence

of the amorphous phase was positive, decreasing with

an increase in the annealing temperature. It was

concluded that orthorhombic crystals with the c-axis

preferentially orientated perpendicular to the fibre axis,

and pseudo-hexagonal crystals were preferentially

formed in the drawing process, irrespective of the

temperature. 15 refs.

JAPAN; USA

Accession no.699617

Item 1155th International Conference on Polyimides - New

Trends in Polyimide Science and Technology. Retec

proceedings.

Ellenville, N.Y., 2nd-4th Nov.1994, p.25. 43C4

FTIR AND FLUORESCENCE MONITORING OFPOLYIMIDE FORMATIONWang F W; Hutton R S; Lowry R E; Wang T T

US,National Inst.of Standards & Technology; AT & T

Bell Laboratories; Rutgers,University

(SPE,Plastics Analysis Div.; SPE,Mid-Hudson Section)

FTIR and fluorescence spectroscopy are used to monitor

the imidisation of a polyamic acid made from 3,3',4,4'-

biphenyltetracarboxylic dianhydride (BPDA) and p-

phenylenediamine (PDA), and fluorescence spectroscopy

is used to monitor the imidisation of a polyamic acid made

from 2,2-bis(3,4-dicarboxyphenyl hexafluoropropane

dianhydride (6FDA) and p-phenylene diamine. A film of

the polyamic acid made from BPDA and PDA is heated

in a nitrogen atmosphere for one hour at 75 deg.C, and

the thermal treatment is repeated at each of the

temperatures from 100 to 400 deg.C in 25 deg.C

increments between successive thermal treatments. After

each treatment, the fluorescence and the excitation spectra

of the film are taken at an excitation wavelength of 460

nm and a fluorescence wavelength of 550 nm,

respectively. Extended abstract only.

USA

Accession no.698382

Item 116Polymer

39, No.26, 1998, p.6899-904

CELLULOSIC BLENDS WITHPOLY(ACRYLONITRILE):CHARACTERIZATION OF HYDROGEN BONDSUSING REGIOSELECTIVELY METHYLATEDCELLULOSE DERIVATIVESShin J-H; Kondo T

Japan,Forestry & Forest Products Res.Inst.

Fourier transform infrared (FTir) spectroscopy was used

to characterise the hydrogen bonds, in terms of hydroxyl

regiochemistry, in blends of cellulose materials with

polyacrylonitrile (PAN). Regioselectively substituted

methylcelluloses were used as the cellulose model

compounds. Wide-angle x-ray diffraction studies of cast

films containing more than 50 wt% cellulose showed them

to be highly amorphous, attributed to interaction between

the cellulose and PAN. FTir analysis showed that the

hydrogen bonds in washed films were only between the

C-6 position in the cellulose and the nitrile group of the

PAN. This was in contrast with the as-cast films, where

the residual dimethylacetamide solvent promoted

additional interaction between the two polymer

components, resulting in enhanced miscibility. 28 refs.

JAPAN

Accession no.697798

References and Abstracts

72 © Copyright 2001 Rapra Technology Limited

Item 117Polymer

39, No.26, 1998, p.6807-17

IN SITU COMPATIBILIZATION OFPOLYPROPYLENE-POLYETHYLENE BLENDS:A THERMOMECHANICAL ANDSPECTROSCOPIC STUDYTselios Ch; Bikiaris D; Maslis V; Panayiotou C

Thessaloniki,University

Polypropylene (PP) and low density polyethylene (LDPE)

were melt blended in various proportions, with

poly(propylene-g-maleic anhydride) and poly(ethylene-

co-vinyl alcohol) added in equal proportions as in situ

reactive compatibilisers. The compatibilisation reaction

was monitored by measuring the torque increase during

mixing and by Fourier transform infrared spectroscopy.

Improvements in tensile strength, elongation at break and

impact strength were observed for all compatibilised

blends, and particularly for the blends which contained

10 wt% compatibiliser. Scanning electron microscopy and

Raman spectroscopy were used to investigate the blend

morphology. 71 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GREECE;

WESTERN EUROPE

Accession no.697789

Item 118RadTech ’98. Conference proceedings.

Chicago, Il., 19th-22nd April 1998, p.363-74. 895

CHARACTERISATION OF RADIATIONCURABLE COATINGS BY CONFOCAL RAMANMICROSCOPYSchrof W; Beck E; Koniger R; Meisenburg U; Menzel

K; Reich W; Schwalm R

BASF AG

(RadTech International)

Increasing amounts of radiation curable materials are

being used in coating films for the surface refinement of

furniture, wooden floor coverings, paper etc. Confocal

Raman spectroscopy is used to examine depth or lateral

profiles of the crosslinking process (e.g. the reaction

progress) in these coatings with a resolution of

approximately 1 mu3. The potential of confocal Raman

microscopy is demonstrated for the problems of the

inhibition of the radical polymerisation reaction by

oxygen, the limited polymerisation reaction in deep layers

due to the restricted penetration of UV light (Lambert-

Beer), the reaction in pigmented coatings and the

distribution of UV stabilisers interacting with the UV

curing process. 11 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.696928

Item 119Macromolecules

31, No. 16, 11th Aug. 1998, p.5450-5

INFRARED DICHROISM AND SURFACECONFORMATIONAL DYNAMICS OFADSORBED POLY(DIMETHYLSILOXANE)Soga I; Granick S

Illinois,University

Polymer conformations at a strongly adsorbing solid surface

and their evolution with elapsed time during the adsorption

process were examined. Poly(dimethyl-siloxane) (weight

average molecular weight 118000, polydispersity index 1.16)

was allowed to adsorb onto oxidised germanium from dilute

carbon tetrachloride solutions. The mean backbone

orientation was found to change even after the mass adsorbed

had saturated. It’s conformation was determined using IR

dichroism spectroscopy in attenuated total reflection (FTIR-

ATR). The dichroic ratio of the Si-O-Si and Si-methyl stretch

vibrations showed the poly(dimethylsiloxane) backbone to

be preferentially horizontal to the surface (dichroic ratio about

0.9 at early adsorption times) and to grow increasingly

flattened with increasing adsorption time. However, as the

adsorbed amount increased with higher solution

concentrations, the average orientation was less flattened.

Chain flattening during the adsorption process was also

slower, the higher the adsorbed amount, reflecting molecular

crowding within more densely occupied layers. During

desorption into the pure solvent, the evolution of the dichroic

ratio could be described by the hypothesis of a bimodal

configurational distribution. 21 refs.

USA

Accession no.696674

Item 120Polymer Bulletin

41, No.2, Aug 1998, p.191-8

CHARACTERISATION OF PET/LLDPE BLENDSCOMPATIBILIZED WITH DEM-GRAFTED-POLYETHYLENEMarquez L; Sabino M A; Rivero I A

Simon Bolivar,Universidad

Blends of polyethylene terephthalate and linear low-

density polyethylene were compatibilised using

diethylmaleate grafted polyethylene, and characterised

using Fourier transform infra-red spectroscopy,

thermogravimetric analysis and scanning electron

microscopy. Interactions between the components in the

blends were observed, which affected the glycol

sequences of the polyester and also improved the thermal

oxidative stability of the blends. The introduction of the

compatibiliser resulted in a particle size reduction of the

dispersed phase and better adhesion between the phase

and the matrix. 15 refs.

VENEZUELA

Accession no.696610

Item 121Polymer

39, No.20, 1998, p.4735-9

References and Abstracts

© Copyright 2001Rapra Technology Limited 73

CHARACTERIZATION OFELECTROCHEMICALLY PRODUCED TWO-COMPONENT FILMS OF CONDUCTINGPOLYMERS BY RAMAN MICROSCOPYSacak M; Akbulut U; Batchelder D N

Leeds,University

Polyaniline/poly(N-vinyl carbazole), polypyrrole/poly(N-

vinyl carbazole) and polypyrrole/polyaniline films (or

reverse order of each pair in the films) were synthesised

on platinum foil electrodes by sequential electrolysis.

Confocal Raman microprobe spectroscopy was used to

characterise both the solution sides and the electrode sides

of the films. Two types of film were observed, depending

on the conditions. Either the second polymer was

incorporated into the initially coated layer or a double-

layer film with a well-defined interface was formed.

Electrolysis of pyrrole and aniline monomer mixtures

gave films rich in pyrrole when the pyrrole:aniline molar

ratios were greater than 0.12. However, polymerisation

of N-vinyl carbazole and pyrrole monomer mixtures gave

only polypyrrole over a wide range of molar ratios. 19

refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.696557

Item 122Polymer

39, No.20, 1998, p.4723-8

ATTENUATED TOTAL REFLECTANCE CELLFOR ANALYSIS OF SMALL MOLECULEDIFFUSION IN POLYMER THIN FILMS WITHFOURIER-TRANSFORM INFRAREDSPECTROSCOPYBalik C M; Simendinger W H

North Carolina,State University

A cell for characterising the diffusion of small molecules

through thin polymer films using attenuated total

reflectance (ATR) FTIR spectroscopy was described. The

cell was designed to be used with precast (commercially

extruded) polymer films, thus enabling the as-processed

transport properties of the film to be studied. The cell

was used to measure the diffusion of carbon dioxide, amyl

acetate and limonene, and simultaneous diffusion of the

individual components from a 50/50 mixture of amyl

acetate and limonene through the thin polymer films

(HDPE, LDPE and PS). Diffusion coefficients measured

with the ATR technique compared favourably with values

obtained from gravimetric measurements with the same

penetrants and polymer samples. 20 refs.

USA

Accession no.696555

Item 123Polymer

39, No.25, 1998, p.6589-96

CHARACTERISATION OF RANDOMPROPYLENE-ETHYLENE COPOLYMERFeng Y; Hay J N

Birmingham,University

The comonomer sequence in a propylene-ethylene

random copolymer was investigated using temperature

rising elution fractionation, nuclear magnetic resonance

spectroscopy, Fourier transform infra-red spectroscopy

and differential scanning calorimetry. There was a wide

range of compositional heterogeneity, the composition

comprising mainly long propylene sequences with an

occasional ethylene unit. The sequence distributions of

the fractions did not fit either Bernoulli or first order

Markovian statistics. The crystallisation kinetics and

melting behaviour were strongly influenced by the

ethylene content and the comonomer distribution. 33 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.694681

Item 124Polymer

39, No.25, 1998, p.6533-9

NEW ACRYLIC TITANIUM POLYMERS: II.SYNTHESIS AND CHARACTERIZATION OFORGANOTITANIUM POLYMERSCamail M; Humbert M; Margaillan A; Vernet J L

Toulon et du Var,Universite

The synthesis of acrylic organotitanium polymers by the

copolymerisation of acrylic organotitanium monomers

with methyl methacrylate via free-radical initiation in

organic solvents, or by esterification of the acid functions

of an acrylic polymer with titanium tetraalkoxide, was

investigated. These polymers have potential application

as a marine anti-fouling coating. With a stoichiometric

molar ratio of titanium:carboxyl, a gel was formed. The

preparation of an esterified polymer, soluble in the usual

organic solvents, required an excess of titanium

tetraalkoxide. The amount of excess required depended

upon the nature of the alkoxide, the concentration and

the nature of the polymer. 11 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.694674

Item 125European Polymer Journal

34, No.8, Aug.1998, p.1199-205

PREPARATION AND CHARACTERIZATION OFGRAFT COPOLYMERS OF POLYACRYLAMIDEAND POLYETHYLENIMINELi D; Zhu S; Pelton R H

McMaster University

The condensation grafting of polyethylenimine (PEI) onto

poly(acrylamide-co-acrylic acid) (PAM-co-AA) was

studied. Fourier transform infra-red spectroscopy was

References and Abstracts

74 © Copyright 2001 Rapra Technology Limited

used to investigate the reaction mechanism, which

proceeded by a two-step reaction, involving the

conversion of AA to acid chloride (AC) using thionyl

chloride, followed by the condensation of AC onto PAM

and with amine onto PEI to form the graft copolymer.

The condensation reaction was fast in formamide solution.

The major factors determining the degree of grafting and

the chain structure were the AA content of PAM, the

molecular weight of PEI and the ratio PEI:PAM. Proposed

structures of the graft copolymer chains are discussed.

16 refs.

CANADA

Accession no.694435

Item 126Journal of Applied Polymer Science

69, No.8, 22nd Aug. 1998, p.1669-74

FOURIER TRANSFORM INFRARED-PHOTOACOUSTIC SPECTROSCOPY OFPOLY(N-BUTYL METHACRYLATE) ADSORBEDFROM SOLUTION ON ALUMINAPekel N; Guven O

Hacettepe,University

The adsorption of poly(n-butyl methacrylate) from

cyclohexane, benzene and carbon tetrachloride onto

alumina was qualitatively and quantitatively analysed

using Fourier transform infra-red-photoacoustic

spectroscopy. The efficiency of adsorption increased

in the order cyclohexane, carbon tetrachloride,

benzene, whilst methanol and tetrahydrofuran showed

negative adsorption. Poly(n-butyl methacrylate) had a

negative temperature coefficient of adsorption. 12 refs.

TURKEY

Accession no.693610

Item 127Journal of Applied Polymer Science

69, No.11, 12th Sept.1998, p.2175-85

IR SPECTROSCOPY AS A QUANTITATIVE ANDPREDICTIVE ANALYSIS METHOD OFPHENOL-FORMALDEHYDE RESOL RESINSHolopainen T; Alvila L; Rainio J; Pakkanen T T

Joensuu,University; Dynoresin Oy

A set of resin samples was characterised by IR and carbon-

13 NMR spectroscopy. The suitability of IR spectroscopy

for the quantitative analysis of resins was evaluated by

statistical methods using the NMR reference data as

calibration. The values of interesting properties, e.g. the

amount of free phenol and the formaldehyde-to-phenol

molar ratio, of the resins being similar to the calibration

resins were predicted from the IR spectra. The predicted

results were compared with those observed by carbon-13

NMR spectroscopy. 15 refs.

FINLAND; SCANDINAVIA; WESTERN EUROPE

Accession no.692990

Item 128Macromolecular Rapid Communications

19, No.8, Aug.1998, p.413-7

DEVELOPMENT OF A SIMPLEEXPERIMENTAL METHOD TO MEASUREINTERPHASE COMPOSITION PROFILESGENERATED BY DIFFUSION IN POLYMERS.FURTHER RESULTS AND COMPARISON WITHRAMAN SPECTROSCOPYTomba P; Carella J M; Pastor J M; Fernandez M R

INTEMA; Mar del Plata,Universidad Nacional;

Valladolid,Universidad

Composition profiles generated by interdiffusion in the

concentrated regime between polyphenylene oxide-

polystyrene blend pairs were experimentally determined by

two techniques. Three-point bending moment measurements

over a convenient temperature range (dynamic mechanical

analysis (DMA)) were used to determine interphase

composition profiles. Confocal micro-Raman spectroscopy

was also used to measure local compositions along a direction

which was perpendicular to the original interface. The study

included some limiting cases to test accuracy, precision and

flexibility of the DMA method. 4 refs.

ARGENTINA; EUROPEAN COMMUNITY; EUROPEAN UNION;

SPAIN; WESTERN EUROPE

Accession no.692051

Item 129Journal of Applied Polymer Science

69, No.4, 25th July 1998, p.645-55

MAPPING PHASES OF POLY(VINYLALCOHOL) AND POLY(VINYL ACETATE)BLENDS BY FTIR MICROSPECTROSCOPY ANDOPTICAL FLUORESCENCE MICROSCOPYDibbern-Brunelli D; Atvars T D Z; Joekes I; Barbosa V C

Campinas,Universidade Estadual

Fluorescence optical microscopy (FOM) of poly(vinyl

alcohol) and poly(vinyl acetate) blends in compositions

9/1, 1/1, and 1/9 (w/w) showed that these blends present

phase separation in the solid state. Each domain of the

solid samples was identified by FOM as poly(vinyl

alcohol)-richer domains by green fluorescence of

fluorescein and poly(vinyl acetate)-richer domains by the

blue fluorescence of anthracene. The dimensions, shapes,

and distributions of these domains were dependent on the

initial composition of the polymeric mixtures in solution.

Specific interactions between both homopolymers were

studied using FTIR microspectroscopy, which allowed

the obtaining of spectra for both poly(vinyl alcohol)-richer

and poly(vinyl acetate)-richer domains. 24 refs.

BRAZIL

Accession no.689629

Item 130Antec ’98. Volume II. Conference proceedings.

Atlanta, Ga., 26th-30th April 1998, p.2085-9. 012

References and Abstracts

© Copyright 2001Rapra Technology Limited 75

IN-LINE FIBRE-OPTIC NEAR-INFRAREDSPECTROSCOPY: FEASIBILITY STUDIES FORTHE SIMULTANEOUS MONITORING OF VINYLACETATE AND ERUCAMIDE ADDITIVECONCENTRATIONS IN POLYETHYLENE-VINYL ACETATE COPOLYMERSVedula S; Hansen M G; Deshpande B J

Tennessee,University

(SPE)

Feasibility studies for the simultaneous monitoring of

vinyl acetate (VA) and erucamide additive concentrations

in EVA copolymers are undertaken using near-infrared

(NIR) spectroscopy. Two groups of samples, each group

containing different erucamide concentrations for a fixed

VA concentration, are used. NIR spectra of flowing molten

polymers are obtained in-line using a flow cell attached

to an extruder. The first derivatives of the NIR spectra in

the region 1900-2000 nm show overlapping peaks of VA

and erucamide. These peaks are deconvoluted using

multivariate analysis methods. 7 refs.

USA

Accession no.687493

Item 131Antec ’98. Volume II. Conference proceedings.

Atlanta, Ga., 26th-30th April 1998, p.2223-7. 012

NEW APPROACH TO THECHARACTERISATION OF MOLECULARORIENTATION IN UNIAXIALLY ANDBIAXIALLY STRETCHED SAMPLES OF PETPCole K C; Daly H B; Sanschagrin B; Nguyen K T;

Ajji A

Canada,National Research Council; Montreal,Ecole

Polytechnique

(SPE)

The usual approach used to characterise the molecular

orientation in biaxially oriented samples by IR

spectroscopy is used to measure spectra with

polarisation in all three directions - machine, transverse

and normal (or thickness). However, the latter

measurement is rather difficult to make experimentally.

A new approach to characterising the molecular

orientation in both uniaxially and biaxially oriented

samples of PETP is employed. It makes use of the ratio

of the absorption bands near 1250 and 1725 cm-1, the

first of which shows parallel dichroism and the second

perpendicular dichroism. An equation is developed that

relates this ratio to the molecular orientation with

respect to the direction of measurement. Thus it is

possible to determine individually the orientation

functions with respect to the machine and transverse

directions. The validity of functions determined in this

way is confirmed by comparison with birefringence

results. 9 refs.

CANADA

Accession no.687420

Item 132Antec ’98. Volume II. Conference proceedings.

Atlanta, Ga., 26th-30th April 1998, p.2215-8. 012

PRACTICAL ANALYSIS TECHNIQUES OFPOLYMER FILLERS BY FOURIERTRANSFORM INFRARED SPECTROSCOPY(FTIR)Coles B J; Hall C J

Hauser Inc.

(SPE)

The identification of polymers by FTIR is often

complicated by the presence of fillers. However for kaolin

clay, an FTIR analysis should be able to identify the filler

and predict its concentration using a standard curve. The

resulting percentage is more reliable than a simple ash,

which may change the chemical composition of the filler.

2 refs.

USA

Accession no.687418

Item 133Polymer

38, No.15, 1998, p.3327-33

FTIR STUDY OF GRAFT COPOLYMERCOMPATIBILIZERS FOR BLENDS OFFUNCTIONALIZED POLYPROPYLENE ANDLIQUID-CRYSTALLINE POLYESTERSek D; Kaczmarczyk B

Polish Academy of Sciences

FTIR spectroscopy was used to characterise mixtures of

PP functionalised with 6 wt% of acrylic acid (PPAA) and

liquid crystalline polyester (PPAA contents of 50% or

70%), graft copolymers of PPAA with the monomers from

which the polyester was derived (sebacic acid, 4,4'-

dihydroxybiphenyl and d-hydroxybenzoic acid, again

with PPAA contents of 50% or 70%) and the fractionation

products of the graft copolymers. The aim of the

investigation was to study the structure of compatibilisers

consisting of the graft copolymers and the grafting was

followed by measuring changes in the amount of

carboxylic and aliphatic-aromatic ester groups. the results

were discussed. 3 refs.

EASTERN EUROPE; POLAND

Accession no.686650

Item 134Applied Spectroscopy

52, No.5, May 1998, p.702-12

ANALYSIS AS A FUNCTION OF TEMPERATUREOF THE DYNAMIC LINEAR INFRAREDDICHROISM SPECTRA OF ISOTROPIC ANDCOLD-DRAWN HIGH-DENSITYPOLYETHYLENELagaron J M; Steeman P A M; Kip B J

DSM Research

References and Abstracts

76 © Copyright 2001 Rapra Technology Limited

A dynamic linear infrared dichroism study was carried

out as a function of temperature on isotropic and cold

drawn HDPE using a rapid-scan setup. The dynamic

in-phase dichroic spectrum and its components

(parallel and perpendicular polarised spectra) were

analysed. 15 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; WESTERN EUROPE

Accession no.685291

Item 135Applied Spectroscopy

52, No.5, May 1998, p.692-701

INVESTIGATIONS OF RADICALPOLYMERISATION AND COPOLYMERISATIONREACTIONS IN OPTICALLY LEVITATEDMICRODROPLETS BY SIMULTANEOUSRAMAN SPECTROSCOPY, MIE SCATTERING,AND RADIATION PRESSURE MEASUREMENTSMusick J; Popp J; Trunk M; Kiefer W

Wurzburg,University

The combination of optical levitation with Raman

spectroscopy, elastic (Mie scattering), and radiation

pressure measurements enables in-situ and real-time

investigation polymerisation and copolymerisation

processes in microdroplets. The time-dependent evolution

of the polymerisation and copolymerisation reactions of

styrene/unsaturated polyester resin was characterised by

observing the educt and product signals in the Raman

spectra. The size, the refractive index, and the wavelength

dependence of the optically levitated microparticle were

determined from the position of the morphology-

dependent resonances observed in Raman spectra, in

elastic light scattering, and in radiation pressure

measurements. 36 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.685290

Item 136Macromolecules

31, No.11, 2nd June 1998, p.3753-5

APPLICATION OF REAL TIME MID-INFRAREDFTIR IMAGING TO POLYMERIC SYSTEMS. I.DIFFUSION OF LIQUID CRYSTALS INTOPOLYMERSSnively C M; Koenig J L

Case Western Reserve University

The FTIR imaging method was extended to the real-time

acquisition of images from systems varying with time.

Emphasis is given to the monitoring of the diffusion of a

low molecular weight liquid crystal pentylcyanobiphenyl

into a solid polybutyl methacrylate film. 22 refs.

USA

Accession no.685003

Item 137Journal of Applied Polymer Science

69, No.3, 18th July 1998, p.461-8

APPLICATION OF ATR-FTIR SPECTROSCOPYCOMBINED WITH SPUTTER ETCHING FORDEPTH PROFILING OF A CHEMICALADDITIVE WITHIN A PULP FIBERTatsumi D; Yamauchi T

Kyoto,University

Attenuated total reflection-Fourier transform infra-red

(ATR-FTIR) spectroscopy was used to determine the

concentration of a chemical additive (cationic

polyacrylamide resin) within a pulp fibre. The depth

distribution of the additive was determined by sputter

etching the fibre surface. The obtained profile was

compared qualitatively with that obtained by the variable-

angle ATR-FTIR depth profiling method. Most of the

additive was located at the surface, with some distributed

within the fibre. It is concluded that the method can be

used to clarify the distribution of other paper additives

within a pulp fibre, and that it can be applied to depth

profiling of minor components within a solid material.

21 refs.

JAPAN

Accession no.684061

Item 138Polymer Testing ’96. Conference proceedings.

Shawbury, 5th-6th Sept.1996, paper 6. 57

IDENTIFICATION OF ADDITIVES IN RUBBERAND PLASTIC MATERIALS BY COMBINEDLIQUID CHROMATOGRAPHY/INFRAREDSPECTROSCOPYSidwell J

Rapra Technology Ltd.

(Rapra Technology Ltd.; Plastics & Rubber Weekly;

European Plastics News)

The application of the Lab Connections LC Transform

Interface for obtaining IR spectroscopic data on additive

components from polymeric systems separated by

chromatographic means is discussed. Examinations based

on molecular size separation in solution using the

techniques of gel permeation chromatography and also

normal phase and reverse phase high performance liquid

chromatography are described. 2 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.683811

Item 139153rd ACS Rubber Division Meeting - Spring 1998.

Conference preprints.

Indianapolis, In., 5th-8th May,1998. Paper 7. 012

APPLICATION OF RAMAN MICROIMAGING INCHARACTERISATION OF POLYMERSAppel R; Zerda T W

References and Abstracts

© Copyright 2001Rapra Technology Limited 77

Texas,Christian University

(ACS,Rubber Div.)

The incorporation of high-resolution optics in a Raman

spectrometer allows sampling from areas of less than one

micron in diameter. The addition of a confocal microscope

improves the axial resolution to a couple of microns.

Those developments, along with the introduction of notch

filters and holographic transmission gratings, allow the

reduction of the acquisition time of Raman spectra from

minutes to seconds. The fast data collection combined

with the high lateral and vertical resolutions makes

possible scanning experiments in which the specimen is

advanced in micron size steps. Analysis of the spectra

provides information on the spatial composition of the

sample. Phase separation in binary mixtures of two

polymers, Exxpro and Budene, is studied for different

composition of the blends. The average domain sizes are

determined. 5 refs.

USA

Accession no.683227

Item 140Polymer

39, No.16, 1998, p.3631-40

XPS AND FTIR STUDIES OF INTERACTIONS INPOLY(CARBOXYLIC ACID)/POLY(VINYLPYRIDINE) COMPLEXESXu Zhou; Goh S H; Lee S Y; Tan K L

Singapore,National University

The nature of the complexes formed by the interactions

between polyacrylic acid (PAA) and polymethacrylic acid

(PMAA) and with poly(4-vinylpyridine) and poly(2-

vinylpyridine) in ethanol/water solution was studied using

Fourier transform infra-red spectroscopy and x-ray

photoelectron spectroscopy. The PMAA complexes

involved hydrogen-bonding interactions, whilst there was

evidence of ionic interactions in the PAA complexes. This

difference in the behaviour between the complexes is

attributed to the higher acidity of PAA compared with

that of PMAA. 23 refs.

SINGAPORE

Accession no.682246

Item 141Journal of Polymer Science : Polymer Physics Edition

36, No.9, 15th July 1998, p.1529-37

DISCRIMINATION OF ETHYLENE/VINYLACETATE COPOLYMERS WITH DIFFERENTCOMPOSITION AND PREDICTION OF THECONTENT OF VINYL ACETATE IN THECOPOLYMERS AND THEIR MELTING POINTSBY NEAR-INFRARED SPECTROSCOPY ANDCHEMOMETRICSShimoyama M; Hayano S; Matsukawa K; Inoue H;

Ninomiya T; Ozaki Y

Hyogo,Prefectural Police Headquarters; Bran &

Luebbe Co.Ltd.; Osaka,Municipal Technical Research

Institute; Kwansei-Gakuin,University

Near-infrared diffuse reflectance spectra were measured

by use of a rotating drawer for pellets of 12 kinds of

ethylene-vinyl acetate copolymers with vinyl acetate

comonomer varying in the 7-44 wt% range. An attempt

was made to predict the melting points of these

copolymers. The potential of near-infrared spectroscopy

with that of Raman spectroscopy in the discrimination of

copolymers and the prediction of their properties was

given. 23 refs.

JAPAN

Accession no.681676

Item 142Journal of Applied Polymer Science

68, No.5, 2nd May 1998, p.785-92

INFRARED SPECTROSCOPIC STUDY OFSILICA FILM FORMATION ANDDECOMPOSITION OF VINYL SILANEDERIVATIVE BY HEAT TREATMENT. II. ONCOPPER SURFACEKim H; Jang J

Seoul,National University

The thermooxidative degradation and SiOx film formation

of poly(vinyl imidazole-co-vinyl trimethoxysilane) on

copper was investigated using Fourier transform infraredreflection and absorption spectroscopy. Thermal

degradation of the copolymer was catalysed by copper in

the film and at the substrate surface. Copper in the

copolymer film contributed to the formation of a copper-

containing SiOx film during thermal degradation. Heat

treatment caused defects in the copper-containing film,

and copper corrosion proceeded through these defects.

In a thickly coated sample, the film cracked because of

residual stress, resulting in the formation of copper oxides

through the crack. Copper oxides in the film interacted

with the SiOx film to form a copper-rich phase in near to

film defects and cracks. 33 refs.

SOUTH KOREA

Accession no.679543

Item 143Macromolecules

31, No. 7, 7th April 1998, p.2141-51

SELECTIVELY DEUTERATED LIQUIDCRYSTALLINE CYANOAZOBENZENE SIDE-CHAIN POLYESTERS. III. INVESTIGATIONSOF LASER-INDUCED SEGMENTAL MOBILITYBY FOURIER TRANSFORM INFRAREDSPECTROSCOPYKulinna C; Hvilsted S; Hendann C; Siesler H W;

Ramanujam P S

Riso National Laboratory; Essen,University

The laser-induced anisotropy in thin films of an extensive

number of cyanoazobenzene sidechain liquid crystalline

References and Abstracts

78 © Copyright 2001 Rapra Technology Limited

polytetradecanedioates, -dodecanedioates, and -adipates

selectively deuterated at different positions was

investigated by FTIR. The analysis of the segmental

orientation based on dichroic ratios of characteristic

absorption bands shows that, in polyesters with long main-

chain spacing (tetradecanedioates and dodecanedioates),

not only the light sensitive azo chromophore, but also the

main-chain methylene segment and to a small extent the

flexible spacer are preferentially oriented perpendicular

to the laser light polarisation. The extent of orientation

increases with increasing spacer length. On the other hand,

in the shorter adipates only the chromophore and the

spacer are likewise oriented. Rapid-scan FTIR analysis

performed on-line with the laser irradiation reveals that

the alignment of the aliphatic segments arises

simultaneously with the chromophore orientation.

Temperature dependent IR investigations of the laser-

induced orientation shows that the preservation of the

photoinduced anisotropy directly relates to the polyester

phase behaviour. Relevance to rewritable optical storage

is suggested. 41 refs.

DENMARK; EUROPEAN COMMUNITY; EUROPEAN UNION;

GERMANY; SCANDINAVIA; WESTERN EUROPE

Accession no.679222

Item 144Colour Quantification: Adding Value With Instruments.

Retec proceedings.

Baltimore, MD, 15th-17th Sept.1997, paper 11. 52

MEASURING STABILISERS IN PIGMENTEDPLASTICS WITH NEAR-INFRAREDSPECTROSCOPYSolera P; Nirsberger M; Castillo N

Ciba Specialty Chemicals Corp.

(SPE,Color & Appearance Div.)

Near-infrared (NIR) spectroscopy has become a

commonplace analytical tool in the plastics industry. NIR

techniques have made quantification of many organic

components in polymer processing easy and quick. The

work presented outlines the methodology for using NIR to

measure stabiliser levels in colour concentrates and natural

polymer formulations. Advantages and limitations are

considered as well as particle size and product form. 4 refs.

USA

Accession no.672730

Item 145Polymer Degradation and Stability

58, Nos.1-2, 1997, p.15-31

FTIR EMISSION SPECTROSCOPY APPLIED TOPOLYMER DEGRADATIONCelina M; Ottesen D K; Gillen K T; Clough R L

Sandia National Laboratories

The thermal degradation of some common polymers is

investigated using IR emission spectroscopy. The potential

of the technique to contribute to polymer degradation

studies is demonstrated by measuring the spectroscopic

changes that occur during thermal degradation, oxidation

or decomposition of polymers under air at temperatures

ranging from 150 to 25 deg.C. Polymer types studied

include EPDM and nitrile rubbers (commercial materials

containing some inorganic fillers), PMMA, PAN, PA, PVC

and PS. The resulting qualitative changes in the polymers

are easily detected, and are correlated with the current

knowledge on the degradation mechanisms of these

materials. These include simple carbonyl formation and

related oxidative reactions, weight loss and volatilisation,

as well as formation of conjugation and specific polymer

reactions. Some fundamental aspects and limitations of the

technique are discussed to demonstrate the intrinsic

difficulties of attempting to determine precise emittances

and ultimately quantitative spectroscopic information.

FTIR emission appears to be promising for studying in

situ polymer degradation. 33 refs.

USA

Accession no.668861

Item 146Polymer

39, No.3, 1998, p.573-82

FTIR. SPECTROSCOPY ON ELECTRONIRRADIATEDPOLYTETRAFLUOROETHYLENEFischer D; Lappan U; Hopfe I; Eichhorn K-J;

Lunkwitz K

Dresden,Institute of Polymer Research

The effect of radiation dose and the hydrolysis conditions

on the chemical structure of electron irradiated PTFE was

studied by different methods of FTIR spectroscopy.

Irradiation produced acid fluoride (COF) groups and

under ambient conditions, these hydrolysed with

atmospheric humidity to form free and associated

carboxylic acid (COOH) groups. The concentration of

these groups was different in the near-surface regions and

in the bulk phase. The formation of carboxylic groups in

different states of association depended on the hydrolysis

conditions. The results were discussed in detail. 9 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.665954

Item 147Applied Spectroscopy

51, No.12, Dec.1997, p.1784-90

DEPTH PROFILING STUDY OF EFFECT OFANNEALING TEMPERATURE ON POLYMER/POLYMER INTERFACES IN LAMINATESUSING CONFOCAL RAMANMICROSPECTROSCOPYHajatdoost S; Olsthoorn M; Yarwood J

Sheffield,Hallam University; Utrecht,University

The effect of annealing temperature on molecular

interactions at the interface of polymer laminates was

References and Abstracts

© Copyright 2001Rapra Technology Limited 79

reported. Depth profiling was carried out using confocal

Raman microspectroscopy to study polyacrylonitrile/

polyvinyl alcohol and polyacrylonitrile/polyacrylic acid

laminates. The laminates were annealed at 65, 75 and 90C.

It was demonstrated that the degree of hydrogen bonding

interaction between the nitrile and alcohol groups near

the interfacial region changes between laminates annealed

at different temperatures. For comparison, Raman

mapping of a polyacrylonitrile-polyvinyl alcohol blend

was used to study the interactions between the polymers

in this (disordered) system. 29 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; UK; WESTERN EUROPE

Accession no.665697

Item 148Applied Spectroscopy

51, No.11, Nov.1997, p.1736-40

GENERALISED TWO-DIMENSIONAL FOURIERTRANSFORM INFRARED PHOTOACOUSTICSPECTRAL DEPTH-PROFILING ANALYSISJiang E Y; McCarthy W J; Drapcho D L;

Crocombe R A

Bio-Rad Laboratories Inc.

A new application of generalised two-dimensional

correlation spectroscopy in photoacoustic depth-profiling

analysis. Both rapid-scan and step-scan photoacoustic

spectroscopy (obtained by using the software-based

digital signal processing technique) of multilayer samples

were used to calculate generalised two-dimensional

correlation maps. Advantages of this unambiguous

analysis method in enhancing spectral as well as depth

resolutions, over conventional two-dimensional

correlation and other spectral depth-profiling methods,

were discussed. 31 refs.

USA

Accession no.665694

Item 149Polymer Degradation and Stability

57, No.3, 1997, p.339-48

CLEARCOAT ANALYSIS IN ISOLATED ANDMULTI-LAYER PAINT SYSTEMS BYCONFOCAL RAMAN MICROSCOPYDupuie J L; Weber W H; Scholl D J; Gerlock J L

Ford Motor Co.

Confocal Raman spectroscopy was used to characterise

the chemical composition of clearcoats in three paint

systems: weathered and unweathered samples of isolated

acrylic/melamine and acrylic/urethane clearcoats,

polyester urethane clearcoats in weathered and

unweathered samples of a complete paint system on

plastic, and UV light cured acrylic clearcoats on

polycarbonate substrates. 11 refs.

USA

Accession no.664076

Item 150Journal of Applied Polymer Science

66, No.13, 26th Dec.1997, p.2465-73

MEASURING WATER DIFFUSION IN POLYMERFILMS ON THE SUBSTRATE BY INTERNALREFLECTION FOURIER TRANSFORMINFRARED SPECTROSCOPYLinossier I; Gaillard F; Romand M; Feller J F

Lyon,Universite; Sud Bretagne,Universite

A method is presented based on multiple internal

reflection-FTIR to measure the diffusion coefficients of

liquid in polymer, e.g. PMMA or PS, films applied to a

substrate. The experimental method here described was

designed primarily to measure in-situ liquid water mass

uptake and diffusion based on sorption kinetics, but it

can also be suitable for vapours, or for other liquids. 24

refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.664045

Item 151Polymer Science Series B

39, Nos.9-10, Sept.-Oct.1997, p.358-64

IR SPECTROSCOPIC STUDY OF RADICALPOLYMERISATION KINETICSKurmaz S V; Roshchupkin V P

Russian Academy of Sciences

An IR spectroscopic technique for the study of kinetics

of radical copolymerisation of acryl and vinyl monomers

was developed. The technique is based on monitoring the

conversion curves and determining copolymerisation rates

in the course of the process separately for each monomer

by measuring variations in the intensity of IR absorption

bands of reacting vinylidene groups. A comparative study

of the copolymerisation of model monomer pairs using

monofunctional and polyfunctional compounds provided

data on the role of structural-physical transformations,

involved in the formation of crosslinked polymers, on

the copolymerisation kinetics and on the non-uniformity

of distribution of crosslinks in the copolymers formed.

17 refs.

RUSSIA

Accession no.662893

Item 152Pigment & Resin Technology

26, No.6, 1997, p.387-8

POLYMER ANALYSIS USING NEAR INFRAREDSPECTROSCOPYBran & Luebbe Ltd.

The use of infrared spectroscopy for polymer analysis is

discussed, with particular reference to developments in

equipment from Bran & Luebbe. The company offers four

individual instruments, each with its own specific area of

application for use at various stages in the manufacture

References and Abstracts

80 © Copyright 2001 Rapra Technology Limited

of polymeric materials. They are the InfraProver,

InfraPrime, InfraAlyzer 600 and InfraAlyzer 200, the

latter representing the most recent breakthrough in the

development technique, providing laboratories with the

ability to analyse solid, powdered, semi-solid and liquid

materials with a single instrument. The use of each

instrument is discussed, and examples of the use of some

by industry are described.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.662760

Item 153Journal of Vinyl and Additive Technology

3, No.3, Sept.1997, p.200-4

FOURIER TRANSFORM INFRARED MICROSPECTROSCOPY MAPPING. APPLICATIONSTO THE VINYL SIDING INDUSTRYGarcia D; Black J

Elf Atochem NA

Applications of FTIR microspectroscopy mapping to the

vinyl siding industry were examined. Particular attention

was paid to determination, in single mapping experiments,

of the compositional changes associated with capstock

to substrate transition and to evaluation of the degradation

species and level observed during weathering exposure

throughout the thickness of the siding panel. 4 refs.

USA

Accession no.661984

Item 154152nd ACS Rubber Division Meeting, Fall 1997.

Conference Preprints.

Cleveland, Oh., 21st-24th Oct.1997, Paper 123, pp.19.

012

HNBR AND LONG-TERM SERVICEABILITY INMODERN AUTOMOTIVE LUBRICANTS. I.ANALYTICAL STUDYTripathy B S; Smith K C

Federal-Mogul Corp.

(ACS,Rubber Div.)

The mechanism responsible for the hardening of

hydrogenated nitri le rubber automotive seal

compounds on prolonged exposure to automatic

transmission fluids at high temperature was

investigated using Fourier transform IR spectroscopy.

The increase in hardness was found to result primarily

from chemical attack at the acrylonitrile (AN) sites.

This chemical attack first resulted in the formation of

isocyanide or isonitrile ions. The proposed mechanism

involved crosslinking at the AN sites through the

formation of isonitrile ions and the subsequent

formation of imides. The isonitrile intermediate formed

ionic bonds resulting in the formation of an ionomer

once the concentration became sufficiently high.

Ultimately these ions crosslinked to form imides in the

presence of oxygen or water. It was proposed that the

increase in hardness was due to the formation of the

ionomer and the imides. 9 refs.

USA

Accession no.659564

Item 155152nd ACS Rubber Division Meeting, Fall 1997.

Conference Preprints.

Cleveland, Oh., 21st-24th Oct.1997, Paper 40, pp.10.

012

THERMAL AND SPECTROSCOPIC(VIBRATIONAL AND NUCLEAR MAGNETICRESONANCE) CHARACTERIZATION OFETHYLENE-PROPYLENE-DIENE (EPDM)ELASTOMERSWinter J M; Edmondson M S; Parikh D R;

Mangold D J; Castille M J

DuPont Dow Elastomers LLC

(ACS,Rubber Div.)

The sequence distribution of EPM and EPDM samples

prepared using vanadium/aluminium chloride and

metallocene catalysts was studied by carbon-13 NMR and

Fourier transform IR spectroscopy. The influence of

sequence distribution on thermal properties was also

investigated. 13 refs.

USA

Accession no.658294

Item 156Biomaterials

18, No.21, 1997, p.1387-409

IN-VIVO DEGRADATION OFPOLYURETHANES: TRANSMISSION-FTIRMICROSCOPIC CHARACTERISATION OFPOLYURETHANES SECTIONED BYCRYOMICROTOMYMcCarthy S J; Meijs G F; Mitchell N; Gunatillake P A;

Heath G; Brandwood A; Schindhelm K

CSIRO; New South Wales,University

A combination of cryomicrotomy and FTIR microscopy

was used to investigate chemical changes in unstrained

sheets of Pellethane 2363-80A, Tecoflex EG80A and

Biomer caused by biodegradation (18 month

subcutaneous ovine implant). Cryomicrotomy was used

to obtain thin sections from the surface into the bulk,

parallel to the plane of the surface. FTIR microscopy was

then used to obtain infra red absorbance spectra.

Comparisons between the IR spectra (by spectral

subtraction) from implant surface, implant interior and

non-implanted controls were used to detect chemical

changes. SEM was used to assess microstructural changes

owing to biodegradation. 94 refs.

AUSTRALIA

Accession no.657629

References and Abstracts

© Copyright 2001Rapra Technology Limited 81

Item 157Applied Spectroscopy

51, No.3, March 1997, p.362-8

ONLINE POST CONSUMER PACKAGEIDENTIFICATION BY NIR SPECTROSCOPYCOMBINED WITH FUZZY ARTMAPCLASSIFIER IN INDUSTRIAL ENVIRONMENTFeldhoff R; Wienke D; Cammann K; Fuchs H

Muenster,Institute of Chemical & Biochemical Sensor

Research; Nijmegen,Catholic University;

Muenster,University

An optical set-up consisting of a high-throughput near-

IR (NIR) spectrograph with an InGaAs-array detector and

specially designed collection optics is used to record

spectra from post consumer packages located on an

industrial conveyor belt. NIR spectra of packages of

different polymers (PE, PETP, PP, PS and PVC) and of a

cardboard/plastic compound are recorded between 900

and 1700 nm with 6.3-ms integration time. The visual

distinction between the spectra is demonstrated by aid of

principal component analysis (PCA) plots. The spectra

are further classified by a Fuzzy ARTMAP neural

network. The method is assessed to be suitable for on-

line identification under industrial conditions. 16 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

NETHERLANDS; WESTERN EUROPE

Accession no.656293

Item 158Applied Spectroscopy

51, No.3, March 1997, p.346-9

AMPLITUDE SPECTRUM APPROACH INDYNAMIC FT-IR SPECTROSCOPY OFUNIAXIALLY ORIENTED POLYETHYLENETEREPHTHALATE FILMS. I. DRAW RATIODEPENDENCESonoyama M; Shoda K; Katagiri G; Ishida H

Toray Research Center Inc.

A method of data manipulation using the dynamic

magnitude spectrum and the static absorbance spectrum is

applied to uniaxially drawn PETP films with five different

draw ratios for the evaluation of the amplitude of dynamic

structural changes under a sinusoidal strain at the level of

a functional group. This analysis reveals that, in the drawn

film, the skeletal structures, such as the C-O bond in the

ethylene glycol unit and the phenyl ring, are susceptible to

deformation by mechanical stretching, while the dynamic

structural changes around the methylene group are small.

It was assumed that the backbone of the polymer is

responsible for the change of the mechanical properties

induced by the drawing of the film. 24 refs.

JAPAN

Accession no.656292

Item 159Macromolecular Rapid Communications

18, No.10, Oct.1997, p.903-9

SIMPLE METHODS FOR ASSESSING THECONFORMATIONAL SENSITIVITY OF IRBANDS BY DICHROISMOu-Yang W-C; Chen H-L

Kaohsiung,National Institute of Technology;

Taiwan,National Tsing Hua University

Two methods for evaluating the conformational

sensitivities of IR bands from the measurement of dichroic

ratio using PEEK as an example. Both methods were

based on the fact that the orientation function calculated

by all conformationally insensitive bands should be

identical. 11 refs.

CHINA

Accession no.656202

Item 160Synthetic Metals

89, No.2, Aug.1997, p.149-52

1320-NM EXCITED FT-RAMAN SPECTRA OFNA-DOPED TRANS-POLYACETYLENEJin-Yeol Kim; Ando S; Sakamoto A; Furukawa Y;

Tasumi M

Tokyo,University

The Fourier transform-Raman spectra of trans-

polyacetylene(t-PA) doped with sodium at various

concentrations were observed with the 1320 nm laser line.Doping-induced Raman bands for lightly doped t-PA were

observed for the first time. The observed wave numbers

of the C:C and C-C stretch bands of lightly doped t-PA

were lower than those of the corresponding bands of

pristine t-PA, whereas the reverse was the case for heavily

doped t-PA. The origins of doping-induced Raman bands

are discussed in terms of solitons and polarons. 20 refs.

JAPAN

Accession no.656141

Item 161Polymer

38, No.22, 1997, p.5699-702

EFFECTIVE WIDTH OF INTERFACE IN ASTRESSED MODEL POLYMER COMPOSITEMEASURED BY MICRO-FTIRLourie O; Wagner H D; Levin N

Weizmann Institute of Science; Israel,Police HQ

Materials Laboratory

The effect of mechanical deformation on a UV-cured

urethane-acrylate polymer and on a silicon carbide/

urethane-acrylate model composite was studied by micro-

FTIR spectroscopy. This technique was used for the first

time to measure the width of the interfacial zone beyond

which the fibre has no influence on the matrix. the results

were discussed. 14 refs.

ISRAEL

Accession no.654334

References and Abstracts

82 © Copyright 2001 Rapra Technology Limited

Item 162Macromolecular Symposia

Vol.119, July 1997, p.277-82

FTIR AND ATR ANALYSES ON APOLYPROPYLENE (PP) SURFACE AFTERPLASMA TREATMENT IN THE STUDY OFCHITOSAN SURFACE GRAFTING TOIMPROVE PP DYEING BEHAVIOURRochery M; Lam T M; Crighton J S

GEMTEX-ENSAIT; Leeds,University

The treatment of a PP film surface to improve its dyeing

behaviour was studied. A plasma treatment was carried

out to try to create oxidising groups on this surface, so

that it could be then easier to apply a specific

polysaccharide chitosan which is reported to be much

more reactive than PP and easy to dye. A study about the

various parameters of the plasma instrument was

necessary to find the optimal treatment. The possible

formed oxidising groups were emphasised by FTIR and

ATR analyses. Chitosan was applied after the plasma

treatment and the dyeing result which was then observed

was quite encouraging in certain conditions. 8 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE; UK;

WESTERN EUROPE

Accession no.653741

Item 163Macromolecular Symposia

Vol.119, July 1997, p.261-8

ORDERING AND MOBILITY OFFERROELECTRIC LIQUID CRYSTAL DIMERAS STUDIED BY FTIR SPECTROSCOPY WITH2-D IR CORRELATION ANALYSISShilov S V; Skupin H; Kremer F; Wittig T; Zentel R

St.Petersburg,Institute of Macromol.Compounds;

Leipzig,University; Mainz,University

Both a conservative rapid-scan FTIR technique and a

novel step-scan FTIR technique with two-dimensional

analysis were used to study the orientation and the

mobility of a ferroelectric liquid crystal dimer during

switching under an electric field. The detailed mutual

arrangements of different molecular segments (mesogen,

poly(methylene) chain, polysiloxane chain) in a smectic

C phase were derived from the static spectra. Temperature

and electric field strength dependencies of the mobility

of these segments are discussed. 18 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

RUSSIA; WESTERN EUROPE

Accession no.653739

Item 164Macromolecular Symposia

Vol.119, July 1997, p.101-11

APPLICATIONS OF PHOTOACOUSTIC STEP-SCAN FTIR SPECTROSCOPY TO POLYMERICMATERIALS

Gregoriou V G; Hapanowicz R

Polaroid Corp.; Nicolet Instrument Corp.

Step-scan photoacoustic data are presented that prove the

ability of the technique to successfully isolate the infrared

signature on the top layer from the infrared spectrum of

the bulk material, proving the sub-micron resolution

capability of the method. Results are shown that underline

the fact that the most serious problem in photoacoustic

spectroscopy is saturation at high absorptivities. 12 refs.

USA

Accession no.653724

Item 165Macromolecular Symposia

Vol.119, July 1997, p.89-100

EVIDENCE OF ELECTRON ACCEPTOR-ELECTRON DONOR INTERACTIONS INTHERMOPLASTIC POLYMER BLENDS BYUSING FTIR-ATR SPECTROSCOPYBrogly M; Nardin M; Schultz J

Institut de Chimie des Surfaces et Interfaces

Specific interactions in binary blends of ethylene-vinyl

acetate copolymer with various low molecular weight

terpene-phenol tackifying resins (TPR) were

systematically investigated, as a function of the

composition of the blend and of the electron acceptor

ability of the resin, by using attenuated total reflectionFTIR spectroscopy. Molecular acid-base were evidenced

between TPR hydroxyl groups and EVA carbonyl groups.

Quantitative information on the fraction of acid-base

bonded entities, the enthalpy and equilibrium constant of

pair formation were obtained. A crystalline transition of

the EVA copolymer was observed and discussed in terms

of enthalpy and entropy considerations based on FTIR

and calorimetric DSC investigations. Fundamental results

are then summarised to predict the interfacial reactivity

of such polymer blends towards acid or basic substrates.

16 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.653723

Item 166Macromolecular Symposia

Vol.119, July 1997, p.65-77

POLYMERS, ADDITIVES, SURFACTANTS ANDTHEIR MIXTURES: COMPUTER-BASEDSEARCH WITH SPECIAL FTIR LIBRARIESHummel D O

Cologne,University

The efficiency of selected search algorithms with specific

FTIR libraries of application-defined chemical systems

was assessed. This investigation was done with a PC of

850 MB/33 MHz, Windows 3.1 and the SPECTACLE

program of LabControl/Cologne. The libraries contained

References and Abstracts

© Copyright 2001Rapra Technology Limited 83

standardised FTIR spectra of 3601 defined polymers, 530

industrial polymers and resins, 1969 additives (pigments,

stabilisers, plasticisers, etc.), 1190 surfactants and 1614

monomers, pyrolysates and educts. For searches, the data

density was reduced to 4/cm. 21 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.653721

Item 167Macromolecular Symposia

Vol.119, July 1997, p.49-63

POTENTIAL OF TWO-DIMENSIONAL NEAR-INFRARED CORRELATION SPECTROSCOPYIN STUDIES OF PRE-MELTING BEHAVIOUR OFNYLON 12Ozaki Y; Yongliang Liu; Noda I

Kwansei-Gakuin,University; Procter & Gamble Co.

This review paper discusses the potential of generalised

two-dimensional near-infrared correlation spectroscopy

in studies of pre-melting behaviour and hydrogen bonds

of nylon 12. A study on dissociation and hydrogen bonds

of N-methylacetamide is also reviewed as a model

compound study of nylon 12. FTIR spectra were measured

over a temperature range of 30-150C where gradual

weakening of inter- or intramolecular associative

interactions and decrease of local order leading to the

eventual fusion of nylon 12 crystals are observed. 24 refs.

JAPAN; USA

Accession no.653720

Item 168Macromolecular Symposia

Vol.119, July 1997, p.1-13

APPLICATIONS OF TWO-DIMENSIONALCORRELATION SPECTROSCOPY IN DEPTH-PROFILING PHOTOACOUSTICSPECTROSCOPY, NEAR-INFRARED DYNAMICRHEO-OPTICS, AND SPECTROSCOPICIMAGING MICROSCOPYNoda I; Story G M; Dowrey A E; Reeder R C;

Marcott C

Procter & Gamble Co.

Some new developments of two-dimensional

spectroscopy are discussed. As a specific example, two-

dimensional correlation analysis of a polymer laminate

film using several different spectroscopic techniques is

presented. The versatility of this technique was developed

using depth-profiling photoacoustic spectroscopy, mid-

and near-IR dynamic rheooptical developments, and

spectroscopic imaging microscopy. Spatial and temporal

variations of near-IR spectra are effectively analysed by

the two-dimensional correlation technique. Step-scanning

FTIR spectrometers provide an opportunity to obtain

desired spectral information often difficult to obtain by

the conventional rapid-scanning technique. 12 refs.

USA

Accession no.653717

Item 169Polymer

38, No.21, 1997, p.5455-62

STRUCTURE OF STYRENE-ACRYLONITRILE/BUTADIENE POLYMER STUDIED BY 2D-IRSPECTROSCOPYSteeman P A M; Meier R J; Simon A; Gast J

DSM Research; Bruker Analytische Messtechnik

GmbH

2D IR spectroscopy involving mechanical excitation is

employed to study the mechanical relaxation phenomena

in an ABS sample, revealing detailed information

regarding the molecular segments involved in

macroscopic mechanical relaxation. From the temperature

dependence of the dynamic signals it is corroborated that

in the ABS sample the polybutadiene rubber relaxes

entirely independently from the SAN matrix, and thus is

present as a separate phase in the material. The rapid-

scan variation developed to perform 2D IR experiments

offers a significantly reduced measurement time in

comparison with the step-scan mode of operation. In

particular, in relation to research in the polymer field, in

which case stress relaxation is expected to occur during

the 2D IR experiment, this presents a major advantage.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

NETHERLANDS; WESTERN EUROPE

Accession no.652565

Item 170Applied Spectroscopy

51, No.8, Aug.1997, p.1245-50

STUDY OF IMPULSE POLYMER RHEO-OPTICSBY STEP-SCAN FT-IR TIME-RESOLVEDSPECTROSCOPYWang H; Palmer R A; Manning C J

Duke,University; Manning Applied Technology

The applicability of step-scan impulse/response FT-IR

spectroscopy to the rheo-optical study of polymer films

is demonstrated by spectral measurements with isotactic

PP. A novel piezoelectrically driven microrheometer is

employed to apply repetitive impulses to a polymer

sample while time-domain spectra are recorded by step-

scan FT-IR spectroscopy. The traditional advantages of

Fourier transform spectroscopy are retained while

providing a second multiplex advantage for the

characterisation of the time-dependence of the sample

response. Reproducible results, consistent with the

frequency-domain literature data and having good signal-

to-noise ratio, are obtained. The spectral changes due to

molecular reorientation are found to be essentially as fast

as the mechanical stretching, also consistent with

frequency-domain results. This is thought to be the first

reported step-scan FT-IR time-domain rheo-optical

References and Abstracts

84 © Copyright 2001 Rapra Technology Limited

measurement. This technique appears to be applicable to

a variety of polymer samples. The advantages of time-

domain measurements over frequency-domain

measurements are briefly discussed. 33 refs.

USA

Accession no.652416

Item 171Applied Spectroscopy

51, No.8, Aug.1997, p.1238-44

PHASE-RESOLVED DEPTH PROFILING OFTHIN-LAYERED PLASMA POLYMER FILMS BYSTEP-SCAN FOURIER TRANSFORMINFRARED PHOTOACOUSTICSPECTROSCOPYJiang E Y; Palmer R A; Barr N E; Morosoff N

Duke,University; Missouri-Rolla,University

After reviewing the background of step-scan

interferometric photoacoustic spectroscopy, a step-scan

Fourier transform photoacoustic phase-resolved technique

and its applications in depth profiling of micrometer-thick

layered plasma polymers are described. In particular, the

power of direct use of the photoacoustic phase spectrum

in both qualitative and quantitative depth profiling of the

layered samples is extensively discussed. The effects of

both spatial origin and intensity of a photoacoustic signal

on its phase are explicitly analysed for both overlapping

and distinctive, non-overlapping bands of thin-layered

plasma polymer samples. The phase spectrum technique

is shown to be a very effective and efficient method of

spectral depth profiling analysis. 29 refs.

USA

Accession no.652415

Item 172Applied Spectroscopy

51, No.8, Aug.1997, p.1083-91

IMPROVEMENTS IN USE OF ATTENUATEDTOTAL REFLECTION FOURIER TRANSFORMINFRARED DICHROISM FOR MEASURINGSURFACE ORIENTATION IN POLYMERSEverall N J; Bibby A

ICI Research & Technology Centre; Graseby-Specac

Ltd.

Improvements in the use of attenuated total reflection (ATR)

Fourier transform infrared (FT-IR) dichroism for measuring

surface orientation in polymer films are described for PETP.

It is shown that normalising band intensifies relative to a

nondichroic band, prior to calculating dichroic ratios,

eliminates the need to maintain identical contact areas/

pressures when removing, rotating and reclamping samples

to the ATR element, which has been a major historical

disadvantage of this technique. The normalisation is vital;

it makes the calculated dichroic ratios largely insensitive

to variations in sample/prism contact area, and less sensitive

to uncertainties in the refractive indices and birefringence

of the polymer. For PETP, it is shown that the birefringence

can be neglected in the analysis, and a single approximate

refractive index used. This is a significant benefit since the

birefringence varies as a function of orientation and

crystallinity. Equations are derived which allow the

calculation of all second-order orientation parameters and

the averaged squared direction cosines, from the normalised

ATR dichroic ratios. It is also shown how a single-reflection

diamond ATR unit is an ideal tool for this work, since it

allows small, hard, or irregularly shaped samples to be

examined without fear of damaging the ATR element. 16

refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.652413

Item 173Macromolecules

30, No.8, 21st April 1997, p.2400-7

RAMAN VIBRATIONAL STUDIES OFSYNDIOTACTIC POLYSTYRENE. II. USE OFTHE FUNDAMENTAL VIBRATIONAL MODE ASA QUANTITATIVE MEASURE OFCRYSTALLINITY WITH ISOTROPICMATERIALKellar E J C; Evans A M; Knowles J; Gaiotis C;

Andrews E H

London,University,Queen Mary & Westfield College

Raman spectra were taken with the 514.5 nm line of an

argon ion laser. Syndiotactic PS was found to exhibit two

distinct vibrational peaks in the Raman spectrum

corresponding to the fundamental vibrational mode. These

features were assigned to the symmetric phenyl ring

breathing mode coupled to the polymer backbone. The

presence of long all-trans sequences gives rise to a peak

at about 773/cm, whereas less well-defined trans/gauche

conformations result in a separate peak at 798/cm. With

increasing levels of crystallinity, the integrated intensity

of the former feature grows at the expense of the high-

frequency feature. The use of a series of annealed isotropic

films of glassy syndiotactic PS of increasing crystallinity

and molten syndiotactic PS has made it possible to

examine the precise relationship between these two

features and other neighbouring vibrational peaks. The

level of crystallinity within each sample was determined

independently using wide-angle X-ray scattering, DSC

and IR spectroscopic measurements. Results indicate that

the relative area under the all-trans fundamental band can

be directly related to the crystalline volume fraction within

each sample. It is proposed that this Raman vibrational

feature centered around 773/cm can be used as a

quantitative measure of crystallinity for syndiotactic PS

once the contribution from the all-trans sequences in the

melt is subtracted from the spectrum. 44 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.651397

References and Abstracts

© Copyright 2001Rapra Technology Limited 85

Item 174Macromolecules

30, No.8, 21st April 1997, p.2391-9

TWO-DIMENSIONAL NEAR-INFRARED (NIR)CORRELATION SPECTROSCOPY STUDY OFPREMELTING BEHAVIOUR OF NYLON 12Ozaki Y; Liu Y; Noda I

Nishinomiya,Kwansei-Gakuin University; Procter &

Gamble Co.

FT-NIR spectra of Nylon 12 in a cast film was measured

over a temperature range of 30-150C. The 2D NIR

correlation analysis reveals that there are at least eight

bands in the 6800-6100/cm region where the first overtone

of an NH stretching mode of Nylon 12 is expected to

appear. They may be ascribed to free- and hydrogen-

bonded NH groups in various environments. The

asynchronous 2D NIR correlation spectrum in the above

region indicates that the amide groups with a free carbonyl

oxygen appears first and then unassociated free amide

and amide with free NH follow as the temperature in

increased. In the 6000-5500/cm region of the synchronous

spectrum, four dominant autopeaks corresponding to the

first overtones of the methylene stretching modes are

observed at 5840, 5770, 5680, and 5640/cm, and negative

cross peaks are found between the 5770/cm band and the

rest. This observation, together with the careful inspection

of the dynamic NIR spectra, suggests that the band at

5770/cm is due to the contribution of the CH stretching

vibration of an ordered or highly associated form of Nylon

12, which decreases with temperature, while other NIR

bands correspond to more disordered forms. 33 refs.

JAPAN; USA

Accession no.651396

Item 175Journal of Vinyl and Additive Technology

3, No.2, June 1997, p.126-9

APPLICATIONS OF INFRAREDSPECTROSCOPY TO CUSTOMER PROBLEMSIN THE VINYL INDUSTRYGarcia D

Elf Atochem North America

This paper outlines procedures used in the identification

of typical PVC formulations, starting with the resin and

proceeding to impact modifier, process aids, lubricants,

stabiliser system and fillers. The emphasis is on FTIR

microscopy as the most versatile approach requiring small

samples and minimal to no sample preparation. Other

commonly used FTIR techniques are also outlined. Wet

separation protocols, applicability and limitations as

related to FTIR analysis are discussed. Typical examples

include vinyl siding, packaging and bottle formulations

as well as contaminants often encountered in these

formulations and raw materials.

USA

Accession no.650270

Item 176Kunststoffe Plast Europe

87, No.7, July 1997, p.12-3

NIR SPECTROSCOPY FOR THE ANALYSIS OFMIXED MATERIALSPahl M H; Grosse-Aschhoff M

Near infrared spectroscopy can be used to analyse the

concentrations of all the components of a PVC mixture.

Unlike conventional methods for the analysis of mixtures,

this technique is not limited to one “critical” component.

NIR, after calibration, can analyse all the components in

a single measuring operation. This technique is therefore

especially suitable for analysing dry blends comprising

several components.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.648051

Item 177Polymer

38, No.14, 1997, p.3435-40

FTIR. INVESTIGATION OF STRUCTURALMODIFICATION OF POLYCARBONATEDURING THERMODYNAMICAL TREATMENTSHeymans N

Bruxelles,Universite

The effects of annealing and ageing on IR absorption

spectra of polycarbonate were studied. The effect ofannealing was primarily a modification of trans-trans and

trans-cis population of the carbonate group, leading to a

more stable structure with a lower internal energy. Ageing

proceeded mainly by extremely local rearrangements

compatible with a densified structure. Ageing was,

however, accompanied by a slight change in

conformational populations. The results were discussed.

34 refs.

BELGIUM; EUROPEAN COMMUNITY; EUROPEAN UNION;

WESTERN EUROPE

Accession no.647751

Item 178Applied Spectroscopy

51, No.6, June 1997, p.856-65

APPLICATION OF A SPECTROSCOPICINFRARED FOCAL PLANE ARRAY(FPA)SENSOR FOR ON-LINE IDENTIFICATION OFPLASTIC WASTEvan den Broek W H A M; Wienke D; Melssen W J;

Feldhoff R; Huth-Fehre T; Kantimm T; Buydens L M C

Nijmegen,Catholic University; Germany,Institute for

Biochemical Sensor Research

A spectroscopic near-IR imaging system, using a FPA

detector, was developed for remote and on-line

measurements on a macroscopic scale. On-line

spectroscopic imaging requires high-speed sensors and

References and Abstracts

86 © Copyright 2001 Rapra Technology Limited

short image processing steps. The use of a FPA detector

in combination with fast chemometric software was

investigated. As these imaging systems generated so much

data, multivariate statistical techniques were required to

extract the important information from the multi-

dimensional spectroscopic images. These techniques

included principal component analysis and linear

discriminant analysis for supervised classification of

spectroscopic image data. The identification system was

constructed, implemented and tested for a real-world

application of plastic identification in municipal solid

waste. 31 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

NETHERLANDS; WESTERN EUROPE

Accession no.647715

Item 179Journal of Polymer Science : Polymer Physics Edition

35, No.9, 15th July 1997, p.1361-72

INFRARED DICHROISM AND POLYMERORIENTATION IN ATTENUATED TOTALREFLECTION. THEORETICALCONSIDERATIONSBelali R; Vigoureux J M; Morvan J

Besancon,University

The partial axial orientation model usually use for strongly

oriented polymers was adjusted to samples of weakly

aligned polymers and the parameters describing the

orientation configuration were related to the dichroic

ratios in four particular molecular chain distributions, i.e.

randomly, totally, partially and elliptically oriented. A new

method that led to the determination of these dichroic

ratios from ATR spectra was developed. This method was

based only on the use of three distinct polarisations of

the beam. All the practical difficulties usually encountered

in the other methods were thus eliminated. 28 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.645643

Item 180Macromolecules

30, No.6, 24th March 1997, p.1782-6

SOLVENT CASTING EFFECT ON THEINFRARED CHARACTERISTIC ABSORPTIONBANDS (1230/1250/CM) OF STEREOREGULARISOTACTIC POLY(ACRYLONITRILE) FILMMinagawa M; Yoshida W; Kurita S; Takada S; Yoshii F

Yamagata,University; Japan,Atomic Energy Research

Institute

The solvent casting effect on the IR characteristic

absorption bands of stereoregular isotactic PAN film was

studied in comparison with those of an atactic sample.

The ratio of intensities of the title IR characteristic bands

of PAN film was strongly dependent on the kind of dipolar

aprotic solvent used in the film preparation. A higher

intensity ratio was obtained when a good solvent such as

dimethyl sulphoxide was used, whereas a lower value was

obtained when a poor solvent such as malononitrile was

used. A linear relationship between the intensity ratio of

the IR bands and the dissolution power of nine different

kinds of dipolar organic solvents was found. The IR

characteristic bands of stereoregular PAN was dependent

on not only configuration, but also conformation through

the difference of the molecular cohesion state in the

solvent-cast film. The effect of configuration and

conformation on the IR results was quantitatively studied

as a function of the film preparation conditions. NMR

and wide angle X-ray diffraction results are given in

addition to IR data. 15 refs.

JAPAN

Accession no.639300

Item 181Macromolecular Symposia

Vol.114, Feb.1997, p.151-7

LOCAL MICROSTRUCTURE DEPENDENCE OFPVC INTERACTION WITH SOLVENTS. A FTIRVERIFICATIONGomez-Elvira J M; Tiemblo P; Martinez G; Millan J

Madrid,Instituto de Ciencia y Tec.de Polim.

Interactions between PVC and either cyclohexanone or

N-methyl-2-pyrrolidone were studied by FTIR. The

occurrence of local configuration based PVC-solvent

interactions, specifically, is demonstrated by studying,

first, the changes in FTIR frequency of both the solvent

carbonyl band and the PVC carbon-chlorine stretching

bands with the composition of PVC-solvent mixtures, and,

secondly, the FTIR dichroic behaviour of the same bands

upon stretching PVC films containing traces of solvent.

The results suggest that the interaction is restricted to a

definite number of polymer sites although no information

as to the exact type of these sites can be drawn. The

number of interaction sites is higher for cyclohexanone

than for N-methyl-2-pyrrolidone. The latter turns out to

be an original path to investigate polymer interactions. 8

refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;

WESTERN EUROPE

Accession no.639107

Item 182Polymer

38, No.11, May 1997, p.2753-8

PHASE TRANSITION IN ETHYLENE-TETRAFLUOROETHYLENE (ETFE)ALTERNATING COPOLYMER. ASPECTROSCOPIC STUDYRadice S; Del Fanti N; Zerbi G

Ausimont; Milano,Politecnico

IR and Raman spectroscopy were used to investigate the

mechanism, at the molecular level, of the phase transition

References and Abstracts

© Copyright 2001Rapra Technology Limited 87

in ethylene-tetrafluoroethylene alternating copolymer

from the orthorhombic to the hexagonal structure. The

study indicated that the transition may result from the

generation and propagation of conformational collective

defects. The results were discussed. 22 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;

WESTERN EUROPE

Accession no.638549

Item 183International Journal of Polymer Analysis and

Characterization

3, No.2, 1997, p.145-58

CHARACTERIZATION OF POLYETHYLENETEREPHTHALATE USING NEAR AND FARFTIR SPECTROSCOPYLachenal G

Universite Claude Bernard

The use of near-IR and far-IR spectroscopies for

characterisation of PETP films was investigated. After a

brief review of previous work, some examples of

transmission spectra of annealed PETP, showing complex

changes in the absorption bands, are presented. Near-IR

spectroscopy was used to follow the crystallinity (or

conformation) of thick PETP films without any sample

preparation. 40 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.637788

Item 184European Polymer Journal

33, No.3, March 1997, p.375-9

QUANTITATIVE IR SPECTROSCOPICANALYSIS OF ETHYLENE-ACRYLATECOPOLYMERSBuback M; Busch M; Droege T; Maehling F O;

Prellberg C

Gottingen,University

IR spectroscopy was used for quantitative analysis of the

composition of three ethylene-acrylate copolymers, i.e.

ethylene-methyl acrylate, ethylene-butyl acrylate and

ethylene-2-ethylhexyl acrylate copolymers. Based on a

simple model which explicitly considered vibrational

band intensities characteristic for CH and for C:O,

copolymer composition could be derived from the ratio

of C:O and CH integrated absorbances with a precision

of + or -3 mol %. It was not necessary to know the optical

path length of the copolymer samples which were

subjected to IR analysis as pressed films. 15 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.636548

Item 185Colloid & Polymer Science

275, No.4, April 1997, p.323-32

FOURIER TRANSFORM INFRARED STUDY OFPOLY(2-HYDROXYETHYLMETHACRYLATE)(PHEMA)Perova T S; Vij J K; Xu H

Dublin,University

The FTIR spectra in the wave number range 450-4500/

cm of PHEMA were studied as functions of water content

in the range 38-2.6 wt % and temps. in the range 300-

373K. The results showed changes in the intensities of

the stretching frequencies of the carbonyl band, H-O-H

bending vibration and O-H stretching vibration with a

change in water content and temp. The results confirmed

two types of water in the hydrogel polymer system, tightly

bound water and loosely bound water. At low

concentrations, water was mainly hydrogen-bonded to the

polymer and was described as tightly-bound water. At

water concentrations greater than 18 wt % , however, part

of the water existed in a different form and behaved as

loosely bound water. For concentrations over 30%, there

was some evidence that excess water behaved more

loosely bound somewhat like bulk water. IR spectroscopic

results supplemented those obtained by means of NMR

by Smyth et al. and by dielectric spectroscopy. The

authors’ results also suggested that some of the water

continued to be hydrogen bonded to the polymer until at

least a temp. of 373K when the bulk water should have

evaporated. FTIR was found to yield greater site-specific

insight into the local behaviour of water in hydrated

PHEMA. 25 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; IRELAND;

WESTERN EUROPE

Accession no.636483

Item 186Journal of Polymer Science : Polymer Physics Edition

35, No.7, May 1997, p.1055-66

EVALUATION BY FOURIER TRANSFORMINFRARED SPECTROSCOPY OF THEDIFFERENT CRYSTALLINE FORMS INSYNDIOTACTIC POLYSTYRENE SAMPLESMusto P; Tavone S; Guerra G; De Rosa C

Italy,National Research Council; Salerno,University;

Napoli,Universita Federico II

FTIR spectra of syndiotactic PS semi-crystalline samples

were examined by using the spectral subtraction approach.

It was shown that FTIR analysis provided a direct method

for the evaluation of the amount of alpha and beta form

crystalline phases, although both contain chains in the

same conformation (trans-planar). 50 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;

WESTERN EUROPE

Accession no.635541

Item 187Polymer

References and Abstracts

88 © Copyright 2001 Rapra Technology Limited

38, No.9, 1997, p.2077-91

RHEO-PHOTOACOUSTIC FTIR STUDIES OFTHERMAL HISTORY-STRAIN DEPENDENCE INPOLY(VINYLIDENE FLUORIDE)Ludwig B W; Urban M W

North Dakota State University

The effect of thermal history on the morphology of PVDF

was studied and rheophotoacoustic FTIR spectroscopy was

used to measure changes in PVDF network permeability

as a function of elongation. The rate at which PVDF was

cooled from the melt and the morphological changes caused

by annealing had a greater influence on the response of the

network to deformations than did molecular weight. Before

deformation, the crystalline phase and individual crystal

size seemed to have the most effect on permeability but

after stresses were applied, the number of tie molecules

and their resistance to being pulled from their anchoring

crystals dominated the permeability of the network.

Annealing PVDF within 20C of its melting point of 170C

increased the yield stress and Young’s modulus. Similar

effects occurred on reducing the cooling rate. 15 refs.

USA

Accession no.634449

Item 188Polymer

38, No.9, 1997, p.2067-75

STUDY OF THE CONFORMATIONS OFPOLY(EPSILON-CAPROLACTAM) ANDPOLY(EPSILON-CAPROLACTAM)-POLYBUTADIENE BLOCK COPOLYMERS BYFTIR SPECTROSCOPY WITHPHOTOACOUSTIC DETECTION AND BYMICRO-RAMAN CONFOCAL SPECTROSCOPYSchmidt P; Fernandez M R; Pastor J M; Roda J

Czech Republic,Academy of Sciences;

Valladolid,Universidad; Czech Institute of Chemical

Technology

FTIR spectroscopy with photoacoustic detection and

micro-Raman confocal spectroscopy were used to study

the conformations of poly(epsilon caprolactam) and

poly(epsilon-caprolactam)-polybutadiene block

copolymers. In the block copolymers prepared by anionic

polymerisation, the fraction of the planar conformation

of poly(epsilon-caprolactam) chains decreased with

increasing polybutadiene content. In the surface layers

formed by rapid saw cutting and in the islands formed by

microtome cutting, the content of the planar conformation

was lowered. This was substantially increased by water

treatment, especially at elevated temperatures. 15 refs.

CZECH REPUBLIC; EUROPEAN COMMUNITY; EUROPEAN

UNION; SPAIN; WESTERN EUROPE

Accession no.634448

Item 189Revista de Plasticos Modernos

71, No.475, Jan.1996, p.42-8

Spanish

DETECTION OF DEGRADATIVEMICROSTRUCTURAL CHANGES INPROPYLENE-ETHYLENE COPOLYMERCOMPONENTS BY FT-IRSPECTROPHOTOMETRYPages P; Carrasco F; Romeu J

Cataluna,Universidad Politecnica; Girona,Universidad

Fourier transform IR spectrophotometry was used to study

the microstructure of propylene-ethylene copolymer

samples taken from seats which had degraded during

storage or aged during outdoor exposure in an Olympic

stadium in Barcelona over a period of 2.5 years. Similar

microstructural changes were observed for both types of

sample, but these changes were more intense in samples

taken from seats which had been subjected to the action

of UV irradiation during outdoor exposure. The changes

observed included increases in aldehyde and ketone

groups and decreases in unsaturation, peroxide, methyl

and methylene groups and isotacticity. The results

indicated that the main processes taking place were

photooxidation and chain scission. 7 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;

WESTERN EUROPE

Accession no.632273

Item 190Journal of Materials Science Letters

16, No.6, 15th March 1997, p.445-7

INFRARED SPECTROSCOPIC STUDIES OFTHE INTERACTION BETWEEN NATURALRUBBER AND CHLORINATED NATURALRUBBERCool J W; Edge S; Packham D E

Bath,University

The interactions that occur within a simple model

consisting of NR and a chlorinated NR were studied using

SEM, supported by electron probe microanalysis. The 1:1

wt% mixture of NR and chlorinated NR was not totally

miscible when cast from xylene. Heating at 170 C for 30

min resulted in a dramatic change. The morphology of

the film appeared to be homogeneous, and there was

evidence for some type of accelerated chemical oxidation,

possibly in the isoprene units in the NR. 7 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.632154

Item 191RadTech ’96 North America. Volume 1. Conference

proceedings.

Nashville, Tn., 28th April-2nd May 1996, p.407-16. 895

ATTENUATED TOTAL REFLECTANCE FTIRMICROSCOPY AS AN ANALYTICAL PROBLEMSOLVING TOOL

References and Abstracts

© Copyright 2001Rapra Technology Limited 89

Buehner R W

UCB Chemicals Corp.

(RadTech International)

Fourier transform IR microscopy has proved useful in

characterising contaminants as small as 50 microns in

diameter in resins and cured films as well as characterising

cured film surfaces. The keys to the successful use of

FTIR microscopy are experience in sample preparation,

an understanding of light microscopy, and ingenuity in

defining solutions. Examples are given of various

problems that have been resolved using the attenuated

total reflectance FTIR microscope technique. 4 refs.

USA

Accession no.628096

Item 192Journal of the Adhesive and Sealant Council. Volume 1.

Fall 1996. Conference proceedings.

San Francisco, Ca. 3rd-6th Nov.1996, p.521-33. 6A1

ATTENUATED TOTAL REFLECTION FOURIERTRANSFORM INFRARED SPECTROSCOPY(ATR FTIR): USEFUL TOOL FOR MOLECULARANALYSIS OF ADHESIVES, SEALANTS ANDCOATINGSIshida H

Case Western Reserve University

(US,Adhesives & Sealants Council)

Attenuated total reflection (ATR) Fourier transform

infrared spectroscopy (FTIR) is a useful molecular

characterisation technique for studying the surface region

of adhesives, sealants, and coatings. As examples of

challenging samples, applications for carbon fibre

surfaces and their interaction with an epoxy coating are

described. Special intensity enhancement observed on

carbon fibre surfaces allows the study of surface species

of oxidised carbon fibres. Another and more unique

application of ATR spectroscopy is optical depth profiling

in which a concentration or structural gradient is probed

near the surface of a material, such as an adhesive, sealant

or coating. Two techniques have been developed. The first

method requires obtaining spectra at multiple angles and

the analysis is done at a single frequency. On the other

hand, the second method utilises multiple frequencies

from only one spectrum. This latter technique allows in-

situ monitoring of structural or concentration changes as

a function of time due to the short data acquisition time.

Unlike traditional ATR depth profiling techniques, the

newly developed methods do not require a guessed profile,

eliminating human errors. High spatial resolution and the

quantitative nature of the analysis have been

demonstrated. 23 refs.

USA

Accession no.626545

Item 193Applied Spectroscopy

50, No.12, Dec.1996, p.1500-4

RAMAN MAPPING OF THE DENTIN/ADHESIVEINTERFACEWieliczka D M; Spencer P; Kruger M B

Missouri,University

The degree of adhesive penetration into dentin was studied

by micro-Raman spectroscopic examination of the dentin/

adhesive interface. In contrast to previous studies, the

Scotchbond multipurpose dentin adhesive penetrated less

than 2 micrometres into the acid-etched and, thus,

decalcified dentin. There was strong spectroscopic evidence

that, upon acid etching of the dentin surface, which was

typically performed immediately before the adhesive was

applied, the collagen matrix collapsed upon itself. 21 refs.

3M CO.USA

Accession no.622477

Item 194Journal of Polymer Science : Polymer Physics Edition

32, No.11, Aug.1994, p.1881-7

DEPTH PROFILING OF POLYMER LAMINATESUSING FOURIER TRANSFORM (ATR)SPECTROSCOPY: THE BARRIER FILMTECHNIQUEPereira M R; Yarwood J

Durham,University; Sheffield,Hallam University

FTIR-ATR spectra of a laminate (PMMA/polyvinyl

alcohol) were presented at different base layer thicknesses

and different angles of incidence on a zinc selenide

substrate. By varying the thickness of the PMMA barrier

film, different effective penetration depths in the polyvinyl

alcohol were achieved. These results agreed well with

the calculated electric fields as a function of distance away

from the substrate surface. The work provided the basis

for depth profiling measurements to detect interfacial

interactions. 18 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.621617

Item 195Macromolecules

29, No.23, 4th Nov.1996, p.7460-9

STRUCTURAL INVESTIGATION OFORTHORHOMBIC-TO-HEXAGONAL PHASETRANSITION IN POLYETHYLENE CRYSTAL.EXPERIMENTAL CONFORMATION OF THECONFORMATIONALLY DISORDEREDSTRUCTURE BY X-RAY DIFFRACTION ANDINFRARED-RAMAN SPECTROSCOPICMEASUREMENTSTashiro K; Sasaki S; Kobayashi M

Osaka,University

Structural changes in the orthorhombic-to-hexagonal

phase transition of PE crystal was investigated by

References and Abstracts

90 © Copyright 2001 Rapra Technology Limited

measuring the DSC, X-ray diffraction, and IR and Raman

spectra for the geometrically-constrained ultradrawn

samples (gel film of Hizex Million 240M HMWPE and

commercial ultrahigh modulus fibre called Dyneema from

Toyobo Co. Ltd.) in the course of heating up to the melting

temperature. The IR and spectral patterns characteristic

of the hexagonal phase were confirmed. In particular, the

bands characteristic of the disordered short trans segments

(shorter than five methylene units) and the bands of the

kink or double gauche linkages were detected definitely.

The degree of orientation of the averaged chain axis, as

detected from the temperature dependence of the X-ray

fibre diagram, was reserved well enough even in the

hexagonal phase, while the orientational degree of the

methylene units, as detected from the polarised IR spectral

measurements, was found to be lowered appreciably. This

finding, combined with the observation of the trans and

gauche bands, has confirmed experimentally and

definitely the existence of the conformationally disordered

chains in the hexagonal phase. 31 refs.

JAPAN

Accession no.621218

Item 196Journal of Applied Polymer Science

63, No.1, 3rd Jan.1997, p.89-101

REACTION OF POLYACRYLIC ACID ANDMETAL OXIDES: INFRARED SPECTROSCOPICKINETIC STUDY AND SOLVENT EFFECTHo-Shing Wu; Heay-Chain Jone; Jiann-Wen Hwang

Yuan Ze,Institute of Technology; Nan Pao Resins

Chemical Co.Ltd.

IR spectroscopic studies were conducted of the reaction

of polyacrylic acid(PAA) and metal oxides (zinc oxide,

calcium oxide, cupric oxide, chromium oxide and

aluminium oxide). Factors such as the amount of metal

oxide, reaction time, solvents, type of metal oxides and

temp. were also evaluated to derive the optimum

conditions for this reaction. The reactions of chromium

oxide and aluminium oxide were far from complete. An

extra solvent added to the reaction system could increase

the solubility of PAA and metal oxide in the solution to

cause complete reaction. The reactivity of the reaction

was increased by using a hydrophilic solvent, particularly

water and methanol. Furthermore, the reaction rate

increased when temp. decreased. The reactivity of the

reaction was proportional to the pH value of the metal

oxide in the aqueous solution. 16 refs.

CHINA; TAIWAN

Accession no.618376

Item 197Polymer

37, No.26, 1996, p.5807-16

FTIR-RHEOOPTICAL CHARACTERISATIONOF THE MOLECULAR ORIENTATION

BEHAVIOUR OF AMINE CURED EPOXYRESINS DURING CYCLIC DEFORMATIONScherzer T

Institut fuer Oberflaechenmodifizierung

Rheooptical FTIR spectroscopy was used to study

molecular orientation in highly crosslinked epoxy resins

based on the diglycidyl ether of bisphenol A and a

polyetherdiamine. The rheooptical characterisation of

these resins during specific cyclic deformation

experiments below the Tg is reported. Epoxy resin films

were subject to various successive loading-unloading

cycles including elongation, recovery, annealing and stress

relaxation to study the reversibility of the orientation

during relaxation processes. 33 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.617807

Item 198Macromolecules

29, No. 22, 21st Oct. 1996, p.7124-9

INVESTIGATION OF POLYMER DIFFUSION INHYDROGEL LAMINATES USING NEAR-FIELDFTIR SPECTROSCOPYSahlin J; Peppas N A

Purdue University

The role of diffusion in gel/gel adhesion was examined

by near-field FTIR microscopy. Using a near-field FTIRmicroscopy technique, compositional maps were obtained

with improved spatial resolution and enhanced signal to

noise ratio. With this technique, the resolution was

enhanced by about a factor of 5. Polymer chain diffusion

across a gel/gel interface was a substantial mechanism of

adhesion. Diffusion of poly(ethylene glycol) free chains

across poly(acrylic acid) gels was investigated. The

diffusivity of poly(ethylene glycol) was on the order of

1/100,000,000 to 1/1000,000,000 sq.cm/s for these

swollen polymer gels. Poly(ethylene glycol) diffusivity

in poly(acrylic acid) gels scaled to the -0.41 power of the

molecular weight. This was similar to values reported for

polyethylene glycol diffusion in aqueous solution. 20 refs.

USA

Accession no.617217

Item 199Applied Spectroscopy

50, No.11, Nov.1996, p.1360-5

DYNAMIC INFRARED LINEAR DICHROICSPECTRA OF PRESTRETCHEDPOLYPROPYLENEIngemey R A; Strohe G; Veeman W S

Duisberg,Gerhard-Mercator University

DIRLD (dynamic infrared linear dichroic) spectra of

prestretched isotactic polypropylene were recorded. The

line shape features in the in-phase spectra are described

on the basis of frequency shifts and absorption amplitude

References and Abstracts

© Copyright 2001Rapra Technology Limited 91

variations during the stretching cycle. Details such as the

dichroism of the bands, direction of the shift, and changes

in the absorption intensities must be considered to explain

signs and shapes of the DIRLD bands. Evidence for chain

reorientations under stress was not found. The general

principal of frequency shifts and changes in absorption

intensities as the origin of DIRLD bands was

demonstrated by spectral simulations. 34 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.616827

Item 200Polymer

37, No. 21, Oct. 1996, p.4705-12

CROSSLINKING COPOLYMERISATION OFEPOXY METHACRYLATES AS STUDIED BYFOURIER TRANSFORM RAMANSPECTROSCOPYSandner S; Kammer S; Wartewig S

Halle,Martin-Luther-Universitat

Bisphenol A bis(2-hydroxypropyl methacrylate) was

copolymerised with methyl derivatives of styrene (alpha-

methylstyrene, 4-methylstyrene and 60/40 3-

methylstyrene/4-methylstyrene mixture) initiated by di-

tert-butyl peroxide in the presence of 76 wt% of silica

filler (quartz) at 150C-200C. The Raman bands of the

carbon-carbon double bond stretching vibrations at 1630

and 1637/cm were found to be suitable for determining

the conversion of double bonds of the styrene and

methacrylate monomer simultaneously in dependence of

the copolymerisation time. The carbonyl bands at 1702

and 1718 /cm were not suitable for assessing conversion

of carbon-carbon double bonds. Relevance to

polymerisable diluents for use with bisphenol A bis(2-

hydroxypropyl) methacrylate) in dental applications like

restorative composite materials, sealants and adhesives,

is suggested. 18 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.616206

Item 201Macromolecules

29, No. 19, 9th Sept. 1996, p.6256-61

RELAXATION OF SEGMENTAL ORIENTATIONAND CHAIN EXTENSION INPOLYCARBONATE STUDIED BY INFRAREDDICHROISM AND SHRINKAGELundberg L; Stenberg B; Jansson J F

Stockholm,Royal Institute of Technology

The relaxation of the segmental orientation and the chain

extension in polycarbonate (Makrolon 1143 from Bayer

AG) were studied by IR dichroism and heat shrinkage

after a step strain deformation to a draw ratio of 1.75.

This makes it possible to distinguish between local

relaxation mechanisms (Rouse) and large-scale relaxation

mechanisms of the molecular orientation. It was found

that the average relaxation time for segmental orientation

is shorter and more temperature dependent than the

average relaxation time for the chain extension. The

segmental orientation relaxes almost totally at 170C (Tg

148C) before the chain extension even starts to relax. 16

refs.

SCANDINAVIA; SWEDEN; WESTERN EUROPE

Accession no.616185

Item 202Journal of Applied Polymer Science

62, No.11, 12th Dec.1996, p.1903-11

SURFACE AND INTERFACIAL FOURIERTRANSFORM INFRARED SPECTROSCOPICSTUDIES OF LATEXES. XVI. QUANTITATIVEANALYSIS OF SURFACTANT INMULTILAYERED FILMSNiu B J; Urban M W

North Dakota State University

Migration and concentration levels of sodium

dioctylsulphosuccinate(SDOSS) surfactant molecules in

silicone-modified 50%/50% styrene/butyl acrylate latex

were detected at the film-substrate and film-air interfaces

in mono- and double-layered films. The SDOSS content

was shown to be influenced by the presence of

trimethoxysilyl propylmethacrylate siloxane. Quantitative

polarised ATR FTIR spectroscopy was used to analyse

the content of the SDOSS molecules. 22 refs. (Pt.XV, ibid,

p.1893-901)

USA

Accession no.616095

Item 203Progress in Organic Coatings

28, No.4, Aug.1996, p.279-83

VIBRATIONAL SPECTROSCOPIC STUDY OFDISTRIBUTION OF SODIUM DODECYLSULPHATE IN LATEX FILMSAmalvy J I; Soria D B

CIDEPINT; La Plata,Universidad Nacional

The migration of the surfactant sodium dodecyl sulphate

to the film-air(F-A) and film-substrate(F-S) interfaces

during coalescence of a methyl methacrylate-ethyl

acrylate latex functionalised with methacrylic acid was

monitored by IR and ATR-FTIR spectroscopic techniques.

Both F-A and F-S interfaces showed surfactant

enrichment, revealing a nearly parabolic distribution of

surfactant throughout the film. 11 refs.

ARGENTINA

Accession no.615836

Item 204Macromolecular Chemistry & Physics

197, No.11, Nov.1996, p.3523-30

References and Abstracts

92 © Copyright 2001 Rapra Technology Limited

CHARACTERISATION OF THE DIFFERENCESIN THE CRYSTALLINITY FROM SURFACE TOBULK OF COMPRESSION-MOULDEDPOLYPROPYLENE SHEETS USINGATTENUATED TOTAL REFLECTION FOURIER-TRANSFORM IR SPECTROSCOPYKawamoto N; Mori H; Nitta K H; Yui N; Terano M

Japan,Advanced Institute of Science & Technology

The crystallinities of compression-moulded PP sheets

were investigated by application of FTIR and ATR FTIR

analyses. Two internal reflection elements, Ge and KRS-

5, with an angle of incidence of 45 degrees, were used to

obtain the depth profiles of the crystallinity of PP sheets

from the surface to the bulk. The crystallinity in the region

from the surface to about 0.7 micrometre depth was

significantly lower than that in the bulk. PP sheets with

higher comonomer content showed the same tendency,

which was enhanced with decreasing moulding temp. 15

refs.

JAPAN

Accession no.615802

Item 205Applied Spectroscopy

49, No. 10, Oct.1995, p.1411-30

RAMAN IMAGING OF HETEROGENEOUSPOLYMERS: A COMPARISON OF GLOBALVERSUS POINT ILLUMINATIONMarkwort L; Kip B; Da Silva E; Roussel B

DSM; Dilor SA

Two alternative methods of Raman imaging via global

illumination and via point illumination in combination

with confocal light collection were applied to the study

of heterogeneous polymer systems. The spectral and

spatial resolving power of the different techniques was

estimated experimentally. The influence of the depth

resolution on the Raman image of a defined sample

structure was demonstrated in a mathematical simulation.

Data are given for PE, PS, polyacrylate, and epoxy resins.

23 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

NETHERLANDS; WESTERN EUROPE

Accession no.615631

Item 206R’95 - Recovery, Recycling, Re-Integration. Volume

III: Mechanical Processes, Logistic Networks,

Separation Technologies. Conference proceedings.

Geneva, 1st-3rd Sept. 1995, p.III.230-5. 8(13)

FAST ONLINE IDENTIFICATION OF PLASTICMATERIALS BY NEAR INFRAREDSPECTROSCOPYEisenreich N; Hrez J; Kull H; Mayer W

Fraunhofer-Institut fuer Chemische Technologie

Edited by: Barrage A; Edelmann X

(EMPA; Swiss Federal Laboratories for Mat.Testing & Res.)

An economic method for recycling of plastics has to

separate the various types of polymeric materials. As

physical methods are not sufficient, the identification has

to monitor structural or molecular properties of the

polymer. In the near infrared spectral range NIR (700 to

2500 nm), molecules absorb light by overtone or

combination vibrations of the C-H, O-H, N-H and C-O

bands. The reduced absorption in the NIR allows

registration of spectra of bulky plastics of practical interest

in recycling. Advantages of the NIR spectral range

compared to the IR are: NIR-photo detectors, like Ge,

InAs, or InGaAs photodiodes with fast response and

higher detectivity; and quartz fibre optics with low

attenuation. For fast scanning of the wavelength region

of 1000 to 2200 nm, two spectrometers are realised based

on acousto-optic tunable filters with a scan speed of 1000

nm/ms and applied to identify the plastics in mass

consumer products and household wastes. 16 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.615266

Item 207Journal of Materials Science Letters

15, No.21, 1st Nov.1996, p.1908-11

ANALYSIS OF STRESS CONCENTRATIONS INMULTI-FIBRE MICROCOMPOSITES BYMEANS OF RAMAN SPECTROSCOPYVan Den Heuvel P W J; Peijs T; Young R J

Eindhoven,University of Technology; UMIST;

Manchester,University

Preliminary results are presented showing that Raman

spectroscopy makes it possible to measure stress

concentration factors in fibres adjacent to a fibre break.

Use is made of a carbon/epoxy resin multi-fibre

microcomposite, in which five different carbon fibres are

aligned parallel in a planar array at a predefined inter-

fibre spacing in a dumbbell-shaped tensile bar. 16 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; UK; WESTERN EUROPE

Accession no.615176

Item 208China Synthetic Rubber Industry

19, No.5, 1996, p.314-6

Chinese

APPLICATION OF FT-RAMAN SPECTROSCOPYIN RUBBER ANALYSISWang G; Xu F

Shenyang,Rubber Industry Products Research Institute

The application of FT-Raman spectroscopy in the analysis

of rubbers and related materials is discussed.

Characteristics of FT-Raman spectroscopy were compared

with FTIR. 23 refs.

CHINA

Accession no.609956

References and Abstracts

© Copyright 2001Rapra Technology Limited 93

Item 209Antec ’96. Volume III. Conference proceedings.

Indianapolis, 5th-10th May 1996, p.3131-5

FAST ON-LINE IDENTIFICATION OF PLASTICSBY NEAR-INFRARED SPECTROSCOPY FORUSE IN RECYCLING PROCESSESEisenreich N; Herz J; Kull H; Mayer W; Rhoe T

Fraunhofer-Institut fuer Chemische Technologie

(SPE)

For economic recycling of plastics, various types of

polymeric materials have to be separated in a short period

of time. The near-infrared spectral range allows the

monitoring of structural or molecular properties of the

plastic under investigation. The spectrometer system

described is based on optical fibres for absorption and

reflexion measurements, an acousto-optic tunable filter

and a transputer system. It is able to detect 1,000 spectra/

s and to identify 20 pieces/second. 10 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.609107

Item 210Polymer

37, No.18, 1996, p.4009-24

FOURIER TRANSFORM RAMAN STUDY OFTHE STRAIN-INDUCED CRYSTALLISATIONAND COLD CRYSTALLISATION OF NATURALRUBBERHealey A M; Hendra P J; West Y D

Southampton,University

Two NR samples (cured and uncured) were studied. In

all studies, the samples were stretched to 500% elongation.

The Fourier-transform Raman spectrum of NR is

presented as a function of time of cold soaking at -25C

and of strain with respect to laser polarisation. Under both

sets of conditions, changes occur in the spectra that can

be attributed to crystallisation. Difference spectra showing

only those bands due to crystallisation (i.e. spectra of

crystalline NR) are presented, which allows the

crystallisation process to be discussed with respect to the

conditions under which crystallites are formed. A

combination of Fourier-transform Raman and Fourier-

transform IR depolarisation spectra was used to deduce

preliminary assignments for some of the vibrational bands

of natural rubber. 40 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.607325

Item 211Polymer

37, No.15, 1996, p.3227-31

ISOTACTICITY DETERMINATION OFPOLYPROPYLENE USING FT-RAMANSPECTROSCOPY

Sundell T; Fagerholm H; Crozier H

Abo,Akademi University; Borealis Polymers Oy

Carbon-13 NMR was used as the reference method to

enable comparison of FT-Raman and FTIR spectroscopies

as isotacticity determination methods. Calibration curves

relating Raman scattering and IR absorption ratios to the

carbon-13 NMR results are presented. The repeatability

for both FT-Raman and FTIR measurements was

comparable to that of carbon-13 NMR analysis and there

was good correlation between between carbon-13 NMR

and FT-Raman/FTIR results. The reliabilities of the three

methods are statistically evaluated and compared. 9 refs.

FINLAND; SCANDINAVIA; WESTERN EUROPE

Accession no.606302

Item 212Composites Science & Technology

56, No.7, 1996, p.749-54

STUDY OF CARBON FIBRE STRAIN IN MODELCOMPOSITES BY RAMAN SPECTROSCOPYLeveque D; Auvray M H

Office National d’Etudes & de Recherches Aerosp.

The application of strain to the molecular structure of

carbon fibre was shown to cause a linear shift of Raman

frequencies. The magnitude of this shift increased with

increasing organisation of the fibre structure, from -7/

cm/% for the T800HB intermediate modulus fibre to -11/cm/% for the M40B high modulus fibre. Raman

spectroscopy was shown to be a useful tool for identifying

the different interfacial load transfer types from strain

profile observation in single fibre model composites under

tensile loading, i.e. fibre debonding with or without

friction, and elastic stress transfer was well described by

the Cox model. The interfacial shear stress distribution,

the possible friction coefficient and the longitudinal

thermal residual strain were derived from the strain

profiles. 9 refs. (9th French National Colloquium on

Composite Materials, Saint-Etienne, France, Nov.1994)

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.605822

Item 213Polymer International

41, No.1, Sept.1996, p.35-41

FTIR-MICROSPECTROSCOPY(FTIR-M) ANDDSC STUDIES OF POLYVINYLIDENEFLUORIDE(PVDF)Benedetti E; Catanorchi S; D’Allesio A; Moggi G;

Vergamini P; Pracella M; Ciardelli F

Pisa,University; CNR

PVDF samples, obtained by casting from THF solutions

and submitted to various thermal treatments, were

examined by FTIR-M and DSC. This type of analysis

permitted examination of microdomains of samples of

References and Abstracts

94 © Copyright 2001 Rapra Technology Limited

different morphological characteristics and an indication

of the polymorphism of PVDF to be obtained. In some

cases, the simultaneous presence of two or three forms

was observed by comparison of FTIR-M and DSC traces.

Vibrational spectra of single crystalline forms could be

recorded by FTIR-M on phase homogeneous

microdomains. 13 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;

WESTERN EUROPE

Accession no.605759

Item 214Polymer

37, No.16, 1996, p.3665-73

ANIONIC POLYMERISATION OF STYRENEAND BUTADIENE INITIATED BY N-BUTYLLITHIUM IN ETHYLBENZENE:DETERMINATION OF THE PROPAGATIONRATE CONSTANTS USING RAMANSPECTROSCOPY AND GEL PERMEATIONCHROMATOGRAPHYAuguste S; Edwards H G M; Johnson A F; Meszena Z

G; Nicol P

Bradford,University

The rate of monomer loss during the n-butyllithium-

initiated anionic polymerisation of styrene in ethylbenzene

was measured using Raman spectroscopy. GPC

measurements on the reaction products were used as an

indirect method of obtaining the concentrations of the

propagating species involved in this reaction. The rate of

propagation for styrene polymerisation was determined

in the temperature range 25-70 C, and for specified live-

end concentrations. 34 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.604626

Item 215Analyst

121, No.8, Aug.1996, p.1069-74

POLYMER ANALYSIS BY COLUMN LIQUIDCHROMATOGRAPHY COUPLED SEMI-ON-LINE WITH FOURIER TRANSFORMINFRARED SPECTROMETRYSomsen G W; Rozendom E J E; Gooijer C; Velthorst N

H; Brinkman U A T

Amsterdam,Free University

Additives in polymers were identified by solvent-

elimination based coupling of reversed-phase column

liquid chromatography(LC) and FTIR spectrometry. A

spray-jet interface was used to deposit the effluent from

a narrow-bore LC column on a zinc selenide window.

The deposited additives were analysed by FTIR

transmission microscopy, yielding identification limits in

the low-nanogram range. High-quality IR spectra were

obtained for components present in PVC and PP samples.

These spectra allowed the characterisation of the additives

by spectral library search and/or spectral interpretation.

The usefulness of the spray-jet interface system for the

coupling of size exclusion chromatography(SEC) and

FTIR spectrometry was examined on the basis of the

analysis of a PS standard mixture. Representative IR

spectra of the SEC effluent indicated that the SEC-FTIR

system could be used for the determination of

compositional changes across the polymer MWD. 25 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; WESTERN EUROPE

Accession no.604342

Item 216Polymer Science Series A

38, No.5, May 1996, p.517-24

RAMAN SPECTROSCOPIC INVESTIGATIONOF THE ORIENTATION PROCESS OF LINEARPOLYETHYLENERussian Academy of Sciences

The potential of polarisation Raman spectroscopy in

probing the structure of oriented polymers was shown

using linear PE as the example. The evolution of the

Raman spectra of PE in the course of drawing from the

isotropic state to that with the highest attainable

orientation was investigated. The mechanism of transition

from the lamellar structure to fibrillar one was shown to

be independent of the particular method of an isotropic

sample preparation. The use of micro Raman attachment

made it possible to study the structure in the necking

region. The data obtained showed that the change in

orientation of the polymer chains along the length of a

neck was continuous. 18 refs.

RUSSIA

Accession no.601403

Item 217Applied Spectroscopy

50, No.7, July 1996, p.900-5

IN SITU NEAR-IR CURE MONITORING OF AMODEL EPOXY MATRIX COMPOSITECossins S; Connell M; Cross B; Winter R; Kellar J

South Dakota,School of Mines & Technology

The curing of an epoxy resin adjacent to an embedded

silica optical fibre was monitored in situ by evanescent

wave spectroscopy. The epoxy resin was partially

fluorinated and had a lower refractive index than the

silica fibre. The lower refractive index of the epoxy resin

allowed the silica optical fibre to be used as a waveguide

for the internal reflection of the near-IR light. The epoxy

resin curing was determined as a function of time and

temp. by analysis of the near-IR spectrum from the epoxy

adjacent to the fibre obtained by the interaction of the

evanescent wave that occurred at each internal reflection

with the low refractive index epoxy resin. The results

obtained showed that epoxy ring-opening and

References and Abstracts

© Copyright 2001Rapra Technology Limited 95

crosslinking reactions could be followed in real time.

Treatment of the fibre with a silane coupling agent had

no observable effect on the curing reaction of the epoxy

resin. 27 refs.

USA

Accession no.600870

Item 218Polymer

37, No.12, 1996, p.2335-43

DYNAMIC TWO-DIMENSIONAL INFRA-REDSPECTROSCOPY OF THE CRYSTAL-AMORPHOUS INTERPHASE REGION IN LOW-DENSITY POLYETHYLENESinghal A; Fina L J

Rutgers,University

Dynamic two-dimensional FTIR was used to study the

nature of the interphase in LDPE. A two-dimensional

correlation analysis on the dynamic spectra indicates that

neat LDPE is comprised of three regions, specifically, an

ordered crystalline region, a disordered liquid-like region,

and a crystal/amorphous interfacial region. The 1468/cm

peak in the methylene bending region is assigned to all-

trans structures which primarily reside in the interfacial

region. A variety of LDPE samples with different additives

are used in order to determine how the additives influence

the dynamic mechanical properties of each morphological

phase. It is found that talc associates with the crystallites,

ethylene vinyl acetate is distributed in all three

morphological phases of the LDPE, and pyrene is

associated only with the non-crystalline regions. 31 refs.

USA

Accession no.599665

Item 219Macromolecules

29, No.10, 6th May 1996, p.3515-20

RAMAN VIBRATIONAL STUDIES OFSYNDIOTACTIC POLYSTYRENE. 1.ASSIGNMENTS IN A CONFORMATIONAL/CRYSTALLINITY SENSITIVE SPECTRALREGIONKellar E J C; Galiotis C; Andrews E H

Queen Mary & Westfield College

A detailed analysis of the Raman spectrum of

syndiotactic PS in the region 600-850/cm was

undertaken. As syndiotactic PS exhibits considerable

polymorphism, spectra of various preparations including

melt-crystallised syndiotactic PS, solvent-crystallised

syndiotactic PS and quenched glassy materials, were

studied. Peaks are assigned to conformational changes

and sequences. Comparison with atactic PS is made.

Study of the cross section of a compression moulded

plaque exhibiting a skin/core structure revealed the

continuous way the structure varied with changing

crystallinity. The various physical forms of syndiotactic

PS and the routes for interchange amongst them are

shown diagramatically. 28 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.597199

Item 220Synthetic Metals

71, Nos.1-3, 1st April 1995, p.1825-6

FTIR AND NIR-FT-RAMAN STUDY OFPOTENTIAL MOLECULARFERROMAGNETICS - POLY(DIACETYLENES)SUBSTITUTED WITH NITROXYL RADICALSShchegolikhin A N; Lazareva O L; Ovchinnikov A A;

Spector V N

Moscow,Institute of Chemical Physics

FTIR spectroscopy and near-infrared-FT-Raman

spectroscopy were used to study the molecular structural

transformations which occurred during thermal treatment

of several nitroxyl substituted diacetylene monomers.

These spectroscopic techniques were also used to

investigate the solid state polymerisation reactions of the

nitroxyl-substituted monomers, “classic” diacetylenes and

of polydiacetylenes. The results were discussed. 7 refs.

RUSSIA

Accession no.596062

Item 221Journal of Applied Polymer Science

61, No.2, 11th July 1996, p.231-54

MICRO-RAMAN IMAGING OFHETEROGENEOUS POLYMER SYSTEMS:GENERAL APPLICATIONS AND LIMITATIONSMarkwort L; Kip B

DSM

Using micro-Raman imaging three blends consisting of

polypropene/polyethene/ethene-propene copolymer,

PBTP/polycarbonate/LDPE, and styrene-acrylonitrile

copolymer/styrene-maleic anhydride copolymer/

polydimethylphenylene oxide were studied with regard

to compositional and morphological heterogeneities. The

general structure of PE fibres in an epoxy resin matrix

was also studied. 59 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; WESTERN EUROPE

Accession no.595775

Item 222Applied Spectroscopy

50, No.6, June 1996, p.708-14

EFFECTS OF SAMPLING PARAMETERS ONPRINCIPAL COMPONENTS ANALYSIS(PCA) OFRAMAN LINE IMAGESHayden C A; Morris M D

Michigan,University

References and Abstracts

96 © Copyright 2001 Rapra Technology Limited

The effects of spectrometer slit width, spatial resolution

and number of spectral variables used for PCA analysis of

Raman line-images were studied. Depth of penetration and

signal-to-noise considerations dominated the proper

selection of slit width for the sample used in this study, 10-

micrometre-diameter PS spheres embedded in an epoxy

resin matrix. With the use of different microscope objectives

to analyse the same sample region, the higher-magnification

objective gave better results, probably due merely to the

larger number of spectra processed. Finally, the number of

spectral variables could be reduced significantly before

degradation of the PCA image had occurred, especially if

the variables were carefully chosen. 9 refs.

USA

Accession no.595341

Item 223Journal of Polymer Science : Polymer Physics Edition

32, No.12, Sept.1994, p.2065-75

FTIR-ATR STUDIES OF DRAWING ANDPOLING IN POLYMER BILAMINATE FILMSGang Chi Chen; Ji Su; Fina L J

Rutgers,University

FTIR-ATR spectroscopy was used to examine the

structural variations as a function of depth for drawn and

poled single nylon-11 and PVDF films and PVDF/nylon-

11 bilaminates. Simple one-way drawing in PVDF and

nylon-11 produced anisotropy in dipole orientation in the

plane transverse to the draw direction. In both single and

bilaminate films, the average direction of the amide plane

in nylon-11 and the CF2 dipoles in PVDF residues resided

in the plane of the film, perpendicular to the subsequent

poling field direction as a result of one-way drawing. The

transverse plane orientation was depth dependent in

nylon-11 in both single and bilaminate films and was

attributed to a surface-induced effect. Poling fields of 1.6

MV/cm produced large differences between the surfaces

of single films and the bilaminates. The PVDF and nylon-

11 dipoles important in polarisation appeared to be

random at the interior interface of the drawn and poled

bilaminates. The results were discussed. 36 refs.

USA

Accession no.593532

Item 224Kautchuk und Gummi Kunststoffe

49, No.5, May 1996, p.354-6

DETERMINATION OF THE SOLUBILITY OFSULPHUR IN ELASTOMERS USING FOURIERTRANSFORM RAMAN SPECTROSCOPYBrimblecombe A; Hendra P J; Wallen P; Chapman A;

Jackson K; Loadman J; Van Duin M; Kip B; Hofstraat J

W; Schreurs H

Southampton,University; Malaysian Rubber Producers’

Research Assn.; DSM Research; Akzo Nobel Central

Research BV

Solubility of elemental sulphur in NR, EPDM, synthetic

polyisoprene and deproteinised NR was determined over

a period of 5 days. By varying the amount of sulphur

added to the elastomers, heating the mixtures and

analysing them on cooling in a Fourier Transform Raman

instrument, both the immediate and long-term solubility

could be assayed. Some of the non-elastomeric

components could influence the rate and level of

crystallisation. 11 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; UK; WESTERN EUROPE

Accession no.592027

Item 225Applied Spectroscopy

50, No.5, May 1996, p.558-63

DEPTH PROFILING OF POLY(METHYLMETHACRYLATE), POLY(VINYL ALCOHOL)LAMINATES BY CONFOCAL RAMANMICROSPECTROSCOPYHajatdoost S; Yarwood J

Sheffield,Hallam University

It is demonstrated that this technique can be successfully

used to study the hydrogen bonding interaction between

the ester and alcohol groups near the interfacial region.

Various laminates have been studied, and it is

demonstrated that the PMMA layers with lower molecular

weight show a greater degree of interpretation for a given

annealing time.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.590639

Item 226Journal of Elastomers & Plastics

28, No.2, April 1996, p.140-60

QUANTITATIVE CHARACTERISATION OFPOLYMER STRUCTURE BY PHOTOACOUSTICFOURIER TRANSFORM INFRAREDSPECTROSCOPYParker J R; Waddell W H

PPG Industries Inc.

The use of photoacoustic FTIR spectroscopy in quantitative

analysis of polymers was investigated with reference to

determination of vinyl acetate in EVA, acrylonitrile in NBR,

ethylene in EPDM, styrene in SBR and vinyl-butadiene in

SBR. The results obtained indicated that, despite the

theoretical complexities of photoacoustic FTIR

spectroscopy, simple quantitative relationships could be

found for many of these polymer analyses. 24 refs.

USA

Accession no.590610

Item 227Polymer

37, No.8, 1996, p.1295-303

References and Abstracts

© Copyright 2001Rapra Technology Limited 97

MONITORING OF REACTIVE PROCESSING BYREMOTE MID INFRA-RED SPECTROSCOPYMijovic J; Andjelic S

Brooklyn,Polytechnic University

An alternative approach to remote mid infra-red

spectroscopy is presented which utilises gold-coated

waveguides instead of fibre optics and which could be

used for in-situ real-time process control in practically

any environment. The principle objects of the paper are

to describe a novel experimental set-up for remote mid

infra-red spectroscopy recently assembled in laboratory,

and to demonstrate the qualitative and quantitative

analysis of the remote mid infra-red data using a

multifunctional epoxy/amine formulation as an example.

18 refs.

USA

Accession no.588252

Item 228Acta Polymerica

47, No.4, April 1996, p.170-6

FTIR SPECTROSCOPIC STUDIES ON THEINTERFACIAL REACTIONS OF OXAZOLINE-FUNCTIONALISED POLYMERSSchaefer R; Kressler J; Muelhaupt R

Freiburg,Universitat

The interfacial reaction of immiscible polymeric systemscontaining oxazoline and carboxylic acid groups,

respectively, was studied by FTIR spectroscopy and FTIR

microscopy. A poly(butadiene-co-acrylonitrile) rubber,

where the nitrile groups are partially converted to

oxazoline groups, was thermally annealed in a two-layer

specimen with poly(ethylene-co-methacrylic acid). The

formation of the esteramide in the interface was measured

quantitatively by FTIR difference spectroscopy. 33 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.588230

Item 229Acta Polymerica

47, No.4, April 1996, p.161-9

SPECTROSCOPIC AND QUANTITATIVECHARACTERISATION OF VARIOUSFRACTIONS OF THE HETEROGENEOUSPOLYMER SYSTEM (EPDM-G-MALEICANHYDRIDE)-G-POLYAMIDE 66 USING HIGHRESOLUTION CARBON-13 SOLID STATE NMRAND IR TECHNIQUESvan der Velden G; Nelissen H; Veermans T

DSM Research Bv

The structure of EPDM grafted onto polyamide 66 was

analysed with high resolution solid state carbon-13 NMR

and IR spectroscopy. Details about the EPDM rubber

include the amount of rubber incorporated into this blend,

the sequence analysis of the EPDM rubber and an estimate

of the type and amount of termonomer used (in this case

only trans 1,4-hexadiene). The sample contains 20%

EPDM rubber, 6% polyamide 66 grafted onto EPDM

rubber and 74% neat polyamide 66. Some evidence was

obtained via IR spectroscopy for the presence of cyclic

imide groups, derived from grafted maleic anhydride

groupings. No evidence for the use of a coupling agent

could be obtained from either the carbon-13 single pulse

excitation-magic angle spinning spectra of the interphase

enhanced polyamide 66 or from the isolated rubber phase.

45 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; WESTERN EUROPE

Accession no.588229

Item 230Journal of Applied Polymer Science

60, No.1, 4th April 1996, p.29-35

STUDY OF DIFFUSION AND SORPTION OF BIS-(2-CHLOROETHYL)SULPHIDE (SM) AND BIS-(2-CHLOROETHYL)ETHER (OM) THROUGHPOLYPROPYLENE (PP) AND BIAXIAL-ORIENTED POLYPROPYLENE (BOPP) FILMSBY THE FTIR-ATR SPECTROSCOPIC METHODSemwal R P; Banerjee S; Chauhan L R; Bhattacharya

A; Rao N B S N

India,Defence Research & Development Organisation

Diffusion of sulphur mustard (SM) and oxygen mustard

(OM) in PP and BOPP were measured using FTIR-ATR

spectroscopy, which permits the study of the diffusion of

liquid through thin polymer films in-situ. The

temperature-dependent diffusion coefficients of OM and

SM for PP and BOPP were also reported; these were in

good agreement with values obtained by the weight gain

method. Activation energy of diffusion was determined

by both methods. The polymer-penetrant interaction

parameter and transport number were calculated for the

system PP/OM and BOPP/OM by weight gain method.

24 refs.

INDIA

Accession no.585950

Item 231Journal of Polymer Science : Polymer Physics Edition

34, No.4, March 1996, p.781-8

ELECTRIC FIELD-INDUCED DIPOLEREORIENTATION IN ORIENTED NYLON 11 BYIN SITU INFRARED SPECTROSCOPYHsin Her Yu; Fina L J

Rutgers,University

Dipole reorientation under the influence of an electric field

was investigated in oriented nylon 11 films with polarised

IR spectroscopy for the amide A (N-H stretching) and

amide I (carbonyl stretching) bands. Butterfly-shaped

hysteresis loops were obtained from peak intensity versus

applied electric field strength. Least-squares Gaussian

References and Abstracts

98 © Copyright 2001 Rapra Technology Limited

curve fitting of the resolved multiple contributions to the

amide I peak show that the components change in either

a continuously reducing S-shaped fashion, or in butterfly-

shaped curves under ac poling fields. Time-dependent

studies of the absorption intensities show that both ordered

and disordered species switch towards the electric field

direction with the application of electric fields higher than

the coercive field. Upon field removal, only the disordered

species show orientation relaxation away from the field

direction. Below the coercive field, neither species

responds orientationally to the field. 12 refs.

USA

Accession no.585313

Item 232Euradh ’94. Conference Proceedings.

Mulhouse, 12th-15th Sept.1994, p.346-9. 9(12)4

USE OF INTERNAL REFLECTION FTIRSPECTROSCOPY FOR IN-SITU STUDY OFWATER-POLYMER-SUBSTRATE SYSTEMSLinossier I; Gaillard F; Romand M

Lyon,Universite Claude Bernard

(Societe Francaise du Vide; Institute of Materials;

Dechema Institut)

Multiple internal reflection FTIR spectroscopy was used for

the in-situ determination of water diffusion coefficient

through thin PMMA films. The technique was also used to

study water uptake at the interface of an adhesive-substrate

system and the effect of surface treatment of the substrate

on this parameter. These studies were done to assess adhesion

loss and durability of polymer-substrate joints. 7 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.584869

Item 233Euradh ’94. Conference Proceedings.

Mulhouse, 12th-15th Sept.1994, p.85-9. 9(12)4

QUANTITATIVE I.R.R.A.S. ANALYSIS OF ACID-BASE INTERFACIAL INTERACTIONS INVARIOUS POLYMER/METAL MODELSYSTEMS: RELEVANCE TO ADHESIONBrogly M; Nardin M; Schultz J

Centre de Recherches sur Physico-Chemie Surf.Sol.

(Societe Francaise du Vide; Institute of Materials;

Dechema Institut)

Ethylene-vinyl acetate copolymer, terpene-phenol resins,

polyethylene oxide, PMMA and some of their blends were

solution cast on basic (aluminium oxide) and acidic

(hydroxylated glass) substrates. Fourier transform infrared

reflection absorption spectroscopy (IRRAS) was used to

determine both the nature and the free energy of interfacial

adduct formation in the polymer/metal systems. A

correlation between IRRAS and adhesive strength may

be used to predict both the acid-base work of adhesion

and the density of interfacial interacting sites. 14 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.584819

Item 234Applied Spectroscopy

50, No.3, March 1996, p.388-93

DENSITY MAPPING IN POLY(ETHYLENETEREPHTHALATE) USING A FIBRE-COUPLEDRAMAN MICROPROBE AND PARTIAL LEAST-SQUARES CALIBRATIONEverall N; Davis K; Owen H; Pelletier M J; Slater J

ICI PLC

Partial least-squares analysis was used to calibrate Raman

microprobe spectra of PETP films in terms of density, to

give insight into changes in crystallinity through the film

thickness. The microprobe uses a static multiplexed

holographic grating to obtain the entire Raman spectrum

in a single shot. 13 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.584714

Item 235Applied Spectroscopy

50, No.3, March 1996, p.377-81

DYNAMIC STEP-SCAN TWO-DIMENSIONALFOURIER TRANSFORM INFRARED STUDIESOF UNIAXIALLY DRAWN POLY(ETHYLENETEREPHTHALATE) FILMSonoyama M; Shoda K; Katagiri G; Ishida H

Toray Research Center Inc.

Dynamic two-dimensional IR spectra of uniaxially drawn

PETP under a sinusoidal strain were examined. 39 refs.

JAPAN

Accession no.584712

Item 236Cellular Polymers III. Conference proceedings.

Coventry, 27th-28th April 1995, paper 3. 6124

USE OF FTIR TO ANALYSE FIRE GASES FROMBURNING POLYURETHANE FOAMSPaul K T

Rapra Technology Ltd.

(Rapra Technology Ltd.)

A large number of different techniques may be used to

analyse fire gases including gas chromatography, mass

spectrometry, infrared absorption, ion chromatography,

chemiluminescence, specific ion electrodes as well as

various colourmetric and titrametric techniques. The use

of Fourier Transform Infrared Analysis (FTIR) enables a

number of the more important gases to be determined

continuously. These gases include those of particular

importance to polyurethane foam containing fires, e.g.

hydrogen cyanide, nitrogen oxides, hydrogen chloride and

References and Abstracts

© Copyright 2001Rapra Technology Limited 99

hydrogen bromide (from flame retardant additives) as well

as carbon monoxide and carbon dioxide which are

produced from all fires. The use and limitations of FTIR

to analyse fire gases in general is discussed and the fire

gases produced by burning polyurethane foams of

different types are compared. 4 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.583878

Item 237Journal of Materials Science

31, No.4, 15th Feb.1996, p.851-60

CHARACTERISATION OF PAN-BASEDCARBON FIBRES WITH LASER RAMANSPECTROSCOPY. I. EFFECT OF PROCESSINGVARIABLES ON RAMAN BAND PROFILESMelanitis N; Tetlow P L; Galiotis C

Queen Mary & Westfield College

Laser Raman spectroscopy was used to characterise the

structure and morphology of a series of carbon fibres, to assess

the ultimate firing temperature and pregraphitisation drawing

during manufacture and to investigate the influence of

oxidative treatment upon the integrity of the fibre surface.

Ten types of polyacrylonitrile-based carbon fibres of varying

modulus, diameter and manufacturing method, were

examined. All their spectral features were recorded and

analysed in terms of position, bandwidth and band intensity.

The observed Raman spectra are discussed in detail and related

to alterations in the conditions of manufacture. 49 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.581295

Item 238Journal of Applied Polymer Science

59, No.9, 28th Feb.1996, p.1417-26

POLYMERISATION KINETICS OFPOLYURETHANE AND VINYL ESTER RESININTERPENETRATING POLYMER NETWORKSBY USING FOURIER TRANSFORM INFRAREDSPECTROSCOPYLian Hua Fan; Chun Pu Hu; Zhi Ping Zhang; Sheng

Kang Ying

East China,University of Science & Technology

FTIR was applied to the study of polymerisation kinetics

of simultaneous interpenetrating polymer networks

composed of PU and vinyl ester resin at a temperature range

from 60-110C within 0.5h, in which the pendant hydroxyl

groups were capped with acetyl groups to minimise the

possibility of chemical binding between the two networks.

The comparison of vinyl ester resin with or without its

pendant hydroxyl groups was also made to examine the

intercomponent chemical binding effect. 18 refs.

CHINA

Accession no.580925

Item 239Macromolecules

29, No.1, 1st Jan.1996, p.239-46

STUDY OF THE MECHANISM AND RATE OFBISMALEIMIDE CURE BY REMOTE IN-SITUREAL TIME FIBRE OPTIC NEAR-INFRAREDSPECTROSCOPYMijovic J; Andjelic S

Brooklyn,Polytechnic University

The formulation comprised 4,4'-methylenebis-

(maleimidobenzene) (Matrimid 5295) and 2,2'-

diallylbisphenol A. In-situ real time study of the progress

of the reaction was conducted in the temp. range from

140 to 250C using remote fibre optic near IR spectroscopy.

The signal was clean, free from noise, and remarkably

reproducible. The principal reaction observed was an

alternating copolymerisation involving maleimide and

allyl double bonds. Maleimide homopolymerisation was

detected only in the initial stages of reaction at

temperatures above 200C. The extent of self-condensation

(or etherification) of hydroxyl groups on the allyl

component, which leads to crosslinking, was observed to

vary with reaction temperature, suggesting a path to tailor-

making networks with desired morphology and physical/

mechanical properties. 23 refs.

USA

Accession no.580381

Item 240Journal of Polymer Science : Polymer Chemistry

Edition

34, No.3, Feb.1996, p.403-11

KINETICS OF CATIONICPHOTOPOLYMERISATIONS OF DIVINYLETHERS CHARACTERISED USING IN-SITURAMAN SPECTROSCOPYNelson E W; Scranton A B

Michigan,State University

In-situ Raman spectroscopy experiments were used to

determine effective kinetic propagation constants for a

series of unsteady-state divinyl ether polymerisations at

different isothermal temperatures and light intensities. A

series of Raman experiments were performed on cationic

photopolymerisations of a divinyl ether initiated with a

diaryliodonium salt of hexafluoroantimonate

photosensitised by anthracene. Isothermal Raman

experiments were performed for a series of reaction

temperatures and were used to determine the overall

activation energy of the polymerisation reaction. 20 refs.

USA

Accession no.578838

Item 241Composite Interfaces

3, No.3, 1995, p.221-30

EFFECT OF THE MOLECULAR WEIGHT ON

References and Abstracts

100 © Copyright 2001 Rapra Technology Limited

THE SURFACE COMPOSITION OFPOLYCARBONATE/POLY(ETHYLENETEREPHTHALATE) BLENDS BY FOURIERTRANSFORM IR ATTENUATED TOTALREFLECTANCE SPECTROSCOPYKugo K; Watanabe E; Kitaura T; Nishino J

Konan,University; Gunze Ltd.

The surface structure of melt-mixed blends of bisphenol

A polycarbonate and PETP was investigated by FTIR

attenuated total reflectance spectroscopy. Based on the

peak intensity of the aromatic carbonate band for

polycarbonate and the aliphatic ester band for PETP by

using germanium and KRS-5 ATR crystals, the

enrichment of the PETP component in the surface layer

of the polycarbonate/PETP blend films was observed.

27 refs.

JAPAN

Accession no.577664

Item 242Journal of Applied Polymer Science

59, No.3, 18th Jan.1996, p.511-20

DYNAMIC FTIR METHOD FOR DETERMININGTHE CURING TEMPERATURE RANGES OF ANACETYLENE-TERMINATED POLYISOIMIDEPREPOLYMERHuang W X; Wunder S L

Temple University

To determine individual curing temperature ranges of the

isoimide-imide isomerisation and crosslinking reactions,

a rapid scan dynamic FTIR method was developed in

which the two reactions were continuously monitored as

the sample was heated at constant rate. Isothermal kinetic

data was obtained on FTIR spectrometers using their fast

scan capability and GC-IR software. Dynamic FTIR was

used with a common kinetics program to monitor the two

separate reactions occurring during thermal curing of the

acetylene-terminated polyisoimide prepolymer Thermid

IP-600 and to determine individual curing temperature

ranges of the isoimide-imide isomerisation and

crosslinking reactions. Results were compared with

dynamic FTIR and the dynamic DSC data obtained for a

model compound, IP-6001. 22 refs.

USA

Accession no.577637

Item 243Polymer Bulletin

36, No.1, Jan.1996, p.87-94

RHEO-OPTICAL FOURIER TRANSFORMINFRARED SPECTROSCOPY OF A LIQUIDCRYSTALLINE BLOCK COPOLYMERZebger I; Pospiech D; Boehme F; Eichhorn K J; Siesler

H W

Essen,University; Dresden,Institute of Polymer

Research

Rheo-optical experiments were conducted in which FTIR

polarisation spectroscopy was used to investigate the

orientational behaviour of the different constituents of a

liquid crystalline block copolymer (copolyester-imide)

during uniaxial elongation at different temps. The results

exhibited differences in the degree of alignment as well

as in the response to the application of the mechanical

load. With increasing temp., the level of the applied stress

and the induced degree of orientation decreased, while

the differences in the orientational behaviour of the

mesogen and the flexible spacer were retained. 12 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.576734

Item 244Macromolecules

28, No.24, 20th Nov.1995, p.8209-15

SULPHONATED POLYSTYRENE IONOMERSNEUTRALISED BY BI- ANDMULTIFUNCTIONAL ORGANIC CATIONS. I.AN INFRARED SPECTROSCOPIC STUDYXiao-Dong Fan; Bazuin C G

Quebec,Universite Laval

An FTIR investigation of lightly sulphonated PS blended

with ten different organic small molecules containing bi-,

tri-, and quadrifunctional amine or pyridine groups was

undertaken. Proton transfer from the sulphonic acid

moieties of the polymer to the nitrogen functions of the

small molecules, giving rise to ion pairs and hence ionic

crosslinking, was clearly detected. the extent of proton

transfer was correlated qualitatively with the relative

basicity of the small molecule. A quantitative calculation

of the degree of proton transfer was performed, based

primarily on the normalised area of the absorption band

and shoulder at 900-906/cm. The results range from about

50% proton transfer or less to purine, 2,2'-pyridil,, and N-

phenyl-1,4-phenylenediamine to almost complete proton

transfer to 1,6-hexanediamine and 1,4-phenylenediamine.

Other small molecules were 1,4-phenylenediamine, 4,4'-

diaminodiphenylsulphone, 3,3-diaminobenzidine,

hexamethylene tetramine and terpyridine. 31 refs.

CANADA

Accession no.575981

Item 245Journal of Polymer Science : Polymer Physics Edition

32, No.11, Aug.1994, p.1881-7

DEPTH PROFILING OF POLYMER LAMINATESUSING FOURIER TRANSFORM (ATR)SPECTROSCOPY: THE BARRIER FILMTECHNIQUEPereira M R; Yarwood J

Durham,University; Sheffield,Hallam University

FTIR-ATR spectra of a laminate (PMMA/polyvinyl

alcohol) were presented at different base layer thicknesses

References and Abstracts

© Copyright 2001Rapra Technology Limited 101

and different angles of incidence on a zinc selenide

substrate. By varying the thickness of the PMMA barrier

film, different effective penetration depths in the polyvinyl

alcohol were achieved. These results agreed well with

the calculated electric fields as a function of distance away

from the substrate surface. The work provided the basis

for depth profiling measurements to detect interfacial

interactions. 18 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.573664

Item 246Antec ’95. Vol.II. Conference Proceedings.

Boston, Ma., 7th-11th May 1995, p.2458-62. 012

FTIR MICROSPECTROSCOPIC METHOD FORCHARACTERISING THE DRYING OF WATER-BASED COATINGSNedea C E; La H M; Campanelli J R

Domco Industries Ltd.

(SPE)

Fourier transform IR microspectroscopy was used to

investigate the drying of water-based acrylic polymer

coatings on an aluminised substrate. Changes in the

absorbance peak heights were monitored as an indication

of the remaining water content. The effects on drying of

humidity, solids content, coating thickness and the

presence of coalescing agents were studied. Coalescing

agents were found to increase drying time while aiding

film formation. Drying time decreased with increasing

solids content and increased with increasing coating

thickness. As expected, relative humidity was found to

have an important effect on the drying process. 7 refs.

CANADA; USA

Accession no.571348

Item 247Antec ’95. Vol.II. Conference Proceedings.

Boston, Ma., 7th-11th May 1995, p.2057-61. 012

QUALITY MONITORING OF RECYCLEDPLASTICS WASTE DURING EXTRUSION. I. IN-LINE NEAR-INFRARED SPECTROSCOPYReshadat R; Cluett W R; Balke S T; Hall J W

Toronto,University; NIRSystems Inc.

(SPE)

The composition of recycled HDPE/virgin PP blends

prepared in a single-screw extruder was monitored in-

line at three different points by near-infrared spectroscopy.

The data were interpreted by simple and multiple linear

regression and multivariate methods. 5 refs.

CANADA; USA

Accession no.571279

Item 248Macromolecules

28, No.22, 23rd Oct.1995, p.7441-6

FOURIER TRANSFORM INFRARED ANALYSISOF A LINEAR, ANHYDRIDE-CURED EPOXYTadros R; Timm D C

Nebraska,University

A linear-chained epoxy resin was formulated from phenyl

glycidyl ether and nadic methyl anhydride catalysed by

benzyldimethylamine. Intermolecular polymerisations

were modelled as a parallel set of propagation reactions.

FTIR spectroscopy was used to determine the

concentrations of the oxirane, anhydride and ester

moieties within the resin as a function of time for two

isothermal cures. Data analyses yielded the propagation

rate constant as a function of temp. and the concentration

of initiator, including contributions from impurities within

the resin. Results obtained compared favourably with

measurements on fractionated resins, using GPC.

Population density distributions are described by Poisson

molar distributions for this resin. 25 refs.

USA

Accession no.569011

Item 249Composite Interfaces

3, No.2, 1995, p.101-19

PHYSICOCHEMICAL CHARACTERISATIONOF THE FIBRE/MATRIX INTERACTION INPOLYETHYLENE FIBRE/EPOXY MATRIXCOMPOSITES. II. CHARACTERISATION OFTHE INTERPHASE WITH FTIRMICROSPECTROSCOPYVan Mele B; Verdonck E

Brussels,Free University

The interphase in PE fibre/epoxy resin matrix composites

was studied by FTIR microspectroscopy using a set-up

for investigation of the matrix as close to the fibre as a

few microns or less. It was shown that moisture present

on the fibre surface could influence the polymerisation

reaction of the epoxy/anhydride matrix in an irreversible

manner. This effect was enhanced for composites from

the more hydrophilic PVAl fibre. The fibre/matrix

interaction in these thermoplastic fibre composites was

also studied by DSC through characterisation of the fibre

melting. A decreased ‘DSC interaction parameter’ was

found if the composition of the interphase was changed

by moisture. For a composite with an epoxy/amine matrix,

on the other hand, the DSC interaction parameter was

unaffected by moisture from the fibre surface. 22 refs.

(Pt.I, ibid, p.83-100)

BELGIUM; EUROPEAN COMMUNITY; EUROPEAN UNION;

WESTERN EUROPE

Accession no.566704

Item 250Polymer

36, No.22, 1995, p.4233-8

References and Abstracts

102 © Copyright 2001 Rapra Technology Limited

RHEO-OPTICAL RAMAN STUDY OF CHAINDEFORMATION IN UNIAXIALLY STRETCHEDBULK POLYETHYLENERodriguez-Cabello J C; Merino J C; Jawhari T;

Pastor J M

Valladolid,Universidad

A rheo-optical study was developed to examine the nature

of the structural changes, other than chain orientation,

that can appear during uniaxial drawing of PE samples.

Stretching was performed at room temperature in samples

of melt crystallised HDPE and LDPE. Raman spectra were

simultaneously collected along with stress and strain data

to gain insight into the molecular basis of the properties

resulting from the mechanical process. The need for real-

time studies was to detect possible transient occurrences

that cannot be observed with non-rheo-optical studies.

15 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;

WESTERN EUROPE

Accession no.566487

Item 251Polymer

36, No.17, 1995, p.3385-92

ORIENTATION AND CONFORMATION INPOLY(ETHYLENE TEREPHTHALATE) WITHLOW DRAW RATIOS AS CHARACTERISED BYSPECULAR REFLECTION INFRAREDSPECTROSCOPYGuevremont J; Ajji A; Cole K C; Dumoulin M M

Canada,National Research Council

A quantitative treatment of the specular reflection spectra

obtained from the surface of uniaxially drawn PETP

samples was performed. A procedure for correcting for

the effect of surface irregularities is presented, and an

overall orientation function based on the orientation and

content of trans-conformers is calculated. The results are

correlated with mechanical modulus and crystallinity

values. In addition, an unconventional dichroic ratio

parameter based on a combination of two major bands is

proposed. Results obtained from the Kramers-Kronig

analysis and directly from the reflection spectra are

discussed. Both are compared with the overall orientation

function obtained before. 21 refs.

CANADA

Accession no.564806

Item 252Macromolecular Reports

A32, No.7, 1995, p.1077-82

FOURIER TRANSFORM INFRAREDSPECTROSCOPIC STUDY OF CONFORMATIONOF FREEZE-DRIED ISOTACTICPOLYSTYRENEDai Q; Liu X; Wang Y

Nanjing,University

Isotactic PS samples were prepared by shock-cooling and

subsequent freeze-drying from very dilute solutions in

benzene. FTIR studies on these samples indicated that

there were conformational differences between them and

a normal isotactic PS. Comparison of the IR spectra

indicated that spectral changes occurred at the bands near

1261, 1085-1050, 982, 923-906 and 550/cm. The changes

in intensities of the crystalline bands showed that the

freeze-dried isotactic PS from a very dilute solution

exhibited a higher crystallinity than the annealed sample.

11 refs.

CHINA

Accession no.564742

Item 253Journal of Applied Polymer Science

58, No.3, 17th Oct.1995, p.501-14

RHEO-OPTICAL FTIR SPECTROSCOPY OFEPOXY RESINSScherzer T

Halle,Martin-Luther-Universitat

The use of rheooptical FTIR spectroscopy to monitor

orientation phenomena in highly crosslinked epoxy/amine

networks during uniaxial deformation above their Tg was

investigated. The resins were prepared from the diglycidyl

ether of bisphenol-A and various polyether di- and

triamines in order to examine the influence of the structure

of the network formed. The molecular orientation was

studied in relation to network density and structure. The

orientation behaviour was mainly determined by the

flexibility of the polyether chain and the homogeneity of

the network structure. The epoxy resins were also

subjected to successive loading-unloading cycles. The

results showed that the orientation of epoxy networks in

their rubbery state was completely reversible and that no

significant fatigue due to gradual chain rupture occurred

until sample failure. 29 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.563380

Item 254Applied Spectroscopy

49, No.8, Aug.1995, p.1073-8

DYNAMIC TWO-DIMENSIONAL INFRAREDSPECTROSCOPY. I. MELT-CRYSTALLISEDNYLON 11Singhal A; Fina L J

Rutgers,University

Two-dimensional FTIR spectroscopy was used to study

the N-H stretching and amide I/amide II region of melt-

crystallised nylon 11 thin films on Teflon substrates. The

samples were dynamic mechanically oscillated at room

temp. at a frequency of 11 Hz. A two-dimensional

correlation analysis on the dynamic spectra indicated that

the N-H stretching region split into two peaks. Analysis

References and Abstracts

© Copyright 2001Rapra Technology Limited 103

of two-dimensional crossplots between the N-H stretching

region and the amide I/amide II region showed that the

prominent peak in the N-H stretching region (about 3300/

cm) was similar in morphological character to the ordered

peak of the amide I region. The amide II region resolved

into two ordered and one disordered peak. 28 refs.

USA

Accession no.563353

Item 255Polymer Science Series B

37, Nos.5-6, May-June 1995, p.289-92

IR SPECTROSCOPIC STUDY OF THESTRUCTURE OF POLY(VINYL ALCOHOL)-POLY(GLYCIDYL METHACRYLATE) GRAFTCOPOLYMERSBuslov D K; Korolik E V; Zhbankov R G; Druzhinina

T V; Nazar’ina L A; Smolenskaya L M

Belarus Academy of Sciences; Moscow,Textile Institute

PVAl, poly(glycidyl methacrylate) and their copolymer

(obtained by radical graft polymerisation of glycidyl

methacrylate onto PVAl fibres) were studied by IR

spectroscopy. The spectrum of the graft copolymer was

also obtained by mathematical modelling. The spectra

regions sensitive to the sites of localisation of the kinetic

chains of grafted poly(glycidyl methacrylate) are found

within 3600-3100, 1450-1300, 1120-1000 and 700-500/

cm, which correspond to the stretching and bending OH

vibrations, stretching carbon-oxygen vibrations, and

torsional vibrations of the hydroxyl groups, respectively.

It was established that grafted poly(glycidyl methacrylate)

molecules are linked to PVAl macromolecules via oxygen

atoms of hydroxyl groups. 12 refs.

BELARUS; RUSSIA

Accession no.562450

Item 256Journal of Polymer Science : Polymer Physics Edition

32, No.8, June 1994, p.1493-502

FTIR STUDY OF PVDF IRRADIATED BYMEANS OF SWIFT HEAVY IONSBetz N; Le Moel A; Balanzat E; Ramillon J M;

Lamotte J; Gallas J P; Jaskierowicz G

DRECAM/SRSIM; CEA-CNRS; ISMRA;

Palaiseau,Ecole Polytechnique

Fourier transform IR measurements were used to

investigate PVDF films which had been irradiated by

means of heavy ions (krypton ions) and electrons.

Irradiation with krypton ions was carried out in the

presence of helium, hydrogen, deuterium and oxygen.

Triple bonds were characteristic of krypton ion irradiation.

Double bonds (isolated and conjugated) occurred with

both types of irradiation but concentrations were higher

with the krypton radiation. The results, including the role

of oxygen on the chemical modifications, were discussed.

36 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.562089

Item 257Journal of Polymer Science : Polymer Physics Edition

32, No.8, June 1994, p.1315-20

FTIR ANALYSIS OF HYDROGEN BONDING INAMORPHOUS LINEAR AROMATICPOLYURETHANES. II. INFLUENCE OFSTYRENE SOLVENTWang F C; Feve M; Lam T M; Pascault J-P

URA CNRS

FTIR studies were carried out on a polyurethane gel

synthesised by reacting the alpha,omega-hydroxy-

terminated random copolyadipate of ethanediol and

butanediol with 4,4'-diphenylmethane diisocyanate in

solution with 30% to 90% (w/w) of styrene. The results

of studying N-H vibrations in the stretching and bending

regions showed that the N-H groups of the PU could

hydrogen bond with C=O groups and other groups in this

system. Some of the aromatic rings of the styrene were

hydrogen bonded with the N-H groups of the PU. The

mole fractions of “free” N-H groups and of N-H groups

hydrogen bonded to C=O groups and to the pi orbitals of

the aromatic rings were calculated. 9 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.562071

Item 258Journal of Polymer Science : Polymer Physics Edition

32, No.7, May 1994, p.1163-74

RAMAN SPECTRAL STUDY OF SOLID ANDDISSOLVED POLY(VINYL ALCOHOL) ANDETHYLENE-VINYL ALCOHOL COPOLYMERCooney T F; Wang L; Sharma S K; Gauldie R W;

Montana A J

Hawaii,University; Warner-Lambert Co.,Novon

Products Group

The Raman spectra of ethylene-vinyl alcohol copolymer

and poly(vinyl alcohol) were measured and compared.

The spectral changes that occurred during the dissolution

of poly(vinyl alcohol) in, and the precipitation of films

of poly(vinyl alcohol) from, both water and deuterium

oxide were studied and the results were discussed. 46 refs.

USA

Accession no.562058

Item 259Journal of Applied Polymer Science

57, No.13, 26th Sept.1995, p.1585-94

QUANTITATIVE ANALYSIS OFFLUOROCARBON POLYMER FINISHES ONWOOL BY FTIR SPECTROSCOPYChurch J S; Evans D J

References and Abstracts

104 © Copyright 2001 Rapra Technology Limited

CSIRO

Two contrasting IR spectroscopic techniques, ATR and

photoacoustic spectroscopy, were investigated as means

for the determination of fluorocarbon polymer finishes

on wool fabric. Based on the experimental conditions

used, the results of the photoacoustic spectroscopy method

are more characteristic of the bulk sample, while the ATR

results are more surface specific. Linear calibrations

between polymer addition, as determined by total fluorine

analysis, and the absorbance of the C-F stretching bands

of the normalised spectral data were obtained for a typical

commercial fluorocarbon polymer. The quantitative

methods developed are used to help access the effects of

wear and the subsequent heating of fluorocarbon polymer-

treated fabric samples. 21 refs.

AUSTRALIA

Accession no.561437

Item 260Polymer Testing

14, No.5, 1995, p.489-94

QUANTITATIVE APPLICATION OF DRIFTSPECTROSCOPY: DETERMINATION OFCOMPOSITION OF SPECIAL ACRYLIC FIBRESPandey G C; Rao K V; Kumar A

Indian Petrochemicals Corp.Ltd.

A fast, direct and non-destructive method involving nosample preparation was developed for recording a well-

resolved and reproducible spectrum of special acrylic fibre

(SAF), a precursor for carbon fibre using diffuse

reflectance infrared Fourier transform (DRIFT)

spectroscopy. A novel method was developed for

determining the composition of SAF containing both

acrylate and carboxylic acid comonomers. The special

feature is that no standard samples (of known

composition) are required. 11 refs.

INDIA

Accession no.559472

Item 261Polymer Engineering and Science

35, No.12, June 1995, p.1011-5

IDENTIFICATION OF PLASTIC WASTE USINGSPECTROSCOPY AND NEURAL NETWORKSScott D M; Waterland R L

Du Pont de Nemours E.I.,& Co.Inc.

A new approach is described for the automated sorting of

post-consumer plastic waste. It is shown that rapid and

reliable identification of polymers can be achieved using

a combination of fixed-filter near-IR spectroscopy and

neural network data analysis. The effectiveness of the

method is demonstrated for sorting PETP, HDPE, and

PVC. 11 refs.

USA

Accession no.558755

Item 262Macromolecules

28, No.15, 17th July 1995, p.5163-6

REAL-TIME ATTENUATED TOTALREFLECTANCE-FOURIER TRANSFORMINFRARED SPECTROSCOPY TO MONITORMULTIACRYLATE POLYMERISATIONREACTIONSDietz J E; Elliott B J; Peppas N A

Purdue,University

Real-time attenuated total reflectance FTIR spectroscopy

was used to follow the conversion during acrylate

polymerisations by measuring the presence of functional

groups at finite depths from the crystal surface. By varying

the film thickness, the reactivity of multiacrylates could

be spatially resolved. These results were compared with

results from different photocalorimetric studies. 22 refs.

USA

Accession no.558238

Item 263Macromolecules

28, No.11, 22nd May 1995, p.4040-3

REAL-TIME INFRARED CHARACTERISATIONOF REACTION DIFFUSION DURINGMULTIFUNCTIONAL MONOMERPOLYMERISATIONSAnseth K S; Decker C; Bowman C N

Colorado,University; Ecole Nationale Superieure de

Chimie de Mulhouse

Reaction diffusion is defined as radicals moving by

propagating through unreacted double bonds and its

significance, rather than segmental diffusion, in the

termination reaction is pointed out. Diethylene glycol

dimethacrylate was polymerised by UV light. Initiation

was stopped at 18% conversion of double bonds and the

dark reaction was monitored for 50s by real-time IR

spectroscopy. The point at which reaction diffusion began

to dominate termination could be accurately determined.

The reaction diffusion parameter was found to be

independent of the length of time the polymerisation was

monitored in the dark. The method was found to be

particularly useful for analysing high conversion kinetics.

Results were obtained also for poly(ethylene glycol 200)

dimethacrylate and poly(ethylene glycol 600)

dimethacrylate. By selecting these monomers, the range

of glassy to rubbery polymer networks was spanned. 19

refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

USA; WESTERN EUROPE

Accession no.557329

Item 264Applied Spectroscopy

49, No.6, June 1995, p.747-53

SIMULTANEOUS DETERMINATION OF

References and Abstracts

© Copyright 2001Rapra Technology Limited 105

RUBBER ADDITIVES BY FTIRSPECTROPHOTOMETRY WITHMULTIVARIATE CALIBRATIONBlanco M; Coello J; Iturriaga H; Maspoch S; Bertran E

Barcelona,Universidad Autonoma

A new method for the determination of vulcanised rubber

additives by FTIR spectrophotometry using partial least-

squares regression (PLSR) for multivariate calibration

was developed. The effect of various wavenumber ranges

and the use of the absorbance and first-derivative spectral

modes on performance were studied by applying the

method to three different sample batches containing

several additives in different proportions all of which were

resolved with satisfactory results. 15 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;

WESTERN EUROPE

Accession no.555868

Item 265Polyurethanes ’94. Conference proceedings.

Boston, Ma., 9th-12th Oct.1994, p.381-3. 43C6

MONITORING THE PRODUCTION OFPOLYURETHANES WITH NEAR-INFRAREDSPECTROSCOPYHall J W; DeThomas F A

NIRSystems Inc.

(SPI,Polyurethane Div.)

By the use of near-infrared instrumentation designed

specifically for the process environment, the isocyanate

content of a urethane polymerisation reaction is monitored

in real-time. A standard error of prediction of 0.15% is

achieved. Real-time chemical process and analysis yields

improvement in product consistency and quality while

maximising process efficiency. 4 refs.

USA

Accession no.555628

Item 266Polyurethanes ’94. Conference proceedings.

Boston, Ma., 9th-12th Oct.1994, p.375-80. 43C6

APPLICATIONS OF RAMAN SCATTERING TOPLASTICS RECYCLING AND PROCESSMONITORINGBen-Amotz D; Laplant F; Jiang Y; Biermann T

Edited by: Purdue,University; BASF Corp.

(SPI,Polyurethane Div.)

The composition of a polymeric material is of interest

throughout its useful life. From process stream to product

fabrication, and finally to post-consumer recycling, it is

desirable to know not only what types of materials are

present, but also their relative concentrations. In many cases,

Raman spectroscopy can provide a quick, convenient and

relatively inexpensive alternative conventional analytical

method for performing these types of determinations. 15 refs.

USA

Accession no.555627

Item 267Polyurethanes ’94. Conference proceedings.

Boston, Ma., 9th-12th Oct.1994, p.280-5. 43C6

IMPROVED TECHNIQUE FOR THEDETERMINATION OF ISOCYANURATE ANDISOCYANATE CONVERSION BYPHOTOACOUSTIC FTIRBhattacharjee D; Engineer R

Dow Chemical Co.

(SPI,Polyurethane Div.)

Conventional rigid polyisocyanurate foams blown with

HCFC-141b often suffer from poorer compressive

strengths, dimensional stability and inferior

inflammability properties when compared to foams blown

with CFC-11. An improved isocyanurate conversion test

by photoacoustic Fourier Transform Infra Red technique

is introduced. The method is not limited to

polyisocyanurate foam, as isocyanate conversion is an

important parameter to follow in PU foams as well,

especially in all carbon dioxide blown foams. The method

is found to be quite reproducible and further statistical

analysis to ensure the validity of this technique is under

way. 8 refs.

USA

Accession no.555511

Item 268Journal of Applied Polymer Science

56, No.12, 20th June 1995, p.1557-60

DETERMINATION OF FILLER CONTENT INTHERMOPLASTIC COMPOSITES BY FTIRANALYSISFuad M Y A; Yaakob I; Rusli O; Ishak Z A M;

Omar A K M

Malaysia,Standards & Industrial Research Inst.; Sains

Malaysia,University

White rice husk ash (predominantly silica) was

incorporated as a filler (10, 20, 30 and 40% by weight)

into PP homopolymer. Absorption peaks at 480, 621 and

790/cm gave good linearity with increasing filler content.

9 refs.

MALAYSIA

Accession no.555101

Item 269Macromolecular Symposia

Vol.94, May 1995, p.75-95

DYNAMIC FTIR SPECTROSCOPY OFPOLYMER FILMS AND LIQUID CRYSTALSGregoriou V G; Palmer R A

Durham,Duke University

The use of continuous-scan and step-scan FTIR

spectroscopic techniques to study the dynamics of the

response of polymer films and liquid crystals to external

perturbations is described. Results are presented for

References and Abstracts

106 © Copyright 2001 Rapra Technology Limited

HDPE, LDPE and SBR, and for pentylcyanobiphenyl and

pentylcyanophenylcyclohexane liquid crystal molecules.

14 refs.

USA

Accession no.554082

Item 270Macromolecular Symposia

Vol.94, May 1995, p.33-49

ROLE OF VIBRATIONAL SPECTROSCOPY-MICROSCOPY TECHNIQUES IN POLYMERCHARACTERISATIONChalmers J M; Everall N J

ICI

Details are given of the use of IR and Raman microscopy/

microprobe spectroscopic techniques for the spatially-

resolved identification, study and characterisation of

polymers. Chemical and physical property

characterisations are discussed. 35 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.554079

Item 271Applied Spectroscopy

49, No.5, May 1995, p.672-8

REAL-TIME, MID-INFRAREDSPECTROSCOPIC IMAGING MICROSCOPYUSING INDIUM ANTIMONIDE FOCAL-PLANEARRAY DETECTIONLewis E N; Levin I W

US,National Institutes of Health

A new approach to mid-IR spectroscopic imaging

microscopy is described in which instrumentation is

designed about an InSb multichannel, focal-plane array

detector and a variable-bandpass dielectric filter. The

system may be configured for either macroscopic or

microscopic applications and high-fidelity, chemically

specific images may be acquired in real time. With the

dielectric filter used in this assembly, continuous tuning

is provided for the IR 4000-2320/cm spectral region with

spectral resolutions of about 35-18/cm at the extremes of

this wavelength interval. The functioning of the imaging

microscope is demonstrated with samples including PS

microspheres, preparation of lipids and an amino acid

embedded in KBr disks, and a tissue sample derived from

a coronal slice of a monkey cerebellum. 10 refs.

USA

Accession no.553706

Item 272147th Meeting, Spring 1995, Conference Preprints.

Philadelphia, Pa., 2nd-5th May 1995, Paper 19, pp.34. 012

USE OF PHOTOACOUSTIC FOURIERTRANSFORM INFRARED SPECTROSCOPY TO

QUANTITATIVELY CHARACTERISEPOLYMER STRUCTUREParker J R; Waddell W H

PPG Industries Inc.,Chemicals Group

(ACS,Rubber Div.)

The potential use of photoacoustic Fourier transform IR

spectroscopy in the quantitative analysis of polymers was

explored by studying the determination of vinyl acetate

in EVA, acrylonitrile in nitrile rubber, ethylene in EPDM,

and styrene and vinyl butadiene in SBR. Despite the

theoretical complexities of this technique, simple

quantitative relationships could be found for many of these

polymer analyses. 24 refs.

USA

Accession no.552356

Item 273Polymer Degradation and Stability

47, No.3, 1995, p.423-33

THERMAL DEGRADATION OF VINYLACETATE-METHACRYLIC ACID COPOLYMERAND HOMOPOLYMERS. 1. AN FTIRSPECTROSCOPIC INVESTIGATION OFSTRUCTURAL CHANGES IN THE DEGRADINGMATERIALMcNeill I C; Ahmed S; Memetea L

Glasgow,University

The thermal degradation in vacuo, up to 500C, of a vinyl

acetate-methacrylic acid copolymer having 65%

alternating units, and of the corresponding homopolymers,

was studied by reflection-absorption FTIR spectroscopy.

PVAc crosslinks form due to double bond formation

through deacetylation. Polymethacrylic acid generates

little unsaturation, but crosslinks by intermolecular

anhydride links. It decomposes above 350C when the

anhydride breaks down with much chain scission. In the

copolymer, both types of crosslinking reactions are

disturbed by lactone formation between alternating vinyl

acetate and methacrylic acid units. The lactone formation

protects the vinyl acetate units from deacetylation and

competes strongly with anhydride formation. Lactone

groups are thermally resistant and can be found in charred

polymer at 440C, next to aromatic rings. At 480C the

lactone decomposes, helping the fusion of the aromatic

rings in the strongly diminished char. 17 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.551478

Item 274Polymer Degradation and Stability

47, No.3, 1995, p.413-21

COMPARISON OF THE THERMALDEGRADATION PRODUCTS OFPOLY(BUTYLENE TEREPHTHALATE) ANDFLAME RETARDANT POLY(BUTYLENE

References and Abstracts

© Copyright 2001Rapra Technology Limited 107

TEREPHTHALATE) FORMULATIONS USING APYROLYSIS FTIR CELLPellow-Jarman M; Hetem M

Southampton,University; General Electric Plastics

Europe

The two flame retardant materials contained two different

heavily brominated aromatic compounds. A simple FTIR

pyrolysis cell was used for the evaluation. On

decomposition, the PBTP polymers gave off mainly water,

carbon dioxide, butadiene, THF and PBTP oligomers. The

flame retardants increased marginally the polymer

decomposition temperature. The merits of the test

equipment are discussed. Results were consistent with

previous TGA results. 7 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION;

NETHERLANDS; UK; WESTERN EUROPE

Accession no.551477

Item 275Applied Spectroscopy

49, No.4, April 1995, p.513-9

ATR SPECTROSCOPIC STUDY OF PMMA/PDMS GRAFT COPOLYMERS USING ABARRIER LAYER METHODMarand E; Smartt L M

Virginia,Polytechnic Institute & State University

The use of an intermediate barrier layer to vary the

penetration depth in an ATR experiment was investigated.Both theoretical and experimental results suggested that

this method could be useful in probing concentration

profiles away from the interface, particularly in the case

of thin films, where variable-angle methods had

limitations. Application of this technique in the study of

PMMA/PDMS graft copolymers deposited onto a copper

oxide surface indicated a preferential presence of the

siloxane component at the oxide interface, a concentration

which tended to decrease with increasing distance into

the bulk of the sample film. 20 refs.

USA

Accession no.550883

Item 276Macromolecules

28, No.8, 10th April 1995, p.2797-806

STUDY OF REACTION KINETICS BY NEAR-INFRARED SPECTROSCOPY. II. COMPARISONWITH DIELECTRIC SPECTROSCOPY OFMODEL AND MULTIFUNCTIONAL EPOXY/AMINE SYSTEMSMijovic J; Andjelic S; Yee C F W; Bellucci F; Nicolais L

New York,Polytechnic University; Napoli,Universita

An investigation of the kinetics of two non-polymer-

forming epoxy/amine model systems and a polymer-

forming multifunctional epoxy/amine formulation (Epon

825 plus 4,4'-methylenedianiline) was carried out by

dielectric and near-IR spectroscopy. Dielectric

measurements were performed in the frequency range

where polarisation by charge migration is the dominant

mechanism and the extent of reaction was calculated from

the measured variation in impedance during reactions.

Near-IR spectroscopy was carried out in the frequency

range between 7100 and 4000/cm, and the extent of

reaction was evaluated from the changes in the

characteristic absorption peaks. Kinetic results determined

by dielectric and near-IR spectroscopy were in excellent

agreement for all systems investigated. 19 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY; USA;

WESTERN EUROPE

Accession no.550458

Item 277Macromolecules

28, No.8, 10th April 1995, p.2787-96

STUDY OF REACTION KINETICS BY NEAR-INFRARED SPECTROSCOPY. I.COMPREHENSIVE ANALYSIS OF A MODELEPOXY/AMINE SYSTEMMijovic J; Andjelic S

New York,Polytechnic University

The model compounds were 1,2-epoxy-3-

phenoxypropane and aniline. In addition other materials

were used to help assign different absorption peaks

observed in the course of the investigation. These included

epoxy resin monomers, i.e. bisphenol A diglycidyl ether

and tetraglycidyl diaminophenyl methane and amine

curing agents, i.e. 4,4'-methylenedianiline and

diaminodiphenyl sulphone. A comprehensive account of

the origin, location, and shifts during reaction of all major

adsorption peaks in the spectral range between 4000 and

7100/cm is provided. Reaction kinetics derived from the

near-IR data were in excellent agreement with the results

obtained by high performance liquid chromatography.

There was a discrepancy between the kinetic predictions

of near-IR and mid-IR analyses. It was established that

the kinetics of epoxy/amine reactions can be accurately

deduced from the near-IR data, while the standard mid-

IR epoxy absorption band at 915/cm was not a unique

measure of the epoxy concentration, and hence its

utilisation in kinetic calculations is questionable unless

appropriate corrections are made. Evidence was presented

for the formation of hydrogen bonding that is directly

related to a critical viscosity of the reactive mixture. 19

refs.

USA

Accession no.550457

Item 278Journal of Polymer Science : Polymer Physics Edition

32, No.3, Feb.1994, p.395-408

TOUGHENING OF A HIGHLY CROSS-LINKEDEPOXY RESIN BY REACTIVE BLENDINGWITH BISPHENOL A POLYCARBONATE. I.FTIR SPECTROSCOPY

References and Abstracts

108 © Copyright 2001 Rapra Technology Limited

Abbate M; Martuscelli E; Musto P; Ragosta G; Scarinzi

G

CAMPEC; Italy,National Research Council

A highly crosslinked epoxy resin was modified by reactive

blending with bisphenol A polycarbonate. The bisphenol

A polycarbonate was dissolved at high temperature in the

uncured epoxy resin before the curing process. The

physical and chemical interactions between the two

components were studied by FTIR spectroscopy and the

reaction mechanisms were discussed. FTIR isothermal

measurements showed that the presence of polycarbonate

did not affect the overall curing mechanism but decreased

both the initial reaction rate and the final conversion of

reactants. 13 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; ITALY;

WESTERN EUROPE

Accession no.548582

Item 279Journal of Polymer Science : Polymer Chemistry

Edition

32, No.3, Feb.1994, p.485-93

PHOTO- AND THERMOINITIATED OXIDATIONOF HIGH-IMPACT POLYSTYRENE. I.CHARACTERISATION BY FT-IRSPECTROSCOPYIsraeli Y; Lacoste J; Lemaire J; Singh R P; Sivaram S

Blaise Pascal,Universite

The photo- and thermooxidative degradation of different

grades of high-impact polystyrene containing various

amounts of polybutadiene were studied using FTIR

spectroscopy. All samples gave similar oxidation products,

but in varying quantities. The results are discussed. 17

refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.548569

Item 280Applied Spectroscopy

49, No.3, March 1995, p.267-72

CHARACTERISATION OF POLYMER-DISPERSED LIQUID CRYSTAL SYSTEMS BYFTIR MICROSPECTROSCOPYChalla S R; Wang S Q; Koenig J L

Case Western Reserve University

IR microspectroscopy was used to generate functional

group images of liquid crystal(E7) droplets dispersed in

poly-n-butyl methacrylate(PBMA). The spatial

concentration fluctuations that occurred within the system

were studied as a function of time. This approach was

possible because spectral information could be obtained

by focusing on regions of the order of tens of micrometers.

The peak intensities were used as a measure of

concentration of the components. The amount of liquid

crystal dissolved in the polymer matrix determined the

extent to which the polymer was plasticised, which in

turn affected the shape and size of the droplets. The growth

of the domains at any temp. was also determined by

whether the system was maintained above or below the

Tg of the matrix. It was observed that the growth of the

droplets followed temporal power laws. The spatially

resolved spectroscopic images provided valuable insights

into the phase separation process and the formation of

microdroplets of E7 in PBMA. 20 refs.

USA

Accession no.546736

Item 281Plastics & Rubber & Composites Processing &

Applications

23, No.1, 1995, p.11-9

ANALYSIS OF COMPOSITE TEST METHODSUSING RAMAN SPECTROSCOPYYoung R J; Huang Y L; Gu X; Day R J

UMIST; Manchester,University

Three test methods, the fragmentation, pull-out and

microbond methods, were used to analyse the

micromechanics for carbon fibre/epoxy composites and

Raman spectroscopy was used to determine the variation

of fibre strain with position along a carbon fibre in a resin.

It was demonstrated that the latter technique was capable

of revolutionising interpretation of composite

micromechanics and the different micromechanical test

methods. In particular, it was shown that the technique

could be used to distinguish between elastic deformation,

interfacial debonding and shear yielding of the matrix at

the interface. 19 refs. (FRC ’94, Institute of Materials,

Newcastle, March 1994)

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.540316

Item 282Polymer

36, No.2, 1995, p.251-7

LOW-FREQUENCY RAMAN SPECTROSCOPYOF PLASTICALLY DEFORMED POLYMETHYLMETHACRYLATEAchibat T; Boukenter A; Duval E; Mermet A;

Aboulfaraj M; Etienne S; G’Sell C

Universite Claude Bernard; Ecole des Mines de Nancy

Low-frequency Raman scattering (2-200/cm range) of

PMMA specimens plastically deformed in pure shear was

compared with that of undeformed samples. The main

observation was an excess of Raman scattering in the 30-

50/cm spectral range induced by plastic deformation. This

excess appeared to be strongly anisotropic and was

maximum when the light polarisation was orthogonal to

the principal tensile strain component, i.e. to the chain

orientation direction. The effect was still present, but with

a weaker anisotropy, after mechanical cycling when the

References and Abstracts

© Copyright 2001Rapra Technology Limited 109

macroscopic deformation was returned to zero by

application of an opposite stress. These results were

interpreted in terms of the non-continuous nature of the

disordered network on the nanometric scale. The

orientation of macromolecular strands induced by plastic

deformation was shown to be higher in the less cohesive

spaces. 24 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.540286

Item 283Applied Spectroscopy

48, No.11, Nov.1994, p.1410-8

POLARISATION-DIVISIONINTERFEROMETRY: FAR-INFRAREDDICHROISMPolavarapu P L; Gang-Chi Chen

Vanderbilt University

A detailed report is given of the first far-infrared dichroism

measurements using a polarisation-division interferometer

(PDI) which uses a free-standing wire grid beamsplitter

made of tungsten wires. The performance of the PDI was

evaluated by measuring the linear dichroism of oriented

polyvinylidene fluoride and circular dichroism of alpha-

pinene, camphor and 3-methylcyclohexanone. The

dichroic multiplex advantage (ability to measure

dichroism in the entire far-infrared region from a single

measurement) and throughput advantage are

demonstrated. These measurements establish the utility

of the PDI in measuring transmission and linear dichroism

spectra simultaneously without the need for any additional

components. 17 refs.

USA

Accession no.539429

Item 284Polymer Bulletin

34, No.1, Jan.1995, p.71-7

DAMAGE OF POLYMERS STUDIED BY MICRO-FOURIER TRANSFORM RAMANSPECTROSCOPYJawhari T; Merino J C; Pastor J M

Valladolid,Universidad

The potential of micro-Fourier transform Raman

spectroscopy for examining specific localised regions in

polymeric materials with some degree of fluorescence

when analysed by conventional Raman spectroscopy was

examined. Analysis of characteristic bands of the

vibrational spectra obtained in a small area damaged by

a visible and near-IR laser beam in commercial PETP

showed a different conformer ratio than that observed in

a non-irradiated zone. 32 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; SPAIN;

WESTERN EUROPE

Accession no.538461

Item 285Journal of Adhesion

46, Nos.1-4, 1994, p.227-41

ZINC COATED STEEL/EPOXY ADHESIVESYSTEMS: INVESTIGATION OF THEINTERFACIAL ZONE BY FTIRSPECTROSCOPYGaillard F; Romand M; Verchere D; Hocquaux H

CNRS; IRSID Unieux

FTIR spectroscopy was used for the analysis of

ultrathin organic films on metals. FTIR in the reflection

mode (IRRAS) was used to study the interaction of

ultrathin films of dicyandiamide (hardener of most one-

pack epoxy resins) with various substrates, model ones

such as gold or zinc and industrial ones such as steel

and zinc-coated steels. Pure zinc surfaces and, to a

lesser extent, zinc-coated steels are shown to react with

dicyandiamide after heating at 180 C, as evidenced by

the frequency shift of the absorption band characteristic

for nitrile groups. Some mechanically tested specimens

are then analysed, after failure, by FTIR

microspectrometry. The spectra obtained,

corresponding to the fracture initiation zone which is

about 100 micrometers in diameter, indicate the

presence of an ultrathin layer of modified polymer still

covering the substrate. 28 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.531582

Item 286Journal of Adhesion

46, Nos.1-4, 1994, p.91-102

STUDY OF FIBRE-MATRIX INTERACTIONSVIA FTIR MICROSCOPY AND NMR IMAGINGMavrich A; Fondeur F; Ishida H; Koenig J L;

Wagner H D

Case Western Reserve University; Weizmann Institute

of Science

Model composites of Kevlar-49 and D-glass fibre/

epoxy systems were analysed using NMR imaging and

FTIR microscopy. The interphase and specific fibre-

matrix interactions of the fibre-reinforced composites

were characterised. The surfaces of both Kevlar-49 and

D-glass fibres were found to affect the curing process

in composite samples significantly. NMR images

revealed non-uniform cure of the matrix in the

composites. The epoxy was found to cure at an

accelerated rate at the surface of these fibres indicating

strong interaction between the fibres and the matrices.

Using FTIR microscopy, these interactions were found

to be preferential segregation of the epoxy on the

Kevlar surface. It was also determined that the amine

group of the Kevlar fibre acted to catalyse the curing

process. 8 refs.

ISRAEL; USA

Accession no.531574

References and Abstracts

110 © Copyright 2001 Rapra Technology Limited

Item 287Macromolecular Chemistry & Physics

195, No.10, Oct.1994, p.3369-80

RAMAN SPECTROSCOPIC STUDY OFHYDROGEN BONDING OF POLY-N-VINYL-2-PYRROLIDONE(PVP) IN HEAVY WATER ANDDIMETHYL SULPHOXIDETanaka N; Ito K; Kitano H

Kyoto,Institute of Technology; Toyama,University

The Raman spectra of solutions of PVP of molec.wt. 1000,

10,000, 40,000 and 360,000 in heavy water and DMSO

were measured at various concentrations. PVP was

hydrated by heavy water in a different way from N-ethyl-

2-pyrrolidone and N-methyl-2-pyrrolidone(NMP),

monomer analogues of PVP. The self-association of

DMSO molecules in the solution of PVP was found to be

different from that in the solution of NMP by using

difference spectroscopy. These phenomena were

attributed to a net-like structure of concentrated solutions

of PVP. 29 refs.

JAPAN

Accession no.530107

Item 288Journal of Environmental Polymer Degradation

2, No.2, April 1994, p.153-60

INFRARED SPECTROSCOPY STUDIES OF THEPHOTOOXIDATION OF A POLYETHYLENENONWOVEN FABRICMartin L K; Yang C Q

Marshall University; Georgia,University

The photooxidation of a nonwoven PE fabric was

investigated using FTIR photoacoustic spectroscopy.

Hydroperoxide, alcohol, aldehyde, ketone, carboxylic

acid, and anhydride groups were formed as the products

of the photooxidation of the PE fabric and the relative

amount of carboxyl among all carbonyls increased as the

photooxidation progressed. Distribution of the

photooxidation products was inhomogeneous between the

two surfaces of the fabric. The highest degree of

photooxidation occurred on the surface of the fabric using

the UV radiation source, whereas the lowest degree of

photooxidation was on the back surface of the fabric. The

PE nonwoven fabric showed a slower photooxidation rate

than the PP nonwoven fabric. The UV radiation at 254

nm caused photooxidation of PE. No photooxidation was

observed in the fabric exposed to the UV radiation at 350

nm under the same conditions. 25 refs.

USA

Accession no.529929

Item 289Macromolecules

27, No.18, 29th Aug.1994, p.5220-2

CHARACTERISATION OF SOLUTE DIFFUSIONIN A POLYMER USING ATR-FTIR

SPECTROSCOPY AND BULK TRANSPORTTECHNIQUESFarinas K C; Doh L; Venkatraman S; Potts R O

Cygnus Therapeutic Systems

ATR-FTIR spectroscopy was used to monitor the uptake of

urea into a silicone polymer. Analysis of the time-dependent

changes in the IR absorbances of urea and silicone leads to

an estimate of the diffusion coefficient for urea that is in

close agreement with a value obtained using a bulk transport

method (involving radiolabelled permeant). The silicone

polymer was medical grade silicone pressure-sensitive

adhesive (X7-4201). ATR-FTIR is proposed as a rapid and

accurate method of rapidly and accurately determining solute

diffusion within a polymer matrix. 12 refs.

USA

Accession no.529399

Item 290Synthetic Metals

55, No.1, 15th March 1993, p.503-8

IN SITU INTERNAL REFLECTION FTIRSTUDIES ON POLYMERISATION OFPOLYPHENYLENEKvarnstrom C; Nyback A-S; Ivaska A

Abo,University

Electrochemical polymerisation involving simultaneous

doping of polyphenylene was studied using in-situ internalreflection FTIR spectroscopy. The results indicated that

the polymer has a complex structure consisting of

crosslinked short chains and oligomers in which the

phenyl rings are ortho-, meta- and para-substituted. The

current densities used for polymerisation were found to

have no effect on the coupling of phenyl rings. 12 refs.

FINLAND; SCANDINAVIA; WESTERN EUROPE

Accession no.527763

Item 291Polymer

35, No.12, June 1994, p.2538-41

MOLECULAR ORIENTATION STUDIES INPOLYMER FILMS BY POLARISATIONMODULATION FTIR SPECTROSCOPYBuffeteau T; Desbat B; Besbes S; Nafati M; Bokobza L

Bordeaux,University; ESPCI

Measurements of molecular orientation in stretched films

of polydimethylsiloxane using IR linear dichroism were

improved by the introduction of polarisation modulation

of the incident electromagnetic field. It was shown that, by

improving the signal-to-noise ratio and minimising errors

generated by repositioning the sample or the polariser for

a second measurement, this technique was capable of

measuring small dichroic effects with high sensitivity, even

for very small sample draw ratios. 14 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; FRANCE;

WESTERN EUROPE

Accession no.526061

References and Abstracts

© Copyright 2001Rapra Technology Limited 111

Item 292Polymer

35, No.12, June 1994, p.2495-500

RAMAN AND IR SPECTROSCOPY OFELECTROCHEMICALLY OBTAINEDCONDUCTING AND NON-CONDUCTING POLY-N-VINYLCARBAZOLESacak M; Akbulut U; Cheng C; Batchelder D N

Leeds,University

Studies of the above spectra showed that the conducting

polymer had a 3,3'-dicarbazyl structure formed by

dimerisation at the 3,6 position. An appropriate

mechanism was proposed. The conducting polymer was

also obtained by electrolysis of the non-conducting

polymer dissolved in dichloromethane. The conducting

polymer obtained by this method was found to have a

similar structure to that obtained by direct electrolysis

of the monomer. The polymerisation was monitored

by use of a specially designed cell, with in situ Raman

spectra being taken from the electrode surface at

different intervals. These spectra showed that there

were no significant structural changes occurring in the

conducting polymer during the polymerisation process.

In addition, the Raman image of the conducting

polymer was taken by using the intense band which

was located at 1600/cm. 33 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; UK;

WESTERN EUROPE

Accession no.526055

Item 293Macromolecular Chemistry & Physics

195, No.9, Sept.1994, p.3261-70

RAMAN SPECTROSCOPIC STUDY ON WATERIN AQUEOUS SOLUTIONS OF TEMPERATURE-RESPONSIVE POLYMERS: POLY(N-ISOPROPYLACRYLAMIDE) AND POLY(N-(3-ETHOXYPROPYL)ACRYLAMIDE)Terada T; Inaba T; Kitano H; Maeda Y; Tsukida N

Kyoto,University; Toyama,University

Property changes of water in the course of the temp.-

responsive solution-aggregate transition phenomenon of

aqueous poly(N-isopropylacrylamide) and poly(N-(3-

ethoxypropyl)acrylamide) solutions were studied by

Raman spectroscopy. Upon the transition of polymers

from coil to globule followed by the aggregation of

individual polymer chains, the height ratio of the peaks

at 3250 and 3400/cm, corresponding to the O-H

stretching of water molecules, was drastically changed.

The contribution of small water domains included in

polymer aggregates (‘interstitial water’) to the change

in the Raman spectra was considered. The effects of

polymer concentration and molec.wt. of polymers on

the spectra were also examined. 14 refs.

JAPAN

Accession no.526038

Item 294Acta Polymerica

45, No.4, July 1994, p.319-24

FTIR SPECTROSCOPIC STUDIES ON THEHETEROGENEOUS TRANSFORMATION OFCELLULOSE I INTO CELLULOSE IIFengel D; Strobel C

Munich,University

The heterogeneous transformation of cellulose I into

cellulose II via sodium-cellulose I was carried out by alkali

treatment of cotton linters followed by stepwise washing.

Two experimental series were conducted, one with sodium

hydroxide/water and the other with deuterated sodium

hydroxide/heavy water. Changes in the cellulose structure

were studied by FTIR spectroscopy. Various reactions

such as the inclusion of alkali and water in the cellulose

lattice, splitting and new formation of inter- and

intramolecular hydrogen bonds were examined with

reference to the absorbance variations and wavenumber

shifts of several bands. 27 refs.

EUROPEAN COMMUNITY; EUROPEAN UNION; GERMANY;

WESTERN EUROPE

Accession no.524205

Item 295Applied Spectroscopy

48, No.7, July 1994, p.900-3

MONOMERS IN POLYMER DISPERSIONS. IV.PARTITION OF ACRYLONITRILE IN RUBBERLATEX AS STUDIED BY RAMANSPECTROSCOPYHergeth W D; Codella P J

General Electric Co.

The partitioning of acrylonitrile between particles and the

aqueous phase of polybutadiene latex was measured by

Raman spectroscopy using rubber latex as substrate.

Overlapping peaks corresponding to acrylonitrile in the

polymer and aqueous phases were resolved with the use

of a peak fit. Peak intensities yielded the partition values

after corrections for internal field effects in the two phases.

23 refs.

USA

Accession no.523456

Item 296Macromolecules

27, No.2, 17th Jan.1994, p.545-52

INFRARED SPECTROSCOPIC STUDY OFBLENDS OF POLY(STYRENE-CO-STYRENESULPHONIC ACID) WITHPOLY(STYRENE-CO-(4-VINYLPYRIDINE))Smith P; Eisenberg A

McGill University

Poly(styrene-co-styrenesulphonic acid) copolymers

containing 2 to 10 mol % acidic units were mixed in

stoichiometric amounts of interacting groups with

References and Abstracts

112 © Copyright 2001 Rapra Technology Limited

poly(styrene-co-(4-vinylpyridine)) copolymers containing

2 to 10 mol % basic units. FTIR spectroscopy revealed

that about 80-90% of the pyridine units in the blend were

protonated, with the pyridinium ions hydrogen-bonded

to the anion. An FTIR temp. study indicated that the

pyridinium units were involved in an equilibrium

involving the hydrogen-bonded pyridinium/sulphonate

ion pair and most likely the hydrogen-bonded but non-

ionic acid/base pair. Previously reported mechanical

property measurements were interpreted in the light of

these results. 38 refs.

CANADA

Accession no.523004

Item 297Die Makromolekulare Chemie- Macromolecular

symposia

Vol.84, July 1994, p.351-63

OXIDATIVE DEGRADATION OF WATER-SOLUBLE POLYETHERS BY HYDROXY ANDHYDROPEROXY GENERATEDPHOTOCHEMICALLY: FTIR STUDIESKaczmarek H; Linden L A; Rabek J F

Copernicus N.,University; Sweden,Royal Institute of

Medicine

Two water-soluble polyethers, polyethylene oxide and

polymethyl vinyl ether, were UV irradiated in hydrogen

peroxide solutions. It was shown that hydroxy and

hydroperoxy radicals accelerate oxidative degradation of

these polymers. Hydroxy and probably hydroperoxy

radicals can abstract hydrogen from methylene groups in

both polymers. As a result of further oxidative reactions,

different carbonyl, hydroxy and hydroperoxy groups are

formed. A mechanism for the formation of these groups

is proposed. 8 refs.

EASTERN EUROPE; POLAND; SCANDINAVIA; SWEDEN;

WESTERN EUROPE

Accession no.521510

Item 298Synthetic Metals

64, No.1, May 1994, p.91-5

TOTAL INTERNAL REFLECTANCE IRSPECTROSCOPY OF POLYPYRROLE ON ASILICON ELECTRODERangamani A G; McTigue P T; Verity B

Melbourne,University; South Australia,University

A new experimental arrangement is described whereby

thin films (about 1 micrometre thick) of polypyrrole were

electrochemically deposited onto a silicon rod single

crystal that formed an element of the cylindrical internal

reflectance accessory of an FTIR spectrometer.

Polypyrrole was deposited from acetonitrile solutions

of pyrrole in the presence of lithium perchlorate,

tetrabutylammonium perchlorate and tetrabutyl-

ammonium tetrafluoroborate. Excellent quality in situ

ATR FTIR spectra were obtained over a range of

potentials, with no solvent interference, showing

systematic changes in spectra with the progressive

oxidation and reduction of the polymer film. Both anions

and cations were found in both oxidised and reduced

polypyrrole. 11 refs.

AUSTRALIA

Accession no.516463

Item 299Makromolekulare Chemie, Rapid Communications

15, No.6, June 1994, p.467-73

ANALYSIS OF ORIENTATIONAL RELAXATIONIN BINARY BLENDS OF UNIFORM PS BYRHEO-OPTICAL FOURIER-TRANSFORM IRSPECTROSCOPYSiesler H W; Hayes C; Bokobza L; Monnerie L

Essen,University; ESPCI

Rheo-optical FTIR spectroscopy was used to measure

orientation and orientational relaxation in binary blends

of long- and short-chain linear PS. Films were stretched

at constant strain rate at various temperatures above Tg.

17 refs.

EUROPEAN COMMUNITY; FRANCE; GERMANY; WESTERN

EUROPE

Accession no.514364

Item 300Journal of Applied Polymer Science

52, No.7, 16th May 1994, p.975-83

SIMULTANEOUS MEASUREMENT OF WATERDIFFUSION, SWELLING AND CALCIUMCARBONATE REMOVAL IN A LATEX PAINTUSING FTIR-ATRBalik C M; Xu J R

North Carolina,State University

An in-situ FTIR-ATR method was used to monitor the

sorption processes of water and pH 1.3 sulphurous acid

in two latex paints and the base polymer common to

both. The sorption kinetics could not be described by

a simple Fickian model. The spectra also showed

evidence of polymer swelling, which was confirmed

in separate swelling measurements. Anomalous

behaviour was noted for the latex paint containing

calcium carbonate when exposed to sulphurous acid.

The amount of water sorbed by this sample went

through a maximum, then decreased to a constant level.

This was accompanied by similar variations in the

degree of swelling of the sample. These changes are

explained by the rapid loss of calcium carbonate from

this particular paint upon exposure to acidic solutions,

followed by structural rearrangement to fill in the voids

left by the calcium carbonate particles. 19 refs.

USA

Accession no.511826

References and Abstracts

© Copyright 2001Rapra Technology Limited 113

Item 301Macromolecular Reports

A31, Nos.3 & 4, 1994, p.261-70

APPLICATION OF FTIR PHOTOACOUSTICSPECTROSCOPY IN THE DETERMINATION OFTHE LEVEL OF CHEMICAL MODIFICATIONOF JUTE FIBRESCherian X M; Satyamoorthy P; Andrew J J;

Bhattacharya S K

Hindustan Lever Research Centre

FTIR photoacoustic spectroscopy was used to determine

the extent of acylation in acetylated jute samples

quantitatively and results were compared with those

obtained by standard wet chemical titrimetric

measurements. 12 refs.

INDIA

Accession no.511745

Item 302Analyst

119, No.4, April 1994, p.693-6

ANALYSIS OF POLYMERS USING EVOLVED-GAS AND DIRECT-PYROLYSIS TECHNIQUESFares M M; Yalcin T; Hacaloglu J; Gungor A; Suzer S

Middle East,Technical University; Tubitak;

Ankara,Bilkent University

Thermal analysis of PS, poly-p-methylstyrene and poly-alpha-methylstyrene was carried out using evolved-gas

analysis by IR and mass spectrometry and direct-pyrolysis

analysis by mass spectrometric techniques. Evolved-gas

analysis, both by IR and mass spectrometry, revealed

features due mainly to the corresponding monomers or

stable, volatile and low relative molec.wt. degradation

products. In direct-pyrolysis mass spectrometry, however,

primary decomposition products and heavier fragments

such as dimers and trimers could also be detected. The

ion-temp. profiles of the corresponding monomer ions

revealed information about the thermal stability of the

polymers. 25 refs. (XXVIII Colloquium Spectroscopicum

Internationale, York, UK, June/July 1993)

TURKEY

Accession no.511583

Item 303Analytical Chemistry

66, No.6, 15th March 1994, p.882-7

FEASIBILITY OF EXTRACTION ANDQUANTIFICATION OF FIBRE FINISHES VIAON-LINE SUPERCRITICAL FLUIDEXTRACTION/FOURIER TRANSFORM IRSPECTROSCOPY(SFE/FTIR)Kirschner C H; Jordan S L; Taylor L T; Seemuth P D

Virginia,Polytechnic Institute & State University;

DuPont Co.

The SFE/FTIR technique was applied to analysis of fibre

finishes on fibre/textile matrices. Three different fibre

polymer types were examined (PU, polyamide and

aramid), each requiring a different finish. Finishes ranged

from a single-component polydimethylsiloxane oil to

more complex multicomponent finishes that included

various surfactants, fatty acid esters and soaps,

antioxidants and oils. Off-line extraction showed all three

finishes to be over 89% extractable with pure carbon

dioxide. Calibration curves were established for the three

finishes, with relatively low error and reasonable detection

limits. 6 refs.

USA

Accession no.509562

Item 304IRC ’93/144th Meeting, Fall 1993. Conference

Proceedings.

Orlando, Fl., 26th-29th Oct.1993, Paper 105, pp.28.

012

APPLICATIONS OF RAMAN SPECTROSCOPYTO THE ANALYSIS OF NATURAL RUBBERHendra P J; Jackson K D O

Southampton,University; Malaysian Rubber Producers’

Research Assn.

(ACS,Rubber Div.)

Applications of Fourier transform Raman spectroscopy

to the analysis of NR are described. Of particular interest

is the observation of main chain modifications during

vulcanisation and the ability to observe the conversion of

insoluble to soluble sulphur under conditions appropriate

to compounding and vulcanisation. The influence of

crystallisation, both temperature and strain induced, on

the Raman spectrum of NR is also demonstrated. 9 refs.

EUROPEAN COMMUNITY; UK; USA; WESTERN EUROPE

Accession no.505679

Item 305Polyolefins VIII. Conference Proceedings.

Houston,Tx., 21st-24th Feb.1993, p.616-33. 42C1

RAPID AND NON-DESTRUCTIVE QUALITYASSESSMENT OF POLYMERIC FILMS USINGNEAR-INFRARED SPECTROSCOPYMiller C E

Dupont Polymers

(SPE,South Texas Section; SPE,Thermoplastic

Materials & Foams Div.)

The ability of near-infrared spectroscopy, combined with

multivariate statistics, to non-destructively determine the

HDPE/LDPE ratio of PE blend films and the individual

layer thickness percentages of LDPE/nylon 6/ethylene-

vinyl alcohol copolymer food packaging laminates is

demonstrated. 19 refs.

USA

Accession no.504961

Item 306Polymer Testing

13, No.1, 1994, p.25-34

References and Abstracts

114 © Copyright 2001 Rapra Technology Limited

CHARACTERISATION OF EPDM RUBBERMODIFIED WITH MALEIC ANHYDRIDE (MAH)BY DIFFUSE REFLECTANCE FTIR (DRIFT)Coutinho F M B; Ferreira M I P

Rio de Janeiro,Universidade Federal

A rapid technique for determining bound MAH content

in maleated EPDM rubbers was established. It is based

on the application of diffuse reflectance FTIR which

permits the analysis of such products directly without any

sample preparation other than removing unreacted

monomer and initiator. The spectrum obtained also allows

the evaluation of the rubber’s relative oxidation extent.

Baseline and band choices as well as calculation methods

required are discussed. 12 refs.

BRAZIL

Accession no.503999

Item 307Journal of Applied Polymer Science

51, No.7, 14th Feb.1994, p.1251-67

POLARISED INTERNAL REFLECTANCESPECTROSCOPIC STUDIES OF ORIENTEDPOLY(ETHYLENE TEREPHTHALATE)Lofgren E A; Jabarin S A

Toledo,University

Polarised internal reflectance spectroscopy was used to

evaluate molecular orientation and crystallinity of PETPfilm surfaces. Uniaxially and biaxially stretched samples

were measured. All bands of interest were normalised

with a reference band near 1410/cm, resulting from

phenylene ring vibrations. Normalisation was performed

in order to overcome problems with sample contact and

effective thickness. Results using bands representing

trans and gauche rotamers at 1340 and 1370/cm,

respectively, were related to data acquired using density

and birefringence techniques. Polarised internal

reflectance spectroscopy was found to be well suited to

investigations of polymer orientation and crystallinity

since it avoided limitations related to sample thickness

and clarity imposed by polarised transmission IR

spectroscopy. Results agreed well with those obtained

by density, birefringence and refractive index

measurements. 34 refs.

USA

Accession no.503928

Item 308Polymer Science Series A

36, No.1, Jan.1994, p.48-51

IR SPECTROSCOPIC STUDY OFPOLYCAPROAMIDE FIBRES WITH GRAFTEDPOLYGLYCIDYL METHACRYLATEKorolik E V; Buslov D K; Zhbankov R G; Mosina N Y;

Nazar’ina L A; Druzhinina T V; Gal’braikh L S

Belarus Academy of Sciences; Moscow,State Textile

Academy

IR spectra of polycaproamide fibre, polyglycidyl

methacrylate and polycaproamide fibre grafted with

polyglycidyl methacrylate were recorded. The

corresponding deconvolution spectra were calculated. A

model spectrum of the graft copolymer was simulated.

The spectral regions that were sensitive to localisation of

the chains of grafted polyglycidyl methacrylate were

identified, i.e. 3500-3100/cm (stretching vibrations of NH

groups), 1700-1500/cm (Amide I and Amide II absorption

bands), 1030-900/cm (Amide IV) and 720-640/cm

(Amide V). It was found that polyglycidyl methacrylate

was grafted to the macromolecules of polycaproamide

via an amide nitrogen. 7 refs. (Full translation of

Vys.Soed.A, 36, No.1, 1994, p.58-62)

BELORUSSIA; CIS; COMMONWEALTH OF INDEPENDENT

STATES; RUSSIA

Accession no.503687

Item 309Applied Spectroscopy

48, No.1, Jan.1994, p.72-8

ANALYSIS OF SOME ERRORS IN THECALCULATION OF ORIENTATION FUNCTIONSFOR POLYMERS FROM INFRAREDDICHROISM MEASUREMENTSMyers C W; Cooper S L

Wisconsin,University; Delaware,University

Several sources of error may influence the calculations

of chain orientation carried with the use of data from

infrared dichroism experiments. Three specific problems

are the improper treatment of chain conformation, the

imperfect polariser behaviour, and the inaccurate

assumptions regarding the value of the angle between a

particular infrared-active transition moment and the

polymer chain axis. In this paper, a quantitative analysis

is presented of the magnitudes of these errors for several

infrared bands commonly employed to characterise

polymer orientation via infrared dichroism. 52 refs.

USA

Accession no.503524

Item 310Journal of Polymer Science : Polymer Physics Edition

32, No.1, 15th Jan.1994, p.29-35

FTIR INVESTIGATION OF ION-DIPOLEINTERACTION IN STYRENE IONOMER/POLY(ETHYLENE OXIDE) BLENDSJong-Chul Lim; Jung-Ki Park; Hae-Young Song

Korea,Advanced Institute of Science & Technology;

Korea,Chungnam National University

FTIR was used to examine specific interactions

contributing to the partial miscibility in blends of styrene-

sodium methacrylate copolymer and PEO. From the shifts

of carboxylate ion and ether group stretching bands, an

important specific interaction was found involving ion-

dipole bonding between the ionic group in styrene

References and Abstracts

© Copyright 2001Rapra Technology Limited 115

ionomer and the ether group in PEO. The asymmetric

stretching vibration frequency of the carboxylate ion

group increases as the fractional amount of PEO in the

blend is increased, while the symmetric stretching

frequency is decreased. The ether group stretching band

is shifted to higher frequencies as the PEO content of the

blend increases. From DSC and FTIR it was concluded

that ion-dipole interaction was the important mechanism

that determines miscibility in these styrene-sodium

methacrylate copolymer/PEO blends. 42 refs.

KOREA

Accession no.502023

Item 311Journal of Polymer Science : Polymer Physics Edition

32, No.2, 30th Jan.1994, p.383-6

USE OF NEAR INFRARED (NIR)SPECTROSCOPY TO STUDY SPECIFICINTERACTIONS IN POLYMER BLENDSGhebremeskel Y; Fields J; Garton A

Connecticut,University

With the use of model systems and blends of

polycaprolactone and phenoxy resin, it is shown that data

obtained from the OH stretch overtone absorption in NIR

is consistent with those from the OH stretch fundamental

in the mid-IR region. The advantages of NIR analysis of

specific interactions are illustrated with spectra obtained

from thick films of blends of nylon 6 and the zinc salt of

sulphonated PS. 9 refs.

USA

Accession no.501517

Item 312Polymer

34, No.24, 1993, p.5099-105

WATER ABSORPTION BY AN EPOXY RESINAND ITS EFFECT ON THE MECHANICALPROPERTIES AND INFRA-RED SPECTRADe’Neve B; Shanahan M E R

Ecole Nationale Superieure des Mines de Paris

A filled epoxy resin used as a structural adhesive and

based on the diglycidyl ether of bisphenol A cured with

dicyandiamide was subjected, in its bulk form, to ageing

at 40, 55 and 70C and about 100% relative humidity.

Gravimetric viscoelastomeric and FTIR studies were

effected after various times of exposure to monitor water

ingress and to link variations in mechanical behaviour

with chemical modifications occurring in the polymer.

34 refs.

EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.499766

Item 313Applied Spectroscopy

47, No.11, Nov.1993, p.1747-50

MID-INFRARED SPECTRA FROM NEAR-INFRARED SPECTRA USING PARTIAL LEAST-SQUARESLew R; Balke S T

Toronto,University

Partial least-squares (PLS) was used to generate mid-

infrared (MIR) spectra from near-infrared (NIR) spectra.

The NIR spectra were obtained by in-line monitoring of

a molten blend of PE with PP during extrusion. Off-line

MIR spectra of blends were used to calibrate the PLS

method, which was then employed to generate the MIR

absorbance spectrum of a 50:50-by-weight blend not

included in the calibration set from its NIR spectrum. The

synthesised MIR spectrum agreed very well with a directly

measured one. 11 refs.

CANADA

Accession no.497783

Item 314Macromolecules

26, No.23, 8th Nov.1993, p.6237-42

DETERMINATION OF SOLUTIONPOLYMERISATION KINETICS BY NEAR-INFRARED SPECTROSCOPY. I. LIVINGANIONIC POLYMERISATION PROCESSESLong T E; Liu H Y:Schell B A; Teegarden D M;

Uerz D S

Eastman Kodak Co.

Near-IR spectroscopy (10000-4000/cm) was successfully

used to monitor conversion during conventional, anionic

solution polymerisation of styrene and isoprene to

homopolymers and block copolymers. The conversion of

the vinyl protons in the monomer to methylene protons

in the polymer was easily monitored under conventional

(10-20% solids) solution polymerisation conditions. In

addition to the need for an inert probe, high sampling

frequencies were required since polymerisation times

ranged from 5s in tetrahydrofuran to 20 minutes in

cyclohexane. Preliminary data indicate that near IR is

capable of detecting sequence distribution for tapered

block copolymers, geometric isomer content, and

reactivity ratios for free-radical copolymerisation. 20 refs.

USA

Accession no.497376

Item 315Macromolecules

26, No.22, 25th Oct.1993, p.5954-8

KINETICS OF DIACETYLENEPOLYMERISATION. AN FT-RAMAN STUDYKamath M; Kim W H; Li L; Kumar J; Tripathy S; Babu

K N; Talwar S S

Massachusetts,University; Indian Institute of

Technology

Changes in the FT-Raman spectrum of 1,4-bis(3-

quinolyl)buta-1,3-diyne as a function of gamma-ray

References and Abstracts

116 © Copyright 2001 Rapra Technology Limited

dosage is used to monitor the degree of monomer to

polymer conversion in a solid-state topochemical

polymerisation reaction. The relative intensities of the

characteristic carbon-to-carbon triple bond peaks in the

nonresonant FT-Raman spectra provide a nondestructive

quantitative means to measure the conversion from

monomer to polymer. 36 refs.

INDIA; USA

Accession no.497334

Item 316Journal of Polymer Science : Polymer Physics Edition

31, No.12, Nov.1993, p.1769-77

DYNAMIC RHEO-OPTICALCHARACTERISATION OF A LOW DENSITYPOLYETHYLENE/PERDEUTERATED HIGHDENSITY POLYETHYLENE BLEND BY TWODIMENSIONAL STEP-SCAN FTIRSPECTROSCOPYGregoriou V G; Noda I; Dowrey A E; Marcott C; Chao

J L; Palmer R A

Duke,University; Procter & Gamble Co.; IBM Corp.

Dynamic mechanical analysis coupled with polarised

step-scan FTIR transmission and two-dimensional

correlation analysis was used to monitor the submolecular

orientational responses of the components of a

semicrystalline 50/50 blend of LDPE with perdeuterated

HDPE to a small amplitude uniaxial 23.47 Hz sinusoidal

mechanical strain. Perdeuteration of the HDPE component

allowed the distinction of its response from that of the

LDPE in the blend samples. Experiments were carried

out at room temp. Analysis of the data indicated that the

crystalline parts of the two components reorient at

different rates, with the functional groups of the high

density portion reorienting faster, in general, than those

of the LDPE in response to the mechanical strain. 29 refs.

USA

Accession no.496076

Item 317Synthetic Metals

59, No.2, July 1993, p.141-9

CHARACTERISATION FROM XPS, FTIR ANDRAMAN SPECTROSCOPIES OF FILMS OFPOLY-P-PHENYLENE PREPARED BYELECTROPOLYMERISATION OF BENZENEDISSOLVED IN KETYL PYRIDINIUMCHLORIDE-ALUMINIUM TRICHLORIDEMELTING SALTLere-Porte J P; Radi M; Chorro C; Petrissans J;

Sauvajol J L; Gonbeau D; Pfister-Guillouzo G; Louarn

G; Lefrant S

Montpellier,University; Pau,Universite;

Nantes,Laboratoire de Physique Cristalline

X-ray photoelectron(XPS) studies of the above films

showed a small amount of residual chlorine. The shape

and strong intensity of the extrinsic part of the

photoluminescence could be related to a large amount of

structural defects in the films, but the distribution of these

defects was relatively homogeneous. Raman spectra

clearly showed the presence of segments with small

conjugation lengths in the films. FTIR spectra showed

that the degree of polymerisation was smaller than those

reported for electrochemical oxidation of benzene in

sulphur dioxide at low temp. These results indicated that

the films obtained by this technique showed some

similarities with ‘Kovacic compounds’. 29 refs.

EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.495093

Item 318Journal of Polymer Science : Polymer Physics Edition

31, No.11, Oct.1993, p.1487-94

PHYSICAL MODIFICATIONS OF PROPYLENE/ETHYLENE-PROPYLENE-DIENE-MONOMERRUBBER SURFACES. I. DETERMINATION OFSURFACE COMPOSITION AND SURFACEORDER BY FOURIER TRANSFORMINFRARED-ATTENUATED TOTALREFLECTANCEBonnerup C; Gatenholm P

Chalmers University of Technology

Results are presented of an investigation of the possibility

of using the FTIR-ATR technique for determining surface

composition and surface crystallinity of PP/EPDM blends

containing varying amounts of EPDM. 37 refs.

SCANDINAVIA; SWEDEN; WESTERN EUROPE

Accession no.494717

Item 319Applied Spectroscopy

47, No.7, July 1993, p.928-32

USE OF WATER AS AN INTERNAL STANDARDIN THE DIRECT MONITORING OF EMULSIONPOLYMERISATION BY FIBRE-OPTIC RAMANSPECTROSCOPYWang C; Vickers T J; Mann C K

Florida State University

The direct analysis of the organic phase of an emulsion

polymerisation is described. Quantification using the

bending mode peak of water, which makes up the bulk of

the reaction medium, as an internal standard is discussed.

The process is demonstrated for methyl methacrylate but

is generally applicable to emulsion polymerisations. It

does not require the introduction of an extraneous internal

standard component into the reaction mixture. 4 refs.

USA

Accession no.490646

Item 320Journal of Applied Polymer Science

References and Abstracts

© Copyright 2001Rapra Technology Limited 117

49, No.5, 5th Aug.1993, p.925-34

MOLECULAR CHANGES IN PETP YARNSDURING STRETCHING MEASURED WITHRHEO-OPTICAL INFRARED SPECTROSCOPYAND OTHER TECHNIQUESvan den Heuvel C J M; Heuvel H M; Faassen W A;

Veurink J; Lucas L J

Akzo Research Laboratories

A method was developed for measuring IR spectra during

the mechanical deformation of yarns. This rheooptical

technique was applied to study the molecular processes

that take place along the stress-strain curve of PETP yarns.

The results were combined with data obtained from size

exclusion chromatography and tensile measurements at

elevated temperatures. The results indicate that the first

modulus maximum marks the breakdown of the

amorphous entanglement network and the start of

molecular uncoiling by gauche-to-trans transitions. In

addition, stress develops on the crystals and particularly

on tie molecules with a short contour length in the

amorphous domains. Ultimately, molecular fracture of

taut-tie molecules causes the modulus to pass through a

second maximum. The chain ends of broken molecules

recoil by trans-to-gauche transitions. Local stress

accumulation will lead eventually to yarn rupture.

EUROPEAN COMMUNITY; NETHERLANDS; WESTERN

EUROPE

Accession no.489164

Item 321Polymer

34, No.14, July 1993, p.3010-8

SYNTHESIS AND INFRA-REDSPECTROSCOPIC CHARACTERISATION OFRANDOM COPOLYMERS OF 4-VINYLPHENOLWITH N-ALKYL METHACRYLATESXu Y; Painter P C; Coleman M M

Pennsylvania,University

Random copolymers of 4-vinylphenol with n-alkyl

methacrylates were prepared by free radical

copolymerisation of 4-t-butyldimethylsilyloxystyrene and

the corresponding alkyl methacrylates in benzene at 60C

using AIBN as initiator. Reactivity ratios were determined

by the Kelen-Tudos method. Selective removal of the t-

butyldimethylsilyl protective group was effected by

tetrabutylammonium fluoride in THF at ambient

temperature. The copolymers were characterised by IR

spectroscopy. 20 refs.

USA

Accession no.488248

Item 322Polymer

34, No.14, July 1993, p.3004-9

PHYSICOCHEMICAL CHARACTERISATIONOF POLYPROPYLENE FILMS GRAFTED BY

POLYACRYLIC ACID. I.Romero M A; Domard A; Petit D

Claude Bernard,Universite; Centre de Recherche de

Voreppe SA

ATR-IR spectroscopy was used to characterise the grafting

of PP films by polyacrylic acid. A technique allowing the

separation of the grafted part from the unmodified part

of the specimen was also used. The effects of pretreatment

of the films to remove additives were investigated. It was

shown that grafting always started from the interface

between the PP and the polymerisation solvent. The results

suggested that it should be possible to control the location

of grafting both by the content of antioxidants and by

their extraction. 27 refs.

EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.488247

Item 323Polymer

34, No.14, July 1993, p.2934-45

FOURIER TRANSFORM INFRA-REDSPECTROSCOPY ON THETHERMOOXIDATIVE DEGRADATION OFPOLYBENZIMIDAZOLE AND OF APOLYBENZIMIDAZOLE/POLYETHERIMIDEBLENDMusto P; Karasz F E; MacKnight W J

Massachusetts,University

The thermooxidative degradation of polyphenylene

bibenzimidazole (PBI) and a blend of PBI with Ultem 1000

polyetherimide (PEI) was investigated by Fourier transform

IR (FTIR) spectroscopy, under conditions which allowed

real time monitoring of molecular changes taking place

during the process. The data provided information on the

kinetics and mechanism of degradation in its early stages.

The FTIR spectra of the blend were analysed by subtraction

spectroscopy, allowing the fate of the two blend

components to be selectively studied. No chemical

interaction between PBI and PEI was detectable by FTIR

during the degradation process. 12 refs.

GENERAL ELECTRIC CO.USA

Accession no.488238

Item 324Antec ’92. Plastics: Shaping the Future. Volume 1.

Conference Proceedings.

Detroit, Mi., 3rd-7th May 1992, p.211-4. 012

ON-LINE FTIR SPECTROSCOPICMEASUREMENT OF ERUCAMIDE AND SILICAIN MOLTEN LDPEFidler R A

Automatik Machinery Corp.

(SPE)

The design of an on-line Fourier transform IR analyser

and its application to the characterisation of an anti-

References and Abstracts

118 © Copyright 2001 Rapra Technology Limited

blocking agent (silica) and lubricant (erucamide) in LDPE

samples are described. 8 refs.

USA

Accession no.483822

Item 325Makromolekulare Chemie

194, No.6, June 1993, p.1545-59

LINEAR-TEMPERATURE PROGRAMMEDPYROLYSIS OF THERMORESISTANTPOLYMERS - MASS AND FTIRSPECTROMETRIES. II. AROMATICPOLYESTERS AND COPOLYESTERSHummel D O; Neuhoff U; Bretz A; Duessel H J

Koln,Universitat; Angewandte Spektrometrie Koeln eV

Results are presented of an investigation of the use of

linear-temp. controlled pyrolysis with subsequent analysis

of the pyrolysates (volatiles and residues) by 18V

electron-impact mass spectrometry and FTIR

spectrometry to provide information on the thermal

degradation mechanisms of aromatic polyesters, in

particular polyhydroxybenzoic acid and oxybenzoate-

oxynaphthoate copolymer (Vectra). 13 refs.

EUROPEAN COMMUNITY; GERMANY; WESTERN EUROPE

Accession no.483277

Item 326Makromolekulare Chemie

194, No.6, June 1993, p.1527-36

NON-DESTRUCTIVE DETERMINATION OFTHE RESIDUAL MONOMER CONTENT INPOLYMERS BY RAMAN SPECTROSCOPYDywan F; Hartmann B; Klauer S; Lechner M D; Rupp

R A; Woehlecke M

Osnabruck,University

Raman spectroscopy was established by means of a

comparative study and by calibration to be a suitable non-

destructive method for determination of monomer

concentration in solid PMMA samples. Although the

effect of the internal field on the refractive index and on

the Raman intensity of a polymer solution in a monomer

was considered, the Raman scattering cross-section of the

carbonyl stretching vibration of the monomer was shown

to be twice as large as that of the polymer. 42 refs.

EUROPEAN COMMUNITY; GERMANY; WESTERN EUROPE

Accession no.483275

Item 327Journal of Applied Polymer Science

48, No.9, 5th June 1993, p.1579-85

CHARACTERISATION OF GRAFTEDPOLYETHYLENE BY CONTACT ANGLEHYSTERESIS AND ESCA STUDIESKonar J; Sen A K; Bhowmick A K

Indian Institute of Technology; Fort Gloster Industries Ltd.

LDPE was functionalised in the bulk through dicumyl

peroxide-initiated grafting of dibutyl maleate and

vinyltrimethoxysilane in the temp. range from 140 to

200C. The functionalised surfaces were characterised

through contact angle and contact angle hysteresis

measurements as well as through ESCA studies. The

degree of grafting was determined by IR

spectrophotometry. From the ESCA patterns of the

modified polymers, the atomic ratios of oxygen to carbon

and silicon to carbon were calculated. Determination of

an empirical relation between contact angle hysteresis and

the oxygen-carbon ratio of the functionalised polymer

surfaces was attempted. It was found that the contact angle

value for PE decreased with increasing oxygen-carbon

ratio. Contact angle hysteresis increased with increase in

the degree of grafting. The total surface energy increased

with grafting. The surface energy of the silane-grafted

PE was found to be lower than that of dibutyl maleate-

grafted PE. 13 refs.

INDIA

Accession no.483225

Item 328Polymer

34, No.11, 1993, p.2445-6

INVESTIGATION OF THE INTERPHASE OF ASILANE-FINISHED GLASS FIBRE/VINYLESTER USING A MICROSCOPIC FTIRSPECTROMETERIkuta N; Suzuki Y; Maekawa Z; Hamada H

Osaka Municipal Industrial Research Institute; Nitto

Boseki Co.Ltd.; Kyoto,Institute of Technology

Glass fibre strand was treated with gamma-

methacryloxypropyltrimethoxysilane as coupling agent

and used to reinforce a vinylester resin. The interface was

studied by FTIR. Silane was able to migrate into the resin

and influence curing at a distance (200 micrometres)

greater than the thickness of the interphase. 3 refs.

JAPAN

Accession no.481357

Item 329Makromolekulare Chemie

194, No.5, May 1993, p.1249-72

STOPPED-FLOW FOURIER TRANSFORMINFRARED STUDIES IN POLYMERCHEMISTRYBrittain W J; Aquino E C; Dicker I B; Brunelle D J

Akron,University; Du Pont Merck Pharmaceutical Co.;

GE Corporate R & D

The application of stopped-flow FTIR spectroscopy to

group transfer polymerisation(GTP) and cyclic oligomeric

carbonate formation was studied. The effect of catalyst

structure, propagating end stereochemistry and degree of

polymerisation on the rate of monomer addition in GTP

was investigated. The main GTP termination process was

References and Abstracts

© Copyright 2001Rapra Technology Limited 119

identified and characterised. Model reactions were used

to study kinetics of acyl ammonium salt formation and

subsequent conversion to urethane. The results were used

to develop further the mechanism of bisphenol-A-

bischloroformate macrocyclisation. 44 refs.

USA

Accession no.478673

Item 330Polymer Science Series A

35, No.3, March 1993, p.311-4

IR SPECTROSCOPIC STUDY OF THE EFFECTOF IONISING IRRADIATION ON THESTRUCTURE OF POLYACRYLONITRILEPlatonova N V; Klimenko I B; Maiburov S P

St.Petersburg,Textile & Light Industry Institute

IR spectroscopic analysis showed that the treatment of

polyacrylonitrile films and fibres by gamma-irradiation

led to cleavage of the polymer chains forming carbonyl-

containing functional groups, the composition of which

depended on the treatment conditions. The presence of

terminal methyl groups in the treated polymer was

detected in its IR spectra only in the presence of residual

basic solvent. The occurrence of conformational changes

was revealed by the behaviour of the absorption bands.

12 refs.

RUSSIA

Accession no.478498

Item 331Polymer

34, No.8, 1993, p.1649-52

FOURIER TRANSFORM-RAMANSPECTROSCOPIC STUDY OF ELECTRICALLYCONDUCTING POLYPYRROLE FILMSJenden C M; Davidson R G; Turner T G

Australia,Defence Science & Technology Org.

The chemical structure of electrically conducting

polypyrrole films doped with p-toluene sulphonate and

dodecyl sulphate was studied by Fourier Transform-

Raman spectroscopy. The spectra were compared with

those from the corresponding reduced polymers after

dedoping and found to be consistent with polaron and

bipolaron descriptions of the electron transport

mechanism in polypyrrole. 15 refs.

AUSTRALIA

Accession no.478461

Item 332Journal of Polymer Science : Polymer Physics Edition

31, No.6, May 1993, p.677-92

FT-RAMAN INVESTIGATION OF THETHERMAL CURING OF PMDA/ODA POLYAMICACIDSJohnson C; Wunder S L

Temple University

The effect of solvent (NMP/xylene) on the curing

reactions of PMDA/ODA polyamic acids was investigated

in depth using Fourier transform-Raman spectroscopy.

The solvent was found to have a dramatic effect both on

the rate of cure and on the final extent of conversion of

the ring closure reaction. The kinetic data is shown to be

consistent with the concept that the amount of solvent

present in the films affects the rate of imidisation. 38 refs.

USA

Accession no.478344

Item 333Cellular Polymers

12, No.1, 1993, p.31-45

IR SPECTROSCOPY OF SITE-DEPENDENTINHOMOGENEITIES IN CONVENTIONALFLEXIBLE PU FOAMSteger W E; Machill S; Herzog K; Gerhards R; Jussofie

I; Schator H

Dresden,University; Goldschmidt Th.,AG

An IR microscope was used to study the cell membranes

of a flexible PU foam. Correlations were made of

absorbance values of methyl signals with absolute

thicknesses calculated from the interference patterns

observed in some spectra. 18 refs.

EUROPEAN COMMUNITY; GERMANY; WESTERN EUROPE

Accession no.477183

Item 334Applied Spectroscopy

47, No.3, March 1993, p.321-9

ANALYSIS OF POLYMER-DISPERSED LIQUIDCRYSTALS BY IR SPECTROSCOPYMcFarland C A; Koenig J L; West J L

Case Western Reserve University; Liquid Crystal

Institute

A comparison is made of the polymer and liquid crystal

droplet regions within polymer-dispersed liquid crystal

films using FTIR microspectroscopy. IR functional group

images of a droplet showed characteristic textures

corresponding to the visual images of the same droplet.

The textures in the IR images changed with IR polarisation

and with an applied electric field. Hysteresis was observed

in the IR region as a function of voltage and temperature.

USA

Accession no.476052

Item 335Polymer International

31, No.4, 1993, p.391-6

RAMAN SPECTROSCOPIC ANALYSIS OF THEMICROSTRUCTURES OF BUTADIENE-ACRYLONITRILE COPOLYMERSEdwards H G M; Johnson A F; Lewis I R; Cowie J M G

References and Abstracts

120 © Copyright 2001 Rapra Technology Limited

Bradford,University; Heriot-Watt University

The polybutadiene microstructures of a number of

copolymers of butadiene and acrylonitrile were studied

by quantitative Raman spectroscopy and a comparison

was made with IR studies of these copolymers. The

intensities of the v(C:C) and the v(CN) bands were also

used to determine the amount of each monomer in the

copolymer. 24 refs.

EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.474667

Item 336Polymer

34, No.5, 1993, p.933-7

ANALYSIS OF PHOTOOXIDATION OFPOLYMER MATERIALS BY PHOTOACOUSTICFTIRDelprat P; Gardette J L

Blaise Pascal,Universite

Injection moulded PP plates, with and without titanium

dioxide pigment, were irradiated in a medium-accelerated

photoageing device to the equivalent of 1 year of outdoor

exposure. Photoacoustic FTIR spectra of photooxidised

samples were recorded. They were analysed also by

transmission micro-FTIR analysis of cross-sectioned

layers. The oxidation profiles monitored were shown to

arise from oxygen diffusion limitation and also from theheterogeneous absorption of light by the titanium dioxide-

pigmented samples. The intensity of the carbonyl

absorbance measured by photoacoustic FTIR was

determined and it was shown that the front layer

degradation monitored by both techniques had identical

values. This rapid and non-destructive technique may be

used to quantitatively measure the surface degradation

of aged polymers. 21 refs.

EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.474356

Item 337Journal of The Textile Institute

84,No.1,1993,p.85-98

ON-LINE MEASUREMENT OF POLYVINYLALCOHOL SIZE ON WARP YARNS USING ANEAR-IR DIFFUSE REFLECTANCESPECTROSCOPY METHODGhosh S

Uniform application of size on warp yarns is essential to

achieve desired weaving efficiency; however, currently

no method is available to measure sizing materials on the

warp while it is being processed on a sizing machine. A

method of on-line measurement of size on the warp using

near-IR diffuse reflectance spectroscopy method is

described. A prediction model regression equation is

developed using a PLS modelling procedure using a

segment of the near-IR spectrum which is most sensitive

to changes in size concentration on the warp. A discussion

of the spectral region sensitive to the analyte (partly

hydrolysed polyvinyl alcohol) but less sensitive to the

substrate (polyester/cotton) is provided. 8 refs.

EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.472430

Item 338European Polymer Journal

29,No.4,April 1993,p.475-81

QUANTITATIVE ANALYSIS OF COPOLYMERSBY FOURIER TRANSFORM IRSPECTROSCOPYMao R; Huglin M B; Davis T P

Salford,University; ICI

Quantitative analysis of a series of copolymers of 2-

((phenylamino)carbonyl)oxyethyl methacrylate and 1-

methyl-2-phenoxyethyl methacrylate was carried out by

FTIR spectroscopy. Emphasis was placed on aspects

optimising the accuracy of the technique. The

irreproducibility resulting from the use of cast films was

shown to be overcome when using solutions. The criteria

for solvent selection were established. Highly satisfactory

calibration was afforded by blends of the two

homopolymers in solution, thus providing an absolute

calibration and obviating the use of model compounds or

copolymers of known composition. 23 refs.

EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.470745

Item 339Journal of Polymer Science : Polymer Physics Edition

30,No.12,Nov.1992,p.1305-10

ANALYSIS OF POLYMER FILMS BY DIFFUSEREFLECTANCE FTIR SPECTROSCOPY:CHARACTERISATION OF TERMINALCARBOXYL FUNCTIONALITIESde Donato P; Cases J M; Humbert B; Lutgen P;

Feyder G

INPL; Nancy,Universite

IR spectra of PETP films were obtained, with an excellent

signal-to-noise ratio, by diffuse reflectance measurements

on a KBr matrix using FTIR spectroscopy. All the spectra

exhibited a new band at 1684 cm/1, characteristic of the

C = 0 stretching vibration of a terminal acidic function in

the presence of internal hydrogen bonds. These acidic

functions may be used to monitor polymerisation rate.

19 refs.

EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.470191

Item 340Progress in Colloid & Polymer Science

Vol.90,1992,p.202-5

FOURIER TRANSFORM INFRARED

References and Abstracts

© Copyright 2001Rapra Technology Limited 121

SPECTROSCOPY STUDIES ON EPOXYNETWORKSScherzer T; Strehmel V; Taenzer W; Wartewig S

Merseburg,Technische Hochschule

Epoxy networks based on the diglycidyl ether of bisphenol

A cured with aliphatic diols of varying chain length in

the presence of magnesium perchlorate or with 4,4'-

diaminodiphenylmethane and imidazole, respectively,

were studied by FTIR spectroscopy. The effect of the

accelerator on the epoxy/amine system was investigated.

10 refs. (29th Europhysics Conference on

Macromolecular Physics,’Physics of Polymer

Networks’,European Physics Society/Technical

University Merseburg,Alexisbad/Harz, Germany,

Sept.1991)

EUROPEAN COMMUNITY; GERMANY; WESTERN EUROPE

Accession no.467804

Item 341Rubber Chemistry and Technology

65,No.4,Sept./Oct.1992,p.836-50

DIRECT CHARACTERISATION OF TYREMATERIALS BY PHOTOACOUSTICALINFRARED AND PROTON INDUCED X-RAYEMISSION SPECTROSCOPYWaddell W H; Parker J R

PPG Industries Inc.

Photoacoustical Fourier transform IR spectroscopy and

proton induced X-ray emission spectroscopy were used

to characterise tread lugs sectioned from two worn off-

the-road tyres. The tyres had experienced similar service

but displayed significantly different performance in that

‘chipping/chunking’ was visible in one tyre brand. The

two techniques were also used to examine a variety of

rubber compounding ingredients, such as polymers and

fillers, and model tyre compounds containing different

levels of these ingredients. 39 refs.

USA

Accession no.464954

Item 342Polymer

33,No.23,1992,p.5085-9

QUANTITATIVE ANALYSIS OF THE SI-HGROUPS FORMED ONPOLY(DIMETHYLSILOXANE) SURFACES. ANATR FTIR APPROACHGaboury S R; Urban M W

North Dakota State University

Silane groups formed on the surface of

polydimethylsiloxane elastomers by argon or nitrogen gas

plasma treatments were determined. Kramers-Kronig

transformation of the ATR spectra of standard solutions

containing Si-H species allowed construction of

calibration plots which were independent of the angle of

incidence, crystal coverage and sample refractive index.

The Si-H concentrations of the plasma-treated

polydimethylsiloxanes were calculated from the

calibration plots, and indicate that gas/plasma treatments

of polydimethylsiloxane substrates result in Si-H

functionality gradients with higher concentrations near

the elastomer surface. Relevance to biocompatibility is

indicated. 23 refs.

USA

Accession no.464495

Item 343European Polymer Journal

28,No.9,Sept.1992,p.1147-50

INFRARED SPECTROPHOTOMETRY OFMALEIC ANHYDRIDE TERPOLYMERSStaudner E; Kysela G; Turayova Z; Slyskova E;

Brissova M

Slovak Technical University

A modified internal standard method has been developed

to determine the compositions of terpolymers of maleic

anhydride with styrene and a methacrylate or an acrylate.

The method involves IR spectrophotometry of the

samples. IR spectra are recorded by means of the

potassium bromide technique. The IR analysis is based

on integrated absorption of the anhydride and ester

carbonyl groups. 9 refs.

CZECHOSLOVAKIA; EASTERN EUROPE

Accession no.464393

Item 344Macromolecules

25,No.24,23rd Nov.1992,p.6621-30

FOURIER TRANSFORM INFRARED ANDELECTRON SPECTROSCOPY FOR CHEMICALANALYSIS STUDIES OF BLOCK COPOLYMERSOF STYRENE AND DIMETHYLSILOXANEChen X; Gardella J A; Kumler P L

Buffalo,State University of New York; New York,State

University

The surface segregation of poly(dimethylsiloxane) in

chloroform solution cast films of styrene and

dimethylsiloxane block copolymers in AB diblock as well

as ABA and BAB triblock types was investigated by

ESCA and ATR FTIR. Poly(dimethylsiloxane) surface

segregation was mainly dependent on the architecture of

the block copolymers and the poly(dimethylsiloxane)

block length. AB-type diblock copolymers exhibited a

relatively thicker pure poly(dimethylsiloxane) surface

layer, and the surface segregation effects were detected

up to the ATR FTIR sampling depth. All three types of

block copolymers presented much higher

poly(dimethylsiloxane) concentrations on their outermost

surface region (about 0.27A from the air interface) than

the bulk materials.

USA

Accession no.464314

References and Abstracts

122 © Copyright 2001 Rapra Technology Limited

Item 345Polymer Bulletin

29,No.5,Nov.1992,p.527-33

IN SITU INFRARED KINETIC STUDY OF THETHERMAL CONVERSION OFPOLYPHENYLENE-1,2-DIBROMOETHYLENETO POLYPHENYLENEACETYLENEPatel V L; Church S P; Khan N

Courtaulds Research

The thermal reaction of polyphenylene-1,2-

dibromoethylene under argon flow was investigated using

in situ kinetic IR spectroscopy. Between 200 and 250C,

the reaction proceeded via elimination of hydrogen

bromide to form a copolymer containing phenylene

acetylene linkages partially interrupted by brominated

units. The activation energy was considerably below the

C-Br bond dissociation energy. 5 refs.

EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.462972

Item 346Polymer

33,No.20,1992,p.4219-29

STRUCTURE OR THE SKIN AND CORE OFULTRADRAWN POLYETHYLENE FILMS BYVIBRATIONAL SPECTROSCOPYAgosti E; Zerbi G; Ward I M

Milano,Politecnico; Leeds,University

Films about 80 micrometres thick were studied by ATR

IR spectroscopy at various angles of incidence, IR

absorption spectroscopy including polarised light and

variable temperature, and Raman spectroscopy under

different scattering geometries. The results were

interpreted on the basis of the theoretical concepts of

the lattice dynamics of ordered and disordered

polymethylene systems previously worked out. A

gradient of molecular and crystalline structures was

found from the surface into the core. The skin was highly

orthorhombic. Moving inside the film, both monoclinic

and orthorhombic lattices coexisted. A new phase with

isolated trans-planar sequences was observed in the core.

Various kinds of collective and oriented or isolated

conformational disorder were identified. A molecular

model is proposed for the process of orientation during

drawing. 47 refs.

EUROPEAN COMMUNITY; ITALY; UK; WESTERN EUROPE

Accession no.462787

Item 347Macromolecules

25,No.19,14th Sept.1992,p.5069-73

POLYMER MUTUAL DIFFUSIONMEASUREMENTS USING INFRARED ATRSPECTROSCOPYvan Alsten J G; Lustig S R

Du Pont de Nemours E.I.,& Co.Inc.

A technique for measuring mutual diffusion coefficients

of polymers in the melt using IR attenuated total

reflectance spectroscopy is described. This method

measures the dissolution of a polymeric diffusant into a

matrix of another polymer and is applicable to any

diffusion couple with IR-distinguishable bands. In situ

measurements of the diffusion of various molecular

weight polystyrenes (deuterated into a matrix of

hydrogenated) and the temp. dependence of the diffusion

of PMMA (deuterated into hydrogenated) are presented.

The method can operate from room temp. to 400C.

Relevance to welding and bonding is indicated. 11 refs.

USA

Accession no.462778

Item 348Macromolecules

25,No.19,14th Sept.1992,p.4996-5001

INFRARED AND THERMAL ANALYSISSTUDIES OF TRANSREACTIONS IN PHENOXY-POLYCARBONATE BLENDSYang X; Painter P C; Coleman M M

Pennsylvania,State University

Bisphenol A phenoxy polymers and bisphenol A

polycarbonates from a variety of sources and with different

molec. wts. were blended in solution and cast. Changes

from aromatic to aliphatic carbonate groups were monitored

by FTIR using a heating cell mounted inside the sample

chamber. Significant ester exchange reactions were seen

at temps as low as 160C. DSC revealed changes in Tg for

repeat scans. Differences between reactions occurring in

solution blending and melt blending are discussed. 9 refs.

USA

Accession no.462768

Item 349Journal of Natural Rubber Research

7,No.2,p.152-5

FTIR STUDIES ON AMINO GROUPS INPURIFIED HEVEA RUBBERAik-Hwee E;Tanaka Y;Seng-Neon G

MALAYA,UNIVERSITY; TOKYO,UNIVERSITY OF

AGRICULTURE & TECHNOLOGY

The FTIR spectrum of NR showed characteristic bands

of attached nitrogenous compounds at 3280 and 1540cm/

1. These bands diminished if the fresh field latex was

treated with enzyme followed by washing in the presence

of surfactant. A band at 3320cm/1 that remained after the

treatment indicated the presence of residual amino acids

bonded to the rubber particles. 8 refs.

JAPAN; MALAYSIA

Accession no.461830

Item 350Makromolekulare Chemie

References and Abstracts

© Copyright 2001Rapra Technology Limited 123

193,No.9,Sept.1992,p.2413-20

FTIR SPECTRA AND CHAIN CONFORMATIONSIN THE CRYSTALLINE FORMS ANDCLATHRATES OF SYNDIOTACTIC POLY-P-METHYLSTYRENEGuerra G;Dal Poggetto F;Iuliano M;Manfredi C

NAPOLI,UNIVERSITA

IR spectra are reported for syndiotactic poly-p-

methylstyrene (PPMS) samples exhibiting various

crystalline forms and clathrate structures. Bands due to

the syndiotactic stereostructure, bands typical of the two

different chain conformations observed in the crystalline

structures, and bands sensitive to intermolecular

interactions typical of the different modes of chain

packing are pointed out. Observed similarities with

syndiotactic PS are indicated. A complete assignment via

Fourier transform IR analysis of chain conformations is

presented for all the known crystalline forms and

clathrates of syndiotactic PPMS. 18 refs.

EUROPEAN COMMUNITY; ITALY; WESTERN EUROPE

Accession no.461408

Item 351Macromolecules

25,No.16,3rd Aug.1992,p.4119-26

POLYSTYRENE PHOTOOXIDATION. I.IDENTIFICATION OF THE IR-ABSORBINGPHOTOPRODUCTS FORMED AT SHORT ANDLONG WAVELENGTHSMailhot B;Gardette J-L

BLAISE PASCAL,UNIVERSITE

PS (Gedex) films were exposed to radiation of long

wavelength (above 300 nm) and short wavelength (253.7

nm) under atmospheric oxygen. Changes in the FTIR

spectra of the photooxidised samples were followed and

several postirradiation treatments including chemical

derivatisation performed. HPLC analysed the low

molec.wt. fragments that were obtained after extraction

by methanol. The absorption maxima which were found

in the carbonyl and hydroxyl regions of the IR were

assigned, and the corresponding photoproducts were

identified. 24 refs.

EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.460096

Item 352SAMPE Journal

28,No.4,July/Aug.1992,p.37-42

EPOXY CURE MONITORING USING FIBRE-OPTIC RAMAN SPECTROSCOPYMyrick M L;Angel S M;Lyon R E;Vess T M

LAWRENCE LIVERMORE NATIONAL

LABORATORY

The curing of an epoxy matrix used for wet-filament-

wound composites was monitored using Raman

spectroscopy measured over fibre optics. The extent of

the reaction of the epoxy resin (DER 332) as a function

of time was measured through changes in peak heights of

several vibrational modes. Temperature measurements

were made over the same fibre optics used to obtain the

cure chemistry data by measuring the intensity of anti-

Stokes Raman scattering from the epoxy resin. Both

single-fibre and dual-fibre probes were evaluated. 20 refs.

USA

Accession no.460085

Item 353Applied Spectroscopy

46,No.7,July 1992,p.1113-6

ATR/IR SPECTROSCOPIC METHOD FORFOLLOWING PHOTO-POLYMER CURINGSnyder R W;Fuerniss S J

IBM CORP.

A method for studying the photo-induced polymerisation

of photoresists and solder masks at the substrate/

photopolymer interface, using ATR and IR spectroscopy

is described. The technique is especially useful for dry

film photoresists and gives information on cure levels

affected by exposure dose and photoresist thickness. The

photoprocessing of Vacrel 8100 series solder mask and

Riston 3100 series photoresists from Dupont are used as

examples. 23 refs.

DU PONT DE NEMOURS E.I.,& CO.INC.USA

Accession no.459390

Item 354Polymer

33,No.7,1992.p.1370-3

CARBON-13 LIQUID- AND SOLID-STATENUCLEAR MAGNETIC RESONANCE ANDINFRA-RED STUDIES OF AMINE-CUREDEPOXY RESINSFischer A;Schlothauer K;Pfitzmann A;Spevacek J

CZECHOSLOVAK ACADEMY OF

SCIENCES,INST.MACR.CHEM.;

MERSEBURG,UNIVERSITY

The final network structure of an epoxy resin system and

the course of reaction of bisphenol a diglycidyl ether with

1-cyanoguanidine as curing agent dissolved in dimethyl

formamide in the presence of different accelerators were

studied by liquid-state carbon-13 NMR spectroscopy,

solid-state carbon-13 cross-polarisation/magic angle

spinning NMR spectroscopy and IR spectroscopy.

Fractions of reactive groups such as oxirane rings, primary

and secondary hydroxyl groups, imide and nitrile groups

were detected as functions of epoxy consumption and

reaction conditions. Structural tautomerism of the curing

agent, the influence of water, the reaction of nitrile groups

and other structural features of the curing system were

examined. 11 refs.

References and Abstracts

124 © Copyright 2001 Rapra Technology Limited

CZECHOSLOVAKIA; EASTERN EUROPE; GERMANY

Accession no.452021

Item 355Die Makromolekulare Chemie- Macromolecular

symposia

No.53,Jan.1992,p.89-103

CHARACTERISATION OF POLYMERDEFORMATION BY RHEO-OPTICAL FOURIER-TRANSFORM INFRARED SPECTROSCOPYSiesler H W

ESSEN,UNIVERSITY

The above technique is explained with emphasis on a

newly constructed computer-controlled variable-temp.

stretching machine which allows monitoring of

vibrational spectra and stress-strain diagrams during

deformation of polymer films up to 523K. Results are

given for a polyetherurethane elastomer and PETP to

identify conformational changes and transitions, chain

alignment and strain-induced crystallisation. 24 refs.

(Presented at Polymer 91,Int.Symp.on Polymer Materials

- Preparation,Characterisation & Properties. IUPAC,

Macromolecular Div., Melbourne,Australia,10t-15th

Feb.1991).

GERMANY

Accession no.448515

Item 356Materiaux & Techniques

79,No.11-12,Nov-Dec.1991,p.69-72

DETERMINATION OF 5-ETHYLIDENENORBORNENE (ENB) BYFOURIER-TRANSFORM INFRAREDSPECTROSCOPY (FTIR)EXXON CHEMICAL FRANCE; EXXON

RESEARCH & ENGINEERING CO.

A sensitive Fourier transform infrared spectroscopic

method for the determination of ENB content in ethylene

propylene diene (EPDM) copolymers is described in

detail. It is applicable for ENB contents in the 0.1 to 10%

weight range. The repeatability standard deviation of the

method is given as 0.020 and the reproducibility standard

deviation, 0.080 at the 5% weight level.

EUROPEAN COMMUNITY; FRANCE; USA; WESTERN

EUROPE

Accession no.445896

Item 357Shawbury, 1992, pp.iii,333. LS.300. 12ins. 14/5/92.

9922

RAPRA COLLECTION OF INFRARED SPECTRAOF RUBBERS, PLASTICS ANDTHERMOPLASTIC ELASTOMERSSidwell J

RAPRA TECHNOLOGY LTD.

This collection of spectra includes both transmission and

pyrolysate (condensed phase) spectra of a comprehensive

range of technically important rubber and plastic based

materials. Included are homopolymers, copolymers and

blended materials, and pyrolysate spectra have by

necessity been obtained for crosslinked rubbers and

thermoset materials. Materials are indexed under both

polymer type and trade name. Photocopies of this source

are not available. The publication can be purchased from

Rapra’s Publication Sales group.

EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.445621

Item 358Die Makromolekulare Chemie- Macromolecular

symposia

No.52,Dec.1991,p.307-12

DEGRADATION BEHAVIOUR OFPOLYURETHANE STUDIED BY LINEARTEMPERATURE PROGRAMMED PYROLYSISFTIR SPECTROSCOPYHerzog K

DRESDEN,TECHNISCHE UNIVERSITAT

PU was produced from MDI and adipate esters. Its thermal

degradation was studied by an FTIR spectrometer with

two measurement beams, i.e. the pyrolysis cell (in the

sample beam) was connected to a gas cell (in the reference

beam). Stages in the decomposition process were

elucidated and degradation products were identified. 3

refs. (9th Eur.Symp.on Polymer Spectroscopy (ESOPS

9),Cologne,Germany, 25th-27th Sept.1990)

GERMANY

Accession no.442543

Item 359Applied Spectroscopy

45,No.7,Aug.1991,p.1193-8

APPLICATION OF ATR-IR TO THE ANALYSISOF SURFACE STRUCTURE AND ORIENTATIONIN UNIAXIALLY DRAWN PETPWalls D J

DU PONT CO.

A critical assessment was made of the use of ATR-IR

spectroscopy for the study of the surface composition and

orientation in uniaxially drawn PETP films. The use of

reference bands commonly used in such analyses was

examined, paying particular attention to the possible

deleterious effects of sample orientation, incident

polarisation and sample contact. The use of conventional

sampling procedures to obtain in-plane surface dichroism

measurements is shown. 25 refs.

USA

Accession no.432374

Item 360Polyurethanes 90.Conference Proceedings.

References and Abstracts

© Copyright 2001Rapra Technology Limited 125

Orlando,Fl.,30th Sept-3rd Oct.1990,p.527-39. 43C6

FT-IR - A PROBE INTO THE REACTIONKINETICS AND MORPHOLOGYDEVELOPMENT OF URETHANE FOAMSPriester R D;McClusky J V;O’Neill R E;Turner R

B;Harthcock M A; Davis B L

DOW CHEMICAL CO.

(SPI,Polyurethane Div.)

An IR technique has been used to obtain spectra of a

reacting PU foam system having a given temperature

profile every 5-10 seconds. Chemical reaction rates and

morphology development were evaluated using computer

assisted spectral analysis to simultaneously monitor both

isocyanate disappearance and the evolution of urethane

and urea carbonyl absorbancies. Quantitation of the

products vs. time is obtained via curve fitting and

deconvolution routines. Applications have been proven

in a wide variety of cellular PU systems. 15 refs.

USA

Accession no.432190

Item 361Polymer

32,No.10,1991,p.1862-6

CONFORMATIONAL STRUCTURE OFBISPHENOL A POLYCARBONATE STUDIED BYIR SPECTROSCOPYSchmidt P;Dybal J;Turska E;Kulczycki A

CZECHOSLOVAK ACADEMY OF SCIENCES;

POLISH ACADEMY OF SCIENCES

An IR spectroscopic study of the conformational

structures of polycarbonate (Bistan AF) was carried out

in the solid state and in solution. Based on the temperature

dependences of the IR spectra, bands sensitive to

transitions between the trans-trans and trans-cis

conformations of the carbonate group were identified. An

assignment of these bands to the specific molecular

conformations of the polymer is proposed. 16 refs.

CZECHOSLOVAKIA; EASTERN EUROPE; POLAND

Accession no.431935

Item 362Applied Spectroscopy

45,No.5,June 1991,p.752-5

IMPROVEMENT OF THE LIMITINGTHICKNESS OF THE MEASURABLE SURFACELAYER ON POLYMER FILMS USING FOURIERTRANSFORM IR ATTENUATED TOTALREFLECTION SPECTROSCOPY WITH THEUSE OF SILVER ISLAND FILMSNiahikawa Y;Ito Y;Fujiwara K;Shima T

KONICA CORP.

The use of silver films under Kretschmann’s attenuated

total reflection geometry has improved the detection limit

of the surface layer on polymer films. An enhancement

factor 10 and 2 is reported for polydimethylsiloxane and

polycarbonate respectively, compared to the conventional

ATR technique. 14 refs.

JAPAN

Accession no.428812

Item 363Polymer Communications

32,No.8,1991,p.229-31

RAMAN SPECTROSCOPY. AN ORIGINAL ANDNON-DESTRUCTIVE METHOD TODETERMINE THE RATE OF POLYMERISATIONPHOTOINITIATED BY LASER BEAMMailhot G;Philippart J L;Bolte M

BLAISE PASCAL,UNIVERSITE

A Raman spectrophotometer was used to measure in situ

the polymerisation rate of acrylamide photoinitiated by

hydrogen chromate anion in aqueous solution upon

irradiation by laser beam (ionised argon) . The progress

of the reaction was monitored at 2930/cm, the absorption

characteristic of the polymer formed. The method was

found to be reliable, but is limited to monomers whose

polymer is soluble in the reaction medium. 10 refs.

EUROPEAN COMMUNITY; FRANCE; WESTERN EUROPE

Accession no.426029

Item 364Journal of Applied Polymer Science

42,No.8,20th April 1991,p.2169-90

ANALYSIS OF REACTION-INJECTION-MOULDED POLYURETHANES BY NEAR-INFRARED DIFFUSE REFLECTANCESPECTROSCOPYMiller C E;Eichinger B E

WASHINGTON,UNIVERSITY

The ability of near-IR diffuse reflectance spectroscopy

to characterise RIM PU elastomers was demonstrated.

The specific effects of composition, density, phase

separation, and moisture content on the near-IR spectra

were identified. The ability of near-IR spectroscopy to

make rapid assessments of physical properties is

discussed. 52 refs.

USA

Accession no.424385

Item 365Polymer Communications

32,No.4,1991,p.125-8

INFRA-RED DETERMINATION OFCONFORMERS OF POLYETHYLENETEREPHTHALATEYang X;Long F;Shen D;Qian R

ACADEMIA SINICA

An IR spectroscopic method is described for analysing

quantitatively the conformers of the ethylene glycoxy

moeity of PETP, in the amorphous and crystalline regions.

References and Abstracts

126 © Copyright 2001 Rapra Technology Limited

The method uses spectral band reconstructions of the

profiles of either the 382/cm band or the 1020/cm band

for a series of specimens annealed at different temps.

Consistent results were obtained from both bands for the

compositions of the three conformers, i.e. the trans

conformer in the crystalline state and both the trans

conformer and the gauche conformer in the amorphous

state. This demonstrates the reliability of the method. 13

refs.

CHINA

Accession no.422551

Item 366Applied Spectroscopy

45,No.2,Feb.1991,p.173-7

QUANTITATIVE ANALYSIS OF ADDITIVES INLOW-DENSITY POLYETHYLENE USINGINFRARED SPECTROSCOPY ANDMULTIVARIATE CALIBRATIONVigerust B;Kolset K;Nordenson S;Henriksen

A;Kleveland K

NORWAY,CENTRE FOR INDUSTRIAL RESEARCH;

STATOIL AS

Multivariate calibration methods were used to establish

a new method for measurement of three selected additives

in LDPE. The determination of the concentration of silica,

erucamide and butylhydroxytoluene was based on IR

spectroscopy and a calibration model. The concentrations

were between 20 and 1100 wt/ppm. Compared with

traditional chemical analyses, the new method was shown

to be both time- and cost-effective and to be more precise.

The method has potential for quality control of PE. 8 refs.

NORWAY; SCANDINAVIA; WESTERN EUROPE

Accession no.421049

Item 367Analyst

115,No.12,Dec.1990,p.1597-9

FOURIER TRANSFORM IR SPECTROMETRICDETERMINATION OF POLYETHYLENEGLYCOL (ANTISTATIC AGENT) IN HDPEKumar T

MOBIL CHEMICAL CO.

A direct IR method using Fourier transform IR

spectroscopy for rapidly determining the low relative

molec.wt. PEG, Carbowax 400, in HDPE is described. It

does not require solvent extraction of PEG from PE and

its speed and simplicity make it suitable for quality control

applications. Measurements on HDPE containing PEG

using this technique are reported. 9 refs.

USA

Accession no.419959

Item 368Plaste und Kautschuk

37,No.6,June 1990,p.185-6

German

IR SPECTROSCOPIC ANALYSIS OF JONOL INPOLYETHYLENE AND ETHYLENE-VINYLACETATE COPOLYMER FILMSWinterberg H;Brunn J;Fuehrling W

MERSEBURG,TECHNISCHE HOCHSCHULE

An IR spectroscopic technique for the analysis of 2, 6-di-

tert-butyl-4-methylphenol stabilisers in PE and EVAc

films is described and its effectivenesss evaluated. 3 refs.

EAST GERMANY; EASTERN EUROPE

Accession no.418941

Item 369Polymer

32,No.2,1991,p.338-42

RAMAN SPECTROSCOPICCHARACTERISATION OF HIGH-VINYLPOLYBUTADIENES PRODUCED FROMANIONIC POLYMERISATIONPoshyachinda S;Edwards H G M;Johnson A F

BRADFORD,UNIVERSITY

n-Butyllithium was the initiator and cyclohexane the

solvent for the above polymerisation. Among

complexing agents used to change the mode of addition

to 1,2 or vinyl, 1,2-dipiperidinoethane and diglyme

were very effective, although their effectivenessdecreased with temp. The microstructure of the

polymers was characterised by Raman spectroscopy

using the Raman active carbon-carbon double bond

stretching bands of vinyl, cis and trans structures at

1640, 1650 and 1664/cm, respectively. A curve analysis

program applied to the computerised data acquisition

enabled the band areas of each component band to be

evaluated. 16 refs.

EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.417574

Item 370Applied Spectroscopy

44,No.10,Dec.1990,p.1719-21

DETERMINATION OF HYDROXYL NUMBER INPOLYMERS BY INFRARED SPECTROSCOPYLee K A B;Hurley S M;Siepler R A;Mills R

D;Handrich K A;Conway J J

JOHNSON S.C.,& SON INC.

An infrared analysis method was developed for

determining the hydroxyl number in samples of polyesters

formed by the copolymerisation of a hydroxy-functional

acrylic oligomer with adipic acid and 1, 6-hexanediol.

The method was shown to be sufficiently accurate, to be

faster than chemical analysis and to reduce exposure to

irritating, toxic and corrosive chemicals. 9 refs.

USA

Accession no.417249

References and Abstracts

© Copyright 2001Rapra Technology Limited 127

Item 371Analyst

115,No.10,Oct.1990,p.1319-22

FOURIER TRANSFORM INFRAREDSPECDTROMETRIC DETERMINATION OFSTEARIC ACID IN STYRENIC POLYMERSKumar T

MOBIL CHEMICAL CO.

The use of additive isolation procedures and Fourier

transform IR spectrometry for quantifying external and

internal stearic acid lubricant in PS resins is discussed

and advantages over previously-used techniques are

considered. 13 refs.

USA

Accession no.413159

Item 372Applied Spectroscopy

44,No.7,Aug.1990,p.1137-42

FIBRE STRUCTURE STUDY BY POLARISED IRATTENUATED TOTAL REFLECTIONSPECTROSCOPY: ORIENTATIONDEVELOPMENT OF NYLON 66 AT VARIOUSSPINNING SPEEDSSamanta S R;Lanier W W;Miller R W;Gibson M E

MONSANTO CHEMICAL CO.

A study was made of orientational development in the

high-speed spinning of high-viscosity and low-viscosity

nylon 66 yarns using IR dichroism. A relationship between

IR dichroism and orientation factor was developed and a

relationship between orientation measured by IR and X-

ray diffraction demonstrated. These were used to obtain

the transition moment direction of a molecular vibration,

which would otherwise be impossible to obtain by a single

technique. 15 refs.

USA

Accession no.411182

Item 373Polymer

31,No.7,July 1990,p.1222-7

VIBRATIONAL ANALYSIS OF THE TIGHT (110)FOLD IN POLYETHYLENEWolf S;Schmid C;Hagele P C

ULM,UNIVERSITY

The defect density of states of the tight (110) fold in PE

is calculated using Green’s functions in the frequency

range 500 to 1400/cm. Resonance modes of the (110) fold

calculated at 1348, 1342 and 1288/cm are assigned to

infrared bands at 1346-1347 and 1342-1343/cm and near

1295/cm. It is shown that the (110) folds (approximately

g’g’ggtg) also contribute to the gtg/gtg’ bands at 1368/

cm. In contrast to the (200) fold, it does not exhibit a

localised gap mode near 700cm. The calculations allow

the observed IR bands to be assigned to the defect modes

of the (110) fold without introducing the qualitative

concept of distorted gg conformations used in the

literature. 29 refs.

EUROPEAN COMMUNITY; WEST GERMANY; WESTERN

EUROPE

Accession no.403740

Item 374Polymer Communications

31,No.7,July 1990,p.290-2

EVIDENCE FOR THE CONDUCTIONMECHANISM IN IODINE-DOPED CIS-POLYISOPRENE RUBBER USING RESONANCERAMAN SPECTROSCOPYWilliams K P J;Gerrard D L

BP RESEARCH CENTRE

Resonance Raman spectroscopy was used to investigate

the products formed upon iodine doping of cis-

polyisoprene. Evidence for the production of polyenes

was found. It is suggested that these are in part responsible

for the increased conductivity of iodine-doped cis-

polyisoprene. A possible chemical reaction is postulated

for polyene production. 18 refs.

EUROPEAN COMMUNITY; UK; WESTERN EUROPE

Accession no.403729

Item 375Applied Spectroscopy

44,No.3,March/April 1990,p.512-8

FT-IR METAL OVERLAYER ATRSPECTROSCOPY USING A COATEDELASTOMER BACKING MATERIALKhoo C G L;Ishida H

CASE WESTERN RESERVE UNIVERSITY

A metal overlayer FT-IR-ATR technique which markedly

enhances the signal-noise ratio of monolayer and

submonolayer film spectra is described. Experimental

evidence of the enhancement is given for, as examples, a

deposited PVAc film of 0.5 or 5nm and a thin film of

adsorbed protein human serum albumin, estimated to be

of the order of 5nm. The metals investigated were gold

and aluminium, with a substrate of polyether-urethane

elastomer. 20 refs.

USA

Accession no.401264

Item 376Applied Spectroscopy

44,No.4,May 1990,p.543-9

DEVELOPMENT OF ASPECTRAL DATA BASEFOR THE IDENTIFICATION OF FIBRES BY IRMICROSCOPYTungol M W;Bartick E G;Montaser A

US,FBI; WASHINGTON G.,UNIVERSITY

A detailed study of the application of IR microscopy for

single fibre analysis was undertaken. A library of 43

References and Abstracts

128 © Copyright 2001 Rapra Technology Limited

polymer fibres, distinguishable by their IR spectra, was

constructed. 23 refs.

USA

Accession no.400336

Item 377British Polymer Journal

22,No.2,1990,p.97-105

STUDY OF THE FORMATION ANDCHARACTERISATION OF OXAZOLIDONE-ISOCYANURATE POLYMERS USINGDIFFERENTIAL SCANNING CALORIMETRYAND INFRARED SPECTROSCOPYLee Y S-K;Hodd K;Wright W W;Barton J M

BRUNEL UNIVERSITY; UK,ROYAL AIRCRAFT

ESTABLISHMENT

The polymers were prepared by reacting five glycidyl

ethers with 4, 4'-diisocyanatodiphenylmethane in the

presence of 2-ethyl-4-methylimidazole. The degree of

cure of the resins was followed by IR spectroscopy and

DSC. The rates of the isocyanurate to oxazolidone

linkages were determined quantitatively by an infrared

method and the glass transition temperatures of the

polymers were measured by DSC and dynamic

mechanical thermal analysis. 16 refs.

UK; EUROPEAN COMMUNITY

Accession no.394426

Subject Index

© Copyright 2001 Rapra Technology Limited 129

Subject Index

1,2-POLYBUTADIENE, 3692,6-DI-TERT-BUTYL-4-

METHYLPHENOL, 368

AABRASION RESISTANCE, 259ABSORBANCE, 259 264 337ABSORPTION, 5 36 87 96 102

127 132 154 164 169 199 260343

ABSORPTION COEFFICIENT,223 257 343

ABSORPTION SPECTRA, 6 151155 156 177 189 246 297 330343

ACCELERATED AGEING, 336ACCELERATED TEST, 18 76ACCELERATOR, 304 340 354ACETONE, 22 272ACETYL GROUP, 238ACETYLENE COPOLYMER, 345ACETYLENE TERMINATION,

242ACID, 2 193ACID FLUORIDE GROUP, 146ACID NUMBER, 152ACID-BASE INTERACTION, 165

233ACIDIC, 233ACOUSTOOPTICAL DEVICE,

152ACRYLAMIDE COPOLYMER,

125ACRYLAMIDE TERPOLYMER,

125ACRYLATE, 124 260ACRYLATE COPOLYMER, 184

343ACRYLIC ACID, 133ACRYLIC ACID COPOLYMER,

125 322ACRYLIC ACID TERPOLYMER,

125ACRYLIC COPOLYMER, 66ACRYLIC ESTER, 124ACRYLIC ESTER COPOLYMER,

184ACRYLIC RESIN, 246 280 282

319 326ACRYLONITRILE, 154 226 272

295ACRYLONITRILE

COPOLYMER, 221 228ACRYLONITRILE GROUP, 154

ACTIVATION ENERGY, 214 230240 242 312 345 347

ACTIVATOR, 304ACYL AMMONIUM, 329ACYLATION, 146 301ADDITIVE, 33 55 68 71 86 87 104

132 137 138 154 156 160 166176 189 202 203 212 215 246248 249 253 264 304 322 340341 354 366 371

ADHESION, 232 233 285ADHESIVE, 88 192 193 232 233

285 289ADIPATE COPOLYMER, 257ADSORPTION, 42 119 126AGEING, 27 33 41 104 112 154

177 189 312AGGREGATE, 93 293ALBUMIN, 375ALCOHOL, 36 288ALCOHOL GROUP, 147 225ALDEHYDE, 154 288ALDEHYDE GROUP, 189ALIGNMENT, 207 243ALIPHATIC, 79 133 241ALKALI, 294ALKALINE DEGRADATION, 50ALKANE, 10 67 189ALKENE, 189ALKYL HYDROXIDE, 36ALKYL METHACRYLATE

COPOLYMER, 321ALKYLBENZENE SULFONATE,

99ALLOTROPIC, 304ALTERNATING COPOLYMER,

182 273ALTERNATING

COPOLYMERISATION, 239ALTERNATING POLYMER, 182ALUMINA, 126 196ALUMINIUM, 375ALUMINIUM BUTOXIDE, 13ALUMINIUM CHLORIDE, 155ALUMINIUM FOIL, 246ALUMINIUM OXIDE, 110 126

196 233ALUMINIUM TRICHLORIDE,

317AMIDE, 154AMIDE COPOLYMER, 308AMIDE GROUP, 154AMINE, 197 227 248 249 253 277

340 354AMINE GROUP, 244 286

AMINO ACID, 349AMMONIA, 154 236AMORPHOUS, 26 52 73 90 107

116 142 257 350 365AMPHOTERIC, 233AMYL ACETATE, 122ANHYDRIDE, 248 249 288 343ANHYDRIDE GROUP, 273ANIONIC, 30 99ANIONIC POLYMERISATION,

188 214 314 369ANISOTROPY, 143 223 282ANNEALING, 23 56 89 94 147

177 183 187 197 225 252 316365

ANTHRACENE, 129ANTI-BLOCKING AGENT, 324

366ANTIFOULING, 42 124ANTIMONY COMPOUND, 271ANTIOXIDANT, 189 303 322 366APODISATION FUNCTION, 155AQUEOUS EMULSION, 246AQUEOUS PHASE, 295AQUEOUS SOLUTION, 65 85 93

258ARGON, 3 345AROMATIC, 89 133 202 241 252

257 271 302 303 325 371ARRHENIUS’S LAW, 58ATACTIC, 57 74 107 219 350AUTOXIDATION, 189AZOBISISOBUTYRONITRILE,

321

BBACK-SCATTERING, 247BANDWIDTH, 237BARRIER FILM, 194 245BARRIER LAYER, 275BASE, 233BEAMSPLITTER, 283BENZENE, 126 142 252 317 321BENZENE RING, 9 272BENZYL DIMETHYLAMINE,

248BIAXIAL ORIENTATION, 131

230BILAYER, 223BINARY BLEND, 11BINARY SYSTEM, 165BIOCOMPATIBILITY, 342BIODEGRADATION, 156BIPOLAR, 102

Subject Index

130 © Copyright 2001 Rapra Technology Limited

BIPOLARON, 331BIREFRINGENCE, 114BISMALEIMIDE COPOLYMER,

239BISPHENOL A, 197 241 312 340BISPHENOL A DIGLYCIDYL

ETHER, 79 354BISPHENOL A

POLYCARBONATE, 177 278361

BISPHENOL DIGLYCIDYLETHER, 79

BLEND, 11 29 45 52 57 92 106116 117 120 128 129 133 139165 166 218 221 229 233 241247 278 279 296 299 304 305310 311 313 316 318 323 348

BLOCK COPOLYMER, 101 188243 344

BLOCK POLYMERISATION, 314BOUND WATER, 185 246BRANCHING, 4 84BREAKAGE, 207BROMINATION, 345BROMINE COMPOUND, 274BULK, 9 17 146 164BUTADIENE, 226 272BUTADIENE COPOLYMER, 188

228BUTADIENE-ACRYLONITRILE

COPOLYMER, 104 154 226228 272 335

BUTADIENE-STYRENECOPOLYMER, 226 269 272

BUTANE ACRYLATE, 60BUTYL ACRYLATE

COPOLYMER, 35 184BUTYL ACRYLATE

TERPOLYMER, 21BUTYL GLYCIDYL ETHER, 28BUTYL HYDROXYTOLUENE,

366BUTYL METHACRYLATE

COPOLYMER, 321BUTYL METHACRYLATE

TERPOLYMER, 124BUTYL METHYLPHENOL, 368BUTYL RUBBER, 33BUTYLDIMETHYLSILYLOXY-

STYRENE COPOLYMER, 321BUTYLLITHIUM, 214

CCALCIUM CARBONATE, 300

304CALCIUM OXIDE, 196CALIBRATION, 110 127 141 176

211 234 247 259 264 283 303313 326 337 338 343

CALORIMETRY, 165CAMPHOR, 283CAPROLACTAM COPOLYMER,

308CAPSTOCK, 76 153CARBON 13, 2 13 127 155 229CARBON BLACK, 48 104 164

304CARBON DIOXIDE, 26 122 236

303CARBON DISULFIDE, 272CARBON FIBRE, 192 207 212

237 260CARBON FIBRE-REINFORCED

PLASTIC, 207 212 237 281CARBON MONOXIDE, 236CARBON TETRACHLORIDE,

126CARBON-13, 2 13 127 155 229

354CARBONATE, 241CARBONYL, 5 330CARBONYL GROUP, 41 50 93

103 154 165 297 343CARBOXY GROUP, 41CARBOXYL GROUP, 41 288 339CARBOXYLATE GROUP, 9CARBOXYLIC ACID, 228 260

288CARBOXYLIC ACID GROUP,

146 228CARBOXYLIC GROUP, 133CAST FILM, 29CASTING, 180 213CATALYST, 2 24 59 155 286CATIONIC POLYMERISATION,

240CAUSTIC SODA, 146CELLULAR MATERIAL, 59 360CELLULOSE, 116 294CETANE, 67CHAIN, 4 78 125 290CHAIN CONFORMATION, 27 51

57 78 309 350CHAIN DEFORMATION, 250CHAIN EXTENSION, 80 201CHAIN FOLDING, 373CHAIN LENGTH, 1 79 80 340CHAIN ORIENTATION, 51 119

195 199 223 250 309CHAIN PACKING, 350CHAIN SCISSION, 189 256 273

278 304 312 320 330CHAIN STRUCTURE, 10 78 125

350CHAR FORMATION, 273

CHEMICAL COMPOSITION, 1966 149 153

CHEMICAL DEGRADATION,154

CHEMICAL MODIFICATION, 941 61 79 108 115 146 196 220256 301 306 312 321 345

CHEMICAL PROPERTIES, 82108 152 154

CHEMICAL RESISTANCE, 154CHEMICAL SHIFT, 155CHEMICAL STRUCTURE, 2 10

19 36 43 54 56 70 72 74 79 8384 93 95 103 104 105 108 111116 122 123 124 125 133 138142 146 155 156 162 163 167174 177 182 189 192 354

CHEMICRYSTALLISATION, 50CHEMOMETRIC ANALYSIS, 73

141CHINA CLAY, 87 132CHITOSAN, 162CHLORINATED, 190CHLORINE, 317CHLOROFORM, 150CHROMATOGRAPHY, 113 138CHROMIUM OXIDE, 196CHROMOGEN, 143CHROMOPHORE, 143 218CIRCULAR DICHROISM, 101CLATHRATE, 350CLEARCOAT, 149CLOUD POINT, 93CLUSTER, 65 155 246COALESCENCE, 203 246COATING, 18 19 42 62 75 98 118

149 191 192 246 227 285COCATALYST, 155COERCIVE FIELD, 231COHESION, 180 282COLD CRYSTALLISATION, 210COLD DRAWN, 94 134COLLOIDAL PROPERTIES, 295COLOURANT, 189COLUMN CHROMATOGRAPHY,

215COMMINGLED, 77COMONOMER, 141 260COMPATIBILISER, 117 120 133COMPLEX, 42 89 140COMPLEX FORMATION, 140

181COMPLEXATION, 89COMPLEXING AGENT, 369COMPOSITE, 109 142 161 166

190 207 212 217 221 237 249279 281 286 328 352 357

COMPOSITION, 11 17 21 44 57

Subject Index

© Copyright 2001 Rapra Technology Limited 131

61 75 112 116 117 121 123 124128 129 133 141 165 278

COMPOUNDING, 304COMPOUNDING INGREDIENT,

341COMPRESSION MOULDED, 155COMPRESSION MOULDING, 86

144 159 204COMPUTER AIDED ANALYSIS,

155 247 356 369COMPUTER AIDED TESTING,

166 355 360COMPUTER PROGRAM, 166COMPUTER SIMULATION, 223COMPUTER SOFTWARE, 152COMPUTERISED ANALYSIS, 81CONCENTRATION

FLUCTUATION, 44 176CONCENTRATION GRADIENT,

44CONDENSATION, 127CONDENSATION REACTION,

12CONDENSED PHASE, 357CONDUCTIVE PLASTIC, 121

331CONDUCTIVE POLYMER, 121

298 345CONDUCTIVE RUBBER, 374CONFOCAL, 17 128 149 225CONFOCAL IMAGING, 62CONFORMATIONAL, 5 182 186

365CONFORMATIONAL

TRANSITION, 294 316 355361

CONJUGATED BOND, 304CONJUGATED POLYMER, 315

317 374CONTACT ANGLE, 327CONTAMINANT, 77 175COOLING, 27 88 155 187 224 247

252COPOLYESTER, 325COPOLYETHERSULFONE, 19COPOLYMER COMPOSITION,

72 73 110 155 184 188 204 321335 338 343

COPOLYMERISATION, 124 135142

COPPER, 108 142COPPER OXIDE, 142 196 275CORRELATION, 12 163 168 254

247 272CORRELATION

SPECTROSCOPY, 16 57 73148 167 168

COUPLING AGENT, 217 229 328

COVALENT BONDING, 154CRACKING, 91 156CRAZE RESISTANCE, 99CRAZING, 99CRITICAL CONCENTRATION,

154CRITICAL SOLUTION

TEMPERATURE, 93CROSS-POLARISATION, 354CROSSLINK, 9 13 58 61 75 151

154 332 377CROSSLINK DENSITY, 61 154

239 253 304CROSSLINKED, 60 75 151 197

253 278 290 304CROSSLINKED COPOLYMER,

61 200CROSSLINKING, 24 34 61 62 63

69 75 154 189 217 242 244 273328 377

CROSSLINKING AGENT, 61 151244

CROSSLINKING PHENOMENA,61 62 75 154

CROSSLINKING RATE, 62CRYOMICROTOMY, 156CRYSTAL, 6 187 223CRYSTAL STRUCTURE, 46 56

84 114 195 350CRYSTAL TRANSITION, 195CRYSTALLINE, 10 52 56 73 155

165 186 187CRYSTALLINITY, 19 23 31 46 52

56 84 90 94 97 114 129 155 165167 173 183 186 187 195 204218 219 223 234 241 251 252258 307 316 318 346 350 365373

CRYSTALLISATION, 23 26 50 5683 155 210 219 254 304 355

CRYSTALLISATION RATE, 123224

CRYSTALLISATIONTEMPERATURE, 56 155

CRYSTALLISED, 250CRYSTALLITE, 187 210CRYSTALLOGRAPHY, 134CUPRIC OXIDE, 196CURE, 58 353CURE RATE, 9 62 239 276 277

278 332CURE TEMPERATURE, 80CURE TIME, 200 304 354CURED, 149 197 312CURING, 9 19 24 34 38 62 63 75

88 118 149 161 191 217 278286 352 353 356

CURING AGENT, 24 59 61 151

154 197 248 249 253 276 277304 312 340 354

CURING REACTION, 62 75 239276 277

CURING SYSTEM, 75CURING TEMPERATURE, 37

242 304 354CYANOAZOBENZENE, 143CYANOBIPHENYL, 88CYANOGUANIDINE, 354CYCLIC DEFORMATION, 197CYCLIC VOLTAMMETRY, 298CYCLISATION, 80CYCLOHEXANE, 126CYCLOHEXAPHENYLENE

SULFIDE, 84CYCLOHEXYLMALEIMIDE

COPOLYMER, 64

DDATA DENSITY, 166DEACETYLATION, 273DEBONDING, 212DECALCIFICATION, 193DECANEDIOL, 79DECARBOXYLATION, 278DECOMPLEXATION, 89DECOMPOSITION, 113 189DECOMPOSITION

TEMPERATURE, 113 273 274DECONVOLUTION, 41DECYL METHACRYLATE

COPOLYMER, 321DEFORMATION, 55 79 94 99 107

161 169 187 197 253 281 282355

DEGRADATION, 27 33 41 50 76104 112 146 154 156 177 189

DEGRADATION PRODUCT, 76112 153 273 274 279 302 351358

DEGRADATION RATE, 112 323DEGRADATION

TEMPERATURE, 112DEGREE OF CONVERSION, 61

315DEGREE OF CRYSTALLINITY,

155 165 186 224DEGREE OF DISPERSION, 203DEGREE OF GRAFTING, 61 327DEGREE OF ORIENTATION, 52

307DEGREE OF

POLYMERISATION, 61 225241 257 293 315 317 329

DEGREE OF SWELLING, 300DEHYDROBROMINATION, 345

Subject Index

132 © Copyright 2001 Rapra Technology Limited

DEHYDROHALOGENAT, 374DENSITY, 20 59 114 234 250 307

364DENTIN, 193DEPOLARISATION, 210DEPROTECTION, 321DEPROTEINISATION, 224DEPTH PROFILING, 17 18 21 62

137 147 148 168 194 225 245336 344

DESILYLATION, 321DETERGENT, 99DEUTERATED, 36 143 347DEUTERATION, 89 258 294DEUTERIUM, 36 256 287 294DEUTERIUM OXIDE, 36 258DI-2-ETHYLHEXYL

PHTHALATE, 17DIACETYLENE, 220DIALLYL BISPHENOL

COPOLYMER, 239DIAMINODIPHENYLMETHANE,

340DIBLOCK COPOLYMER, 101

344DIBUTYL MALEATE

COPOLYMER, 327DIBUTYLTIN DILAURATE, 24DICHLOROETHYL ETHER, 230DICHLOROFLUOROMETHYL

THIOPHTHALIMIDE, 17DICHLOROMETHANE, 292DICHROIC RATIO, 52 102 143

179 251DICHROISM, 6 39 46 52 55 101

114 119 134 143 159 179 181197 199 201 283 359 372

DICUMYL PEROXIDE, 304 327DICYANDIAMIDE, 285 312DICYANODIAMIDE, 354DIELECTRIC SPECTROSCOPY,

276DIELS-ALDER REACTION, 273DIENE COPOLYMER, 335DIETHYL CARBAMATE, 100DIETHYL MALEATE

COPOLYMER, 120DIETHYLENE GLYCOL

DIMETHYL ETHER, 369DIFFERENTIAL SCANNING

CALORIMETRY, 11 23 29 5384 89 93 94 123 155 165 173188 195 213 249 310 348 377

DIFFERENTIAL THERMALANALYSIS, 11 23 29 53 84 8993 94 123 155 165 173 188 195213 249 310 348 377

DIFFUSION, 22 26 36 40 53 68 99

122 128 136 150 230 246 300312

DIFFUSION COEFFICIENT, 36122 150 230 232 289 347

DIFFUSIVITY, 26 68 198 347DIGITAL SIGNAL

PROCESSING, 16 148DIGLYCIDYL ETHER, 197 312

340DIGLYME, 369DIHYDROXYBIPHENYL, 133DIMER, 163 302DIMERISATION, 292DIMETHYL ACETAMIDE, 116DIMETHYL FORMAMIDE, 354DIMETHYL SULFOXIDE, 147

287DIMETHYLACETAMIDE, 116DIMETHYLOLPROPIONIC

ACID, 60DIMETHYLSILOXANE

COPOLYMER, 275 344DIOCTYL PHTHALATE, 17DIOL, 79 340DIPHENYLMETHANE

DIISOCYANATE, 377DIPIPERIDINOETHANE, 369DIPOLE INTERACTION, 310DIPOLE ORIENTATION, 223 231DIPROPYLENE GLYCOL, 246DISORDERED POLYMER, 73

147 195DISPERSION, 88 120 334DISPERSIVITY, 203DIVINYL BENZENE, 61DIVINYL ETHER, 240DODECANE, 67DODECANEDIOL, 79DODECYL SULFATE, 331DOMAIN, 39 55 88 129 213 280

293DOPANT, 160 298 331DOPING, 54 290 298 331 374DOUBLE BOND, 80 103 189 200

263 272 304DRAW RATIO, 1 92 94 201 216

251 291DRAWING, 99 114 158 216 223

235 237DRIFT SPECTROSCOPY, 2DRY BLEND, 176DRYING TIME, 246DURABILITY, 232DYNAMIC, 16 55 102 134 168

242 254DYNAMIC INFRARED LINEAR

DICHROISMSPECTROSCOPY, 199

DYNAMIC INFRAREDSPECTROSCOPY, 102

DYNAMIC MECHANICALANALYSIS, 128 316

DYNAMIC MECHANICALPROPERTIES, 254

DYNAMIC MECHANICALTHERMAL ANALYSIS, 251377

EEFFICIENT VULCANISATION,

304ELASTIC LIGHT SCATTERING,

135ELASTIC MODULUS, 10 79 187

216ELECTRIC FIELD, 6 101 163 194

223 231 245 334ELECTRICAL CONDUCTIVITY,

30 160 292 345 374ELECTRICAL PROPERTIES, 30

112 121 160 223 292 345ELECTROCHEMICAL

POLYMERISATION, 290ELECTROCHEMICAL

PROPERTIES, 54ELECTROCLINIC PROPERTIES,

101ELECTROINITIATED

POLYMERISATION, 121 290292 298 317

ELECTRON ACCEPTOR, 165ELECTRON BEAM

IRRADIATION, 256ELECTRON DONOR, 165 233ELECTRON IMPACT MASS

SPECTROSCOPY, 325ELECTRON IRRADIATION, 146ELECTRON MICROGRAPH, 99ELECTRON SCANNING

MICROSCOPY, 117 120ELECTRON SPECTROSCOPY

FOR CHEMICAL ANALYSIS,327 344

ELECTRON TRANSFER, 331ELECTROPOLYMERISATION,

121 292 298 317ELEMENTAL ANALYSIS, 259

272ELEVATED TEMPERATURE, 188

320ELONGATION, 51 181 187 197

243ELONGATION AT BREAK, 117

216EMERALDINE BASE, 108

Subject Index

© Copyright 2001 Rapra Technology Limited 133

EMERALDINE SALT, 108EMULSION, 60 246EMULSION

COPOLYMERISATION, 35EMULSION POLYMERISATION,

35 319END GROUP, 189 330 339ENGINEERING PLASTIC, 323ENTHALPY, 165 177 233 262ENVIRONMENTAL STRESS

CRACKING, 94 99EPICHLOROHYDRIN

GLYCIDYL ETHER, 28EPOXY COMPOUND, 13EPOXY GROUP, 75EPOXY METHACRYLATE

COPOLYMER, 200EPOXY RESIN, 18 41 63 75 79

112 197 205 207 217 221 222227 248 249 253 276 277 278281 285 286 312 340 352 354377

EPOXY SILANE, 13EPOXYHEXENE, 13EPOXYPROPANE, 13EPOXYTRIMETHYLPENTANE,

32EPSILON-CAPROLACTAM

COPOLYMER, 188EQUILIBRIUM CONSTANT, 165EQUIVALENT WEIGHT, 30ERUCAMIDE, 71 130 324 366ESTER, 154 241 248 343ESTER COPOLYMER, 243 325ESTER GROUP, 133 146 225ESTER URETHANE

COPOLYMER, 95 96ETCHING, 193ETHANOL, 12 140 146ETHENE COPOLYMER, 46 117

120 123 184 189 221ETHERETHERSULFONE

COPOLYMER, 19ETHERIFICATION, 354ETHERSULFONE COPOLYMER,

19ETHYL ACETATE, 60 187ETHYL ACRYLATE

COPOLYMER, 92 203ETHYL ACRYLATE

TETRAPOLYMER, 124ETHYL ALCOHOL, 12 140 146ETHYL BENZENE, 89ETHYL METHACRYLATE

COPOLYMER, 321ETHYL METHACRYLATE

TETRAPOLYMER, 124ETHYL METHYLIMIDAZOLE,

377ETHYL PYRROLIDONE, 287ETHYLENE, 226 272ETHYLENE COPOLYMER, 46

117 120 123 184 189 221 228327

ETHYLENE OXIDE, 152 248 354ETHYLENE OXIDE

COPOLYMER, 85ETHYLENE-ETHYL ACRYLATE

COPOLYMER, 106ETHYLENE-PROPYLENE

COPOLYMER, 44 110 123 155189

ETHYLENE-PROPYLENE-DIENE COPOLYMER, 356

ETHYLENE-PROPYLENE-DIENE TERPOLYMER, 104145 155 224 226 229 272 306318

ETHYLENE-TETRAFLUOROETHYLENE,182

ETHYLENE-VINYL ACETATECOPOLYMER, 72 73 87 105130 132 141 165 218 226 233270 272 368

ETHYLENE-VINYL ALCOHOLCOPOLYMER, 258 305

ETHYLENIMINETERPOLYMER, 125

ETHYLHEXYL ACRYLATECOPOLYMER, 184

ETHYLIDENE NORBORNENE,272 356

EVANESCENT WAVESPECTROSCOPY, 217

EVOLVED GAS ANALYSIS, 302EXCITATION, 108EXCLUSION

CHROMATOGRAPHY, 215257

EXPOSURE TIME, 154 189EXTRACTION, 4 272 303 322EXTRUDER, 45 247EXTRUDER BARREL, 247EXTRUDING, 29 45 68 86 130

144 176 189EXTRUSION, 29 45 68 86 130

144 176 189 247 313EXTRUSION MIXING, 247

FFACTOR ANALYSIS, 222 272FAR-INFRARED

SPECTROSCOPY, 183 283FAST FOURIER TRANSFORM,

52 53FATTY ACID ESTER, 303FERROELECTRIC, 163FERROELECTRIC POLYMER,

101FERROELECTRIC PROPERTIES,

231FERROMAGNETIC, 220FIBRE, 114 137 207 234 260 286

301 303 308 320 330 337 376FIBRE BUNDLE, 247FIBRE OPTIC, 110 152 227 319

352FIBRE SPACING, 207FIBRE STRUCTURE, 114FIBRE TREATMENT, 114FIBRE-REINFORCED PLASTIC,

207FIBRILLAR, 216FIBROIN, 16FIBROUS FILLER, 212 237 301FICK’S SECOND LAW, 53FIELD STRENGTH, 163 231FILLED, 312FILLER, 33 44 48 87 104 132 175

176 212 218 304 341FILLER CONTENT, 268FILM, 8 9 15 16 17 18 19 21 22 26

29 36 44 50 51 56 60 68 72 75102 108 116 121 122 136 142150 155 158 159 161 162 168171 175 177 180 181 183 184194 197 202 203 223 230 233234 235 241 251 256 258 262269 272 290 291 298 299 305311 317 322 330 331 339 344346 359 362 368 375

FILM FORMING, 21 246FIRING TEMPERATURE, 237FIRST-ORDER, 278FLAME RETARDANT, 274FLAMMABILITY, 236FLEXIBILITY, 10 128 253FLEXIBLE, 10 128FLOW, 46 250FLUID RESISTANCE, 154FLUORESCEIN, 129FLUORESCENCE, 129 266 284

304FLUORINATION, 217FLUORINE, 259FLUOROPOLYMER, 30 213FOAM, 59 236 267 333 360FOLDED CHAIN, 10FORMALDEHYDE, 127FORMULATION, 76 175 176 377FRACTION, 133 354FRACTIONATION, 123 133 229

Subject Index

134 © Copyright 2001 Rapra Technology Limited

FRACTURE, 79 270 285FRACTURE MORPHOLOGY, 33

50 120 135FRAGMENTATION, 281FREE RADICAL, 189FREE RADICAL

COPOLYMERISATION, 142238

FREE RADICALPOLYMERISATION, 103 124142 238

FREQUENCY SHIFT, 134 199FRICTION COEFFICIENT, 212FUNCTIONAL GROUP, 189 262

272 280 330 334FUNCTIONALISATION, 133 203

228 327FUNCTIONALITY, 30 165 233 339

GGALVANOSTATIC, 290GAMMA-IRRADIATION, 330GAS CHROMATOGRAPHY, 113GAS-PHASE, 122GASES, 122GEL, 2 124 198 257GEL CHROMATOGRAPHY, 242GEL PERMEATION

CHROMATOGRAPHY, 214242 248

GELATION, 65GERMANIUM, 104 241 290GLASS, 233GLASS FIBRE-REINFORCED

PLASTIC, 286 328GLASS TRANSITION

TEMPERATURE, 27 29 53 5578 107 128 140 165 177 197201 253 280 310 312 348 377

GLASSY, 79 150 173GLOW DISCHARGE

POLYMERISATION, 171GLYCIDYL AMINE, 277GLYCIDYL ETHER, 377GLYCIDYL METHACRYLATE

COPOLYMER, 255 308GLYCOL ETHER, 246GOLD, 108 227 285 375GRAFT, 61 78 125 133 162 322GRAFT COPOLYMER, 61 74 125

133 255 275 322GRAFT COPOLYMERISATION,

255 308 322GRAFT DENSITY, 125GRAFT POLYMERISATION, 61

125 229 327GRAFT YIELD, 61 74 125

GRAFTED, 125GRAFTING, 61 78 125 133 162GRAPHITE, 48GRATING, 234GRAVIMETRIC ANALYSIS, 113

120 122 312GROUP I METAL COMPOUND,

30GROUP TRANSFER

POLYMERISATION, 329

HHARD SEGMENT, 39 55HARDENER, 285HARDNESS, 154HEAT DEGRADATION, 113 145

189HEAT RESISTANCE, 113 189HEAT SHRINKAGE, 201HEAT TREATMENT, 114 142 259HEATING RATE, 242HEAVY ION, 256HEAVY WATER, 287 294HELICAL, 6 89 350HELIUM, 256HETEROGENEOUS, 229 294HEXADECANE, 67HEXADIENE, 229HEXAGONAL, 182 195HEXANEDIOL, 79HIGH CONVERSION, 263HIGH DENSITY

POLYETHYLENE, 20 81 94134 247 250 261 269 305 316

HIGH IMPACT POLYSTYRENE,279

HIGH PERFORMANCE LIQUIDCHROMATOGRAPHY, 138351

HIGH PRESSURE, 7 26HIGH TEMPERATURE, 80 110

278HINDERED AMINE, 86 144HOMOGENEITY, 253HOMOGENEOUS, 61 88 213 317HOMOPOLYMER, 129HOT PRESS MOULD, 3HUMAN SERUM ALBUMIN, 42HUMIDITY, 41 189 246HYDRATION, 41 287HYDROCHLORIC ACID, 12 236HYDROGEL, 40 185 198HYDROGEN, 256 297HYDROGEN BOND, 28 39 55

102 116 167 185 287 294 296339

HYDROGEN BONDING, 50 60

93 140 146 147 174 225 257276 277

HYDROGEN BROMIDE, 236 345HYDROGEN CHLORIDE, 12 236HYDROGEN CYANIDE, 236HYDROGEN PEROXIDE, 297HYDROGENATED

ACRYLONITRILEBUTADIENE RUBBER, 154

HYDROLYSIS, 142 146 154HYDROLYTIC DEGRADATION,

50HYDROPEROXIDE, 288HYDROPEROXY GROUP, 297HYDROPHILIC, 196 246 249 322HYDROPHOBIC, 93 322HYDROXY GROUP, 50 165 297HYDROXY VALERATE

COPOLYMER, 114HYDROXYBENZENE, 127HYDROXYBENZOIC ACID, 133HYDROXYBUTYRATE

COPOLYMER, 114HYDROXYETHYL ACRYLATE,

60HYDROXYL GROUP, 50 165 238

297 354HYDROXYL NUMBER, 152 370HYDROXYLATED, 233HYDROXYVALERATE

COPOLYMER, 114HYSTERESIS, 327 334

IIMAGING, 19 52 53 88 105 178

222 271IMIDAZOLE, 3 340IMIDE, 154 354IMIDE COPOLYMER, 243IMIDE GROUP, 9 229IMIDISATION, 9 115 332IMINE, 154IMMERSION, 154IMMISCIBLE, 45 228IMMUNOGLOBULIN G, 42IMPACT MODIFIER, 175IMPACT PROPERTIES, 117IMPACT STRENGTH, 117IMPURITY, 189 248IN-LINE, 247 313IN-SITU, 26 31 32 35 42 54 78 80

94 135 150 217 227 230 232240 290 292 300 345

IN-VIVO, 156INCIDENCE ANGLE, 194 245INDENTATION, 161INDIUM ANTIMONIDE, 271

Subject Index

© Copyright 2001 Rapra Technology Limited 135

INDIUM COMPOUND, 271INDUCTION PERIOD, 38INFRARED ABSORPTION, 130

151 156 177 258 356INFRARED DICHROISM, 114

134 309INFRARED IMAGING, 18 19INFRARED POLARISATION, 52INHOMOGENEITY, 105 234INITIATION, 32INITIATOR, 32 75 118 161 306INJECTION MOULDING, 29 97INSOLUBLE, 133INTENSITY, 7INTENSITY RATIO, 272INTERACTION PARAMETER,

230 249INTERDIFFUSION, 128 328INTERFACE, 108 128 147 161

193 203 212 215 218 232 233281 353

INTERFACIAL ADHESION, 198281

INTERFACIAL AGENT, 328INTERFACIAL BONDING, 233INTERFACIAL ENERGY, 233INTERFACIAL INTERACTION, 8

194 233 245 249INTERFACIAL LAYER

THICKNESS, 10 328INTERFACIAL

POLYMERISATION, 322INTERFACIAL PROPERTIES, 8

147 161 165 194 202 225 228229 233 285

INTERFACIAL STRUCTURE, 9INTERFACIAL WIDTH, 161INTERMOLECULAR BONDING,

140INTERMOLECULAR

COMPLEXATION, 140INTERMOLECULAR

INTERACTION, 65 93 181 273278 310 350

INTERMOLECULARREACTION, 248

INTERNAL REFLECTIONSPECTROSCOPY, 150 194 232245 290

INTERNAL ROTATION, 307INTERNAL STANDARD, 319INTERPENETRATING

POLYMER NETWORK, 75238

INTERPHASE, 10 128 218 229249 286 328

INTERPOLYMER, 140INTRAMOLECULAR

INTERACTION, 65 93INTRAMOLECULAR

VIBRATION, 257IODINE, 374ION, 154ION BEAM IRRADIATION, 256ION EXCHANGE RESIN, 30ION PAIR, 296IONIC BOND, 154 244IONIC INTERACTION, 92 140

154IONISATION, 244 330IONISING RADIATION, 256IONOMER, 92 154 244 310IRRADIATION, 41 146 315 322

330ISOBUTYLENE COPOLYMER,

33ISOCYANATE, 59ISOCYANIDE, 154ISOCYANURATE, 377ISOIMIDE GROUP, 9ISOMER, 27 365 369ISOMERISATION, 242ISOMERISM, 304 365 369ISONITRILE, 154ISOPHORONE DIISOCYANATE,

60ISOPHORONE DIISOCYANATE

COPOLYMER, 37 38ISOPROPYL GROUP, 93ISOTACTIC, 4 16 31 74 170 180

189 199 211 252ISOTHERMAL, 240 242 248 278

323ISOTROPIC, 53 94 134 216ITACONIC ACID, 260

JJUTE, 301

KKAOLIN, 87 132KETONE, 288KETONE GROUP, 189KETYL PYRIDINIUM

CHLORIDE, 317KINETIC, 24 26 32 38 41 48 58

112 123 150 151 186 196 214227 240 242 262 276 277 278279 286 300 323 332 345

KRYPTON ION, 256

LLACTONISATION, 273

LAMELLA, 10LAMELLAR, 94 216LAMINATE, 147 164 168 194 198

223 225 233 245 305LANGMUIR-BLODGETT FILM, 9LASER POLYMERISATION, 363LASER TREATMENT, 48LATEX, 21 202 203 295 300 349LATTICE, 21 202 203 294LAYER, 121 194 245LEAST-SQUARES ANALYSIS,

81 234LIGHT AGEING, 112LIGHT DEGRADATION, 18 104

112 189 279 297 336 351LIGHT INTENSITY, 240 247LIGHT SCATTERING, 135 304LIGHT STABILISER, 112 189LIMONENE, 122LINEAR DICHROISM, 134LINEAR DISCRIMINANT

ANALYSIS, 178LINEAR LOW, 247LINEAR LOW DENSITY

POLYETHYLENE, 20 86 120144

LINEAR REGRESSIONANALYSIS, 247 272

LIPID, 6LIQUID CHROMATOGRAPHY,

138 215 351LIQUID CRYSTAL, 37 38 39 53

88 136 243 269 280 334LIQUID CRYSTAL POLYMER,

101 133 143 163LIQUID CRYSTALLINE, 1 10 133LIQUID PHASE, 354LIQUID POLYMER, 7LIVING POLYMERISATION, 32

314 329LOAD TRANSFER, 212LOADING, 197 253LOSS FACTOR, 377LOSS TANGENT, 377LOW DENSITY

POLYETHYLENE, 20 71 81110 117 218 221 247 250 269305 316 324 327 366

LOW FREQUENCY, 282LOW TEMPERATURE, 43LOWER CRITICAL SOLUTION

TEMPERATURE, 93LUBRICANT, 154 175 176 324

371LYSOZYME, 42

Subject Index

136 © Copyright 2001 Rapra Technology Limited

MMACHINERY, 45 247MACROCYCLISATION, 329MAGIC ANGLE, 229 354MAGNESIUM PERCHLORATE,

340MAGNETIC PROPERTIES, 220MAIN CHAIN, 189 304MALEATION, 306MALEIC ANHYDRIDE, 306MALEIC ANHYDRIDE

COPOLYMER, 117 221 229343

MALEIC ANHYDRIDE GROUP,229

MAPPING, 17 19 76 129 147 148153 234

MATRIX, 53 161 278 286MECHANICAL DEFORMATION,

94 161MECHANICAL LOSS, 177MECHANICAL PROPERTIES, 1

10 16 28 36 46 55 79 91 92 9499 102 117 128 134 154 158161 177 187 197 199 201 207210 212 216 235 237 243 250251 253 259 278 281 282 285296 299 304 312 320 327 334

MECHANICAL RELAXATION,169

MELAMINE RESIN, 149MELAMINE-FORMALDEHYDE

RESIN, 149 221MELT, 10 31 187 219 247 254 324MELT BLEND, 247MELT MIX, 241MELT PROPERTIES, 31MELT STATE, 173MELTING, 155 165 249MELTING POINT, 89 141 187MELTING TEMPERATURE, 123

155MEMBRANE, 6 61 333MEMORY EFFECT, 101MERCAPTOBENZTHIAZOLE,

304MESOGEN, 39 101 163 243MESOMORPHIC, 350METAL, 108 285 375METAL ADHESION, 285METALLISATION, 108 285METALLISED, 227METALLOCENE, 155METHACRYLATE

COPOLYMER, 308 321 338343

METHACRYLIC ACID, 124

METHACRYLIC ACIDCOPOLYMER, 203 228 273

METHACRYLIC ACIDTERPOLYMER, 21 124

METHACRYLIC ACIDTETRAPOLYMER, 124

METHACRYLOXYPROPYLTRIMETHOXYSILANECOPOLYMER, 328

METHANOL, 126 196METHYL ACRYLATE

COPOLYMER, 166 184METHYL ALCOHOL, 126 196METHYL ANHYDRIDE, 248METHYL CELLULOSE, 116METHYL ETHYL KETONE, 154METHYL GROUP, 93 189 272 330METHYL ISOBUTYL KETONE,

47METHYL METHACRYLATE

COPOLYMER, 64 203 275METHYL METHACRYLATE

TERPOLYMER, 124METHYL METHACRYLATE

TETRAPOLYMER, 124METHYL PYRROLIDINONE,

332METHYL PYRROLIDONE, 60

287METHYL STYRENE

COPOLYMER, 33 200METHYLACETAMIDE, 167METHYLCELLULOSE, 116METHYLCYCLOHEXANONE,

283METHYLENE GROUP, 189 272

297METHYLENE BISPHENYLENE

DIMALEIMIDE, 239METHYLMETHACRYLATE

COPOLYMER, 64 203METHYLPHENOXYETHYL

METHACRYLATECOPOLYMER, 338

METHYLSTYRENECOPOLYMER, 33 200

MICROBOND, 281MICROCOMPOSITE, 207MICRODOMAIN, 213MICRODROPLET, 135MICROEMULSION, 60MICROGRAPHY, 156MICROHARDNESS, 154MICROMECHANICAL, 161 281MICROPHASE SEPARATION,

101MICROPROBE, 121 234MICROSPHERE, 78 271

MICROSTRUCTURE, 156 181189 223 235 335 369

MICROTOME, 188MICROWAVE, 3MIGRATION, 202 203 218 304MISCIBILITY, 29 92 116 310MIXING, 29 176 247 347 348MIXTURE, 122 129 166 224MODEL COMPOUND, 9 13 94

151 167 242 276 277 304 341MODIFICATION, 79 196 233 278MODULUS, 1 134 212 237MOISTURE CONTENT, 152 185

249 364MOLAR RATIO, 79 121 127 229MOLE FRACTION, 257 343MOLE RATIO, 79 121 127MOLECULAR

CONFIGURATION, 27 51 5657 67 78 89 119 177 180 182183 188 195 218 219 251 252309 330 346 350 361 365 369373

MOLECULAR DISORDER, 189MOLECULAR INTERACTION, 8

65 93 147 278 311MOLECULAR MASS, 10 30 32

52 69 119 165 187MOLECULAR MOBILITY, 17

163MOLECULAR MOTION, 83 101MOLECULAR ORDER, 163 167MOLECULAR ORIENTATION, 1

5 19 79 91 92 94 101 102 119131 134 163 179 197 201 251253 291 307 316 355 372

MOLECULAR PACKING, 350MOLECULAR

REARRANGEMENT, 177 316MOLECULAR RELAXATION, 92MOLECULAR VIBRATION, 272MOLECULAR WEIGHT, 10 30 32

52 69 84 119 165 187 225 241257 293 314 321 347 367

MONOCLINIC, 94MONOFUNCTIONAL, 151MONOLAYER, 9 375MONOMER, 12 84 124 141 151

166 214 220 229 272MONOMER INSERTION, 155MONOMER REACTIVITY, 64MORPHOLOGICAL

PROPERTIES, 19 21 33 50 5266 94 117 120 135 187 203 213218 221 237 247 254 270 323346 360

MOULDING, 86 144 159 204MULTI COMPONENT, 166

Subject Index

© Copyright 2001 Rapra Technology Limited 137

MULTI FIBRE, 207MULTIFUNCTIONAL, 227 263MULTILAYER, 8 42 148 149 202MULTI PHASE, 88MULTIPLE INTERNAL

REFLECTANCESPECTROSCOPY, 150 232

NN-CYCLOHEXYL-2-

BENZOTHIAZOLESALFENAMIDE, 304

NADIC METHYL ANHYDRIDE,248

NANOPARTICLE, 23NAPHTHA, 82NATURAL RUBBER, 91 190 210

224 304 349NEAR-INFRARED

CORRELATIONSPECTROSCOPY, 73 167

NEAR-INFRAREDSPECTROSCOPY, 20 77 82 86105 109 141 144 152 157 168174 176 183 206 209 217 239247 265 276 277 305 311 313

NEMATIC, 37 53NEOPRENE, 104NETWORK STRUCTURE, 278

354NEURAL NETWORK, 157NEUTRALISATION, 244NITRIC OXIDE, 236NITRILE, 354NITRILE GROUP, 147 228 260

285NITRILE RUBBER, 104 154 228

272NITROGEN COPOLYMER, 335NITROGEN DIOXIDE, 236NITROGEN OXIDE, 236NITROGEN-CONTAINING

POLYMER, 42 287 292 293NITROXYL RADICAL, 220NOISE REDUCTION, 47NON-DESTRUCTIVE TESTING,

70 109 139 232 260 305 326336 341 363

NUCLEAR MAGNETICRESONANCE, 2 4 13 113 123127 154 155 180 211 229 286321 354

NUCLEOPHILIC, 154

OOCTANE, 67OCTANEDIOL, 79OIL, 303OIL ABSORPTION, 154OLEFIN, 7OLEFIN GROUP, 103OLIGOMER, 10 290 329ON-LINE INSPECTION

SYSTEM, 152ON-LINE MEASUREMENT, 178

303OPACITY, 247OPTIC FIBRE, 110 152 227 247

319 352OPTICAL DENSITY, 260 330OPTICAL FIBRE, 45 49 59 71 80

217OPTICAL LEVITATION, 135OPTICAL MICROSCOPY, 15 129

162OPTICAL PROPERTIES, 16 114

129 135 136 159 205 221 243247 253 267 269 270 283 284299 315 330 376

OPTICAL RECORDING MEDIA,143

OPTICAL STORAGE, 143OPTIMISATION, 162 196 338OPTORHEOLOGICAL

PROPERTIES, 96ORIENTATION, 1 39 46 51 52 55

79 83 90 114 119 131 143 158159 172 195 199 201 216 243250 270 282 291 299 346 359372

ORIENTATION FACTOR, 372ORIENTATION FUNCTION, 251ORIENTATIONAL, 6ORIENTED, 283ORTHORHOMBIC, 73 94 182

195OVERLAYING, 375OXAZOLIDONE, 377OXAZOLINE, 228OXIDATION, 54 100 104 112 120

142 154 189 237 279 306OXIDATIVE DEGRADATION,

54 100 104 154 162 189 237279 297

OXIDISATION, 162 189OXIRANE, 152 248 354OXIRANE COPOLYMER, 85OXYBENZOATE COPOLYMER,

325OXYDIANILINE, 332

OXYGEN, 3 154 256OXYGEN MUSTARD, 230OXYGEN UPTAKE, 336OXYNAPHTHOATE

COPOLYMER, 325OZONE, 189

PPACKAGING FILM, 272PAINT, 62 106 149 300PARACRYSTALLINE, 52 186PARTIAL LEAST SQUARES, 82

247 272 313 337PARTICLE SIZE, 77 86 120 135

144 176PARTITIONING, 295PEAK INTENSITY, 154 241PENDANT GROUP, 238PENTACYANOBIPHENYL, 136PENTYLCYANOBIPHENYL, 53

269PENTYLCYANOPHENYL

CYCLOHEXANE, 269PERDEUTERATION, 316PERFLUOROOCTYL GROUP, 12PERMEABILITY, 150 187PERMEATION, 36PEROXIDE GROUP, 189PH, 196 300PHASE BEHAVIOUR, 7 93 94

129 143 163 164 186 199 218219 229

PHASE DIAGRAM, 37PHASE SEGREGATION, 247PHASE SEPARATION, 33 88 101

129 280 323 344 364PHASE SHIFT, 7PHASE STRUCTURE, 10 88 213PHASE TRANSITION, 37 89 93

182 195 219 223PHENOL, 127PHENOL FORMALDEHYDE

RESIN, 58PHENOL-FORMALDEHYDE

RESOL RESIN, 127PHENOLIC RESIN, 34PHENOXY COPOLYMER, 348PHENOXY RESIN, 311 348PHENOXYPHENYLETHYNYL

BENZOPHENONE, 80PHENYL GLYCIDYL ETHER, 28

248PHENYLAMINOCARBONYLOXY-

ETHYL METHACRYLATECOPOLYMER, 338

PHENYLENE ACETYLENE

Subject Index

138 © Copyright 2001 Rapra Technology Limited

COPOLYMER, 345PHOTOCALORIMETRY, 262PHOTOCHEMICAL

DEGRADATION, 112 297PHOTOCHEMICAL STABILITY,

112PHOTOCROSSLINKING, 75PHOTOCURING, 75PHOTODECOMPOSITION, 112PHOTODEGRADATION, 76 112PHOTOINDUCED, 143PHOTOINITIATOR, 75 118 161PHOTOLUMINESCENCE, 317PHOTOMICROGRAPHY, 156PHOTOOXIDATION, 112 288PHOTOOXIDATIVE

DEGRADATION, 104 112 189279 336

PHOTOOXIDATIVE STABILITY,112

PHOTOPOLYMERISATION, 75240 263 353 363

PHOTORESIST, 353PHOTOSENSITISATION, 240PHOTOSTABILISER, 62PHYSICAL AGEING, 27PHYSICAL PROPERTIES, 45 82

141 151 152 187 270 364PHYSICOCHEMICAL

PROPERTIES, 249 322PHYSICOMECHANICAL

PROPERTIES, 28PIGMENT, 86 166PINENE, 283PLANAR, 5 188PLASMA, 3PLASMA POLYMERISATION,

171PLASMA TREATMENT, 162 342PLASTICISATION, 154 280 312PLASTICISER, 17 55 166PLASTICITY, 282PLATINUM, 121POLAR GROUP, 74POLARISATION, 5 6 108 179 223

243 282 291 334 359POLARISATION DIVISION

INTERFEROMETRY, 283POLARISATION MODULATION,

92POLARISED LIGHT, 346POLARISER, 52POLARON, 160 331POLING, 223 231POLY-ALPHA-

METHYLSTYRENE, 302 350POLY-N-VINYL CARBAZOLE,

121

POLY-P-METHYLSTYRENE, 302POLY-P-PHENYLENE, 317POLYACETAMIDO

ACRYLAMIDE, 65POLYACETYLENE, 160 345POLYACRYLAMIDE, 137 293

363POLYACRYLATE, 60 202 205 262POLYACRYLIC, 42 118 149 184

185 196 202 203 246 260 280282 319 326

POLYACRYLIC ACID, 40 42 147196 198

POLYACRYLIC ESTER, 202 205POLYACRYLONITRILE, 113 116

145 147 180 237 330 376POLYALKENE, 4 16 67 74 89 97

110 204POLYAMIC ACID, 115 332POLYAMIDE, 86 144 145 254 303

372POLYAMIDE-11, 36 223 231 254POLYAMIDE-12, 167 174POLYAMIDE-6, 102 305 311 376POLYAMIDE-6,12, 376POLYAMIDE-6,6, 229 372 376POLYANILINE, 108 121POLYBENZIMIDAZOLE, 323POLYBENZOPHENONE, 80POLYBENZYL ASPARTATE, 6POLYBENZYL GLUTAMATE, 6POLYBISPHENOL-A, 276 277POLYBISPHENOL A

BISHYDROXYPROPYLMETHACRYLATE, 103

POLYBISQUINOLYLBUTADIYNE,315

POLYBUTADIENE, 214 279 295335

POLYBUTYL ACRYLATE, 35 202POLYBUTYL METHACRYLATE,

53 126 136 280POLYBUTYLENE, 32 49POLYBUTYLENE

TEREPHTHALATE, 221 274POLYCAPROLACTONE, 311POLYCARBONATE, 83 149 177

201 221 241 329 348 361 362POLYCARBOXYLATE, 30POLYCARBOXYLIC ACID, 140POLYCHLOROPRENE, 104POLYDIACETYLENE, 43 111 220

315POLYDIETHYLENE GLYCOL

DIMETHACRYLATE, 263POLYDIMETHYL PHENYLENE

ETHER, 57POLYDIMETHYL PHENYLENE

OXIDE, 221POLYDIMETHYL SILOXANE, 7

83 119 291 362POLYDIVINYL ETHER, 240POLYELECTROLYTE, 42POLYENE, 374POLYEPICHLOROHYDRIN, 28POLYEPOXIDE, 18 41 63 75 79

112 197 205 207POLYEPSILON-

CAPROLACTAM, 188POLYESTER FILM, 1POLYESTERIMIDE, 243POLYETHER, 2 297POLYETHER ACRYLATE, 118POLYETHER DIAMINE, 197POLYETHER ETHERKETONE,

159POLYETHER SULFONE, 270POLYETHERIMIDE, 323POLYETHERURETHANEUREA,

355POLYETHOXYPROPYL-

ACRYLAMIDE, 293POLYETHYLENE, 4 10 11 20 45

46 67 70 71 81 86 94 99 110120 134 144 148 157 164 195205 206 216 218 221 247 249250 261 266 269 288 305 313316 324 327 346 366 368 373

POLYETHYLENE GLYCOL, 52198 367

POLYETHYLENE GLYCOLDIMETHACRYLATE, 263

POLYETHYLENE IMINE, 42 125POLYETHYLENE

NAPHTHALATE, 56POLYETHYLENE OXIDE, 52 85

233 297 309 310POLYETHYLENE

TEREPHTHALATE, 5 19 2627 50 81 90 92 120 131 157158 164 183 234 235 241 251261 266 284 307 320 339 355359 365 376

POLYFLUOROCARBON, 259POLYFLUOROETHYLENE, 146POLYFUNCTIONAL, 151POLYGLYCIDYL

METHACRYLATE, 255POLYHEXADIYNE, 43POLYHYDROXYBENZOIC

ACID, 325POLYHYDROXYETHYL

METHACRYLATE, 103 185POLYIMIDE, 7 9 115 332POLYIONENE, 92 154POLYISOBUTYLENE, 32 49

Subject Index

© Copyright 2001 Rapra Technology Limited 139

POLYISOCYANURATE, 59 267POLYISOIMIDE, 242POLYISOPRENE, 224 314 374POLYISOPROPYL

ACRYLAMIDE, 93 293POLYLAURYLLACTAM, 174POLYMER DISPERSED LIQUID

CRYSTAL, 37 38 88 280POLYMER MELT, 152POLYMERIC ADDITIVE, 137POLYMERIC ANTISTATIC

AGENT, 367POLYMERIC COMPATIBILISER,

133POLYMERISATION, 32 35 38 49

66 75 80 88 103 108 121 124135 142 151 155 171 188 214240 249 262 290 321 322

POLYMERISATION CATALYST,155 329

POLYMERISATION INITIATOR,214 238 240 321 327

POLYMERISATION KINETICS,32 38 151 238 263 314 315 363

POLYMERISATIONMECHANISM, 32 239 263 292308 314 322 329

POLYMERISATION MODIFIER,369

POLYMERISATION RATE, 88322 329 339

POLYMERISATIONTEMPERATURE, 103 321

POLYMERISATION TIME, 103POLYMETHACRYLATE, 185POLYMETHACRYLIC ACID, 140

273POLYMETHYL

METHACRYLATE, 52 145 150164 194 225 232 233 245 282319 326 347

POLYMETHYL STYRENE, 302350

POLYMETHYL VINYL ETHER,297

POLYMETHYLENE, 163POLYMETHYLENE OXIDE, 309POLYMORPHISM, 186 213 219POLYOLEFIN, 4 16 67 74 89 97

110 204 215 249 252 271 302318 366 371

POLYORGANOSILOXANE, 7POLYOXYETHYLENE, 85POLYOXYMETHYLENE, 309POLYPARAPHENYLENE

SULFIDE, 84POLYPEPTIDE, 6POLYPERFLUOROCARBOXYLATE,

30POLYPHENYLENE, 290 317POLYPHENYLENE

ACETYLENE, 345POLYPHENYLENE

BIBENZIMIDAZOLE, 323POLYPHENYLENE

DIBROMOETHYLENE, 345POLYPHENYLENE ETHER, 128POLYPHENYLENE OXIDE, 128POLYPROPYLENE, 4 16 22 31 44

45 70 74 77 81 97 110 117 133157 162 164 170 199 204 221

POLYPROPYLENE OXIDE, 85128

POLYPYRROLE, 121 298 331POLYSACCHARIDE, 162POLYSILOXANE, 163 291POLYSTYRENE, 23 29 35 57 77

78 81 89 92 107 128 135 145150 157 173 186 202 205 214215 219 222 252 266 271 279299 302 311 314 344 347 350351 371

POLYSTYRENESULFONATE,244

POLYSULFIDE, 9POLYTETRAFLUOROETHYLENE,

146 270POLYTETRAHYDROFURAN, 2POLYTETRAMETHYLENE

OXIDE, 2POLYTHIOETHER, 9POLYTHIOPHENE, 54POLYURETHANE, 18 39 55 59 60

100 102 106 149 156 206 236238 257 265 266 267 303 333355 358 360 375

POLYURETHANE ACRYLATE,161

POLYURETHANEDIACRYLATE, 161

POLYURETHANE ELASTOMER,24 55 95 156 364 375

POLYVINYL, 175POLYVINYL ACETATE, 52 129

273POLYVINYL ALCOHOL, 129 147

194 225 245 249 255 258 337POLYVINYL CARBAZOLE, 121

292POLYVINYL CHLORIDE, 3 17 51

76 81 145 153 157 175 176 181206 215 261 376

POLYVINYL CYANIDE, 113 116POLYVINYL ESTER, 238 328POLYVINYL HALIDE, 3 51POLYVINYL METHYL ETHER,

92POLYVINYL PYRIDINE, 140POLYVINYL PYRROLIDONE,

287POLYVINYLBENZENE, 29 57 77

78 128 135 186POLYVINYLIDENE CHLORIDE,

376POLYVINYLIDENE FLUORIDE,

61 187 213 223 256 283POTASSIUM BROMIDE, 339 343POTASSIUM COMPOUND, 30POTENTIOSTATIC, 290POWER LAW, 53 280PREGRAPHITISATION, 237PREHEAT, 167 174PREMELTING, 167 174PREPARATION, 278PREPOLYMER, 242PRESSURE-SENSITIVE

ADHESIVE, 289PRESTRETCHING, 199PRETREATMENT, 82 322PRINCIPAL COMPONENTS

ANALYSIS, 178 222PROBE, 247 314 352PROCESS CONTROL, 152 227

314PROCESSING, 204 237PROCESSING AID, 175PROOFED FABRIC, 259PROPAGATION, 32 214 248 329PROPAGATION RATE

CONSTANT, 214 240PROPENE COPOLYMER, 74 117

123 189 204 221PROPYL ETHER, 246PROPYLENE COPOLYMER, 74

117 123 189 204 221PROPYLENE GLYCOL, 246PROPYLENE-ETHYLENE

COPOLYMER, 110 123 189PROTEIN, 42PROTON, 341PROTON CONDUCTING, 61PROTON TRANSFER, 244PROTONATION, 296PSEUDO CROSSLINK, 154PULSE EXCITATION, 229PYRENE, 218PYROLYSATE, 166PYROLYSIS, 274 302 325 358PYROLYSIS GAS

CHROMATOGRAPHY, 113PYROMELLITIC

DIANHYDRIDE, 332PYRROLE POLYMER, 121

Subject Index

140 © Copyright 2001 Rapra Technology Limited

QQUALITY CONTROL, 14 77 109

128 152 247 356 366 367QUANTITATIVE ANALYSIS, 3 4

8 72 74 126 176 184 202 226272 338 356

QUANTUM MECHANICS, 67QUATERNARY AMMONIUM

GROUP, 244QUENCHING, 177 219

RRADIATION CURING, 118 191RADIATION DEGRADATION,

330RADIATION DOSE, 146RADICAL POLYMERISATION,

124 135 151RADIO LABELLING, 289RAMAN SCATTERING, 9 108

304RANDOM COPOLYMER, 123

321RAPID HEATING, 31RAPID SCAN, 134 148 163RATE CONSTANT, 24 58 228 248

345RATE OF POLYMERISATION, 88REACTION INJECTION

MOULD, 364REACTION MOULD, 364REACTION RATE, 278 360REACTIVE BLENDING, 278REACTIVE PROCESSING, 227REACTIVE SITE, 3REACTIVITY, 165 189 196 262

354REACTIVITY RATIO, 64 314 321REAL TIME, 38 80 135 227 250

262 263 271 323RECYCLING, 77 157 209 247 261REDOX STATE, 298REDUCTION, 331REFLECTANCE, 5 247REFLECTANCE

SPECTROSCOPY, 6 21 49 112137 172 192 307

REFLECTION ABSORPTIONSPECTROSCOPY, 50 233 273

REFRACTIVE INDEX, 5 6 135217 326

REGIOCHEMISTRY, 116REGIOSELECTIVITY, 116REGRESSION ANALYSIS, 58 73

81 82 141 247 264 272REINFORCED PLASTIC, 109 161

166 190 207 212 217 221 237249 279 281 286 328 352 357

RELATIVE HUMIDITY, 246 312RELAXATION RATE, 92RELAXATION TIME, 201REORIENTATION, 16 199RESIDUAL MONOMER, 306 326RESIDUAL SOLVENT, 330RESIDUAL UNSATURATION,

154RESOLUTION, 164 222RESONANCE, 135 374REVERSE PHASE, 215REVERSIBLE, 65 197 253RHEOLOGICAL PROPERTIES,

16 96 117 170 243 253 304RICE HUSK ASH, 268RING OPENING, 13 217RING-CLOSURE, 332ROTATIONAL ISOMER, 307ROTATIONAL ISOMERIC STATE

THEORY, 309ROUGHNESS, 108

SSAPPHIRE, 110SATURATED POLYESTER, 133

143 183 284 325 353 365SATURATION, 164SAW, 188SCANNING ELECTRON

MICROSCOPY, 99 117 120156

SCRAP POLYMER, 81SCREW SPEED, 247SEAL, 154 192 200SEBACIC ACID, 133SECTIONING, 156SEGMENT, 163SEGMENTAL MOBILITY, 83 143SEGMENTAL ORIENTATION,

143 201SEGREGATION, 286 344SELECTIVITY, 30 116SELF-ASSOCIATION, 65 287SELF-DRYING, 86 144SEMI-EFFICIENT

VULCANISATION, 304SEMICRYSTALLINE, 26 52 186SENSOR, 110 178SEPARATION, 206 209SEQUENCE ANALYSIS, 10 123SEQUENCE DISTRIBUTION,

123 155 229 314SEQUENTIAL ELECTROLYSIS,

121SERVICE PROPERTIES, 341

SHEAR, 282SHEAR PROPERTIES, 281SHEAR STRESS, 212SHEAR YIELDING, 281SHEET, 156 204SHORT CHAIN, 4SHORT ITEM, 144 164 190 279SIDE CHAIN, 1 39SIDING, 76 153 175SIGNAL TRANSMISSION, 7SILANE COPOLYMER, 327SILANOL, 2 7SILICA, 33 142 217 268 304 324

366SILICATE, 44SILICON, 42SILICON CARBIDE FIBRE-

REINFORCED PLASTIC, 161SILICON DIOXIDE, 33 142SILICON-29, 2SILICONE COPOLYMER, 275SILICONE POLYMER, 163 289

291 303SILOXANE, 202SILOXANE COPOLYMER, 275SILVER, 9 108 362SIMULTANEOUS

INTERPENETRATINGPOLYMER NETWORK, 238

SINGLE CRYSTAL, 213 373SINGLE FIBRE, 161 212SINGLE SITE CATALYSIS, 155SINGLE-SCREW EXTRUDER,

247SIZE EXCLUSION

CHROMATOGRAPHY, 215257

SKIN-CORE MORPHOLOGY,346

SLIP AGENT, 366SMALL ANGLE X-RAY

SCATTERING, 10SMECTIC, 39 163SMOKE CHAMBER, 236SODIUM, 160SODIUM BOROHYDRIDE, 288SODIUM CELLULOSATE, 294SODIUM DIOCTYL

SULFOSUCCINATE, 21 202SODIUM DODECYLSULFATE,

21SODIUM HYDROXIDE, 146 288

294SODIUM METHACRYLATE

COPOLYMER, 310SODIUM THIOCYANATE, 65SOFT SEGMENT, 39 55SOFTWARE, 148 152 242

Subject Index

© Copyright 2001 Rapra Technology Limited 141

SOL-GEL, 13SOLID, 129 258 326SOLID PHASE, 7SOLID STATE, 2 113 129 229 354

361SOLID STATE

POLYMERISATION, 220 315SOLIDS CONTENT, 246SOLITON, 160SOLUBILITY, 17 26 37 55 88 124

133 180 196 224 304SOLUTION CASTING, 233 344SOLUTION POLYMERISATION,

35 321 363SOLUTION PROPERTIES, 287

293SOLVENT, 47 65 89 150 154 196

257 321 322 330 332 338SOLVENT ABSORPTION, 154SOLVENT CAST, 3 180 298SOLVENT EXTRACTION, 4 272SORPTION, 26 150 230 300SPACER, 243SPACER LENGTH, 143SPECIFIC VOLUME, 150SPECIFICATION, 356SPECTRAL SUBTRACTION,

156 186 189 323SPECULAR REFLECTANCE, 5

247 251SPHERULITE, 52 187SPRAY DRYING, 86 144SPUTTER ETCHING, 137SQUALENE, 9STABILISER, 62 86 144 166 175

176 189 368STABILITY, 113 189STANDARDISATION, 166STATIC ABSORPTION, 96 169STATISTICAL EXPERIMENTAL

DESIGN, 211STEARIC ACID, 304 371STEEL, 285STEP POLYMERISATION, 238STEP SCANNING, 8 18 163 168STEP-SCAN FTIR

SPECTROSCOPY, 7 164 235STEP-SCAN PHOTOACOUSTIC

SPECTROSCOPY, 7 18 44 103148

STEREOCHEMISTRY, 219 258329

STEREOREGULARITY, 211STEREOSEQUENCE

DISTRIBUTION, 219STERIC HINDRANCE, 154STOICHIOMETRY, 154 165 296STOPPED-FLOW

SPECTROSCOPY, 329STORAGE, 189STRAIN, 16 39 51 55 94 102 134

161 187 210 212 235 250 281282 304

STRAIN-HARDENING, 210STRAND, 247STRATIFICATION, 8STRESS, 99 154 187 199 243 250

282STRESS CONCENTRATION,

207STRESS CRACK RESISTANCE,

99STRESS RELAXATION, 92 197

201STRESS TRANSFER, 161 212STRESS-INDUCED

ENVIRONMENTDIFFUSION, 99

STRESS-STRAIN PROPERTIES,79 161 187 197 207 250 282299 320 355

STRETCH, 1 9 55 92 99 102 199291

STRUCTURAL ADHESIVE, 312STRUCTURAL PROPERTIES, 4

58 151 177 250STRUCTURE-PROPERTY

RELATIONSHIP, 79STYRENE, 60 226 257 272STYRENE COPOLYMER, 35 61

92 101 221 296 310 343 344STYRENE TERPOLYMER, 21STYRENE-BUTADIENE-

STYRENE BLOCKCOPOLYMER, 29

STYRENE-METHACRYLICACID COPOLYMER, 310

STYRENESULFONIC ACIDCOPOLYMER, 92 296

STYRENESULPHONIC ACIDCOPOLYMER, 92 296

SUBMICRON, 164SUBSTRATE, 149 150 153 165

194 202 232 233 245 246 285290

SUCCINIC ANHYDRIDECOPOLYMER, 74

SULFONATION, 61 311SULFUR, 224 304SULFUR DIOXIDE, 236SULFUR MUSTARD, 230SULFUROUS ACID, 300SUPERCRITICAL FLUID, 26 303SURFACE, 3 17 121 146 194 245SURFACE ACTIVE AGENT, 21

166 202 203 303

SURFACE ANALYSIS, 21 285342 344 359 362 375

SURFACE CRACKING, 156SURFACE ENERGY, 327SURFACE ENHANCED RAMAN

SCATTERING, 9 108SURFACE MODIFICATION, 342SURFACE MORPHOLOGY, 21SURFACE PROPERTIES, 8 21

156 202 204 241 259 288 318327

SURFACE STRUCTURE, 21 111241 318 359

SURFACE TREATMENT, 108 162193 232 237 285 303 322 342

SURFACTANT, 21 166 202 203303 349

SURGICAL ADHESIVE, 193 200SYNDIOTACTIC, 23 89 173 186

219 350SYNTHESIS, 2 35 88 115 124 125

214 240 319SYNTHETIC FIBRE-

REINFORCED PLASTIC, 221249

SYNTHETIC RUBBER, 224

TTACKIFIER, 165TACTICITY, 129 180 211 219 350TAPERED, 314TAUTOMERISM, 354TEMPERATURE, 26 53 77 89 94

128 134 147 154 155 163 165176 177 185 188 189 196 204217 240 243 246 248 280 302304 312 323 325 327 345

TEMPERATURE DEPENDENCE,56 78 112 113 114 126 146 163167 182 230 279 334 361

TEMPERATURE RANGE, 128167 214 238 240 242

TEMPERATURE RISINGELUTION FRACTIONATION,123

TEMPERATURE SENSITIVITY,293

TENSILE DRAWING, 99TENSILE MODULUS, 320TENSILE PROPERTIES, 46 79

117 161 207 212 237 251 282320 355

TENSILE STRAIN, 161TENSILE STRENGTH, 79 117TERMONOMER, 229TERNARY BLEND, 11

Subject Index

142 © Copyright 2001 Rapra Technology Limited

TERPENE PHENOL RESIN, 165233

TERPOLYMER, 66 343TETRABUTYLAMMONIUM

FLUORIDE, 321TETRACHLOROMETHANE, 126TETRAETHOXYSILANE, 2TETRAHYDROFURAN, 84 126

175 213 321TETRAMETHOXYSILANE, 13TETRAMETHYLTHIURAM

DISULFIDE, 304THERMAL ANALYSIS, 23 84

113 155 242 302 323THERMAL ANNEALING, 177

228THERMAL CONVERSION, 345THERMAL CURING, 242THERMAL DEGRADATION, 113

145 189 273 274 279 358THERMAL POLYMERISATION,

80THERMAL PROPERTIES, 29 53

93 113 120 128 141 155 165174 197 212 304

THERMAL STABILITY, 113 189302 325

THERMAL TRANSITION, 53THERMAL TREATMENT, 213

220THERMODYNAMIC

PROPERTIES, 177THERMOGRAVIMETRIC

ANALYSIS, 89 113 120 274323

THERMOMECHANICALPROPERTIES, 28 117 177

THERMOOXIDATION, 120 142THERMOOXIDATIVE

DEGRADATION, 104 279 323THERMOOXIDATIVE

STABILITY, 120THERMOPLASTIC

ELASTOMER, 39 304 364THERMOPLASTIC RUBBER, 39THERMOREVERSIBLE, 65THICK FILM, 72THIN FILM, 50 108 122 142 155

230 232 254 272 275 285 362THIOLENE, 38TIE MOLECULE, 187TIME DEPENDENCE, 112 135

352TIME RESOLVED

SPECTROSCOPY, 101TITANIA, 76TITANIUM ALKOXIDE, 124TITANIUM DIOXIDE, 76

TITANIUM TETRAALKOXIDE,124

TOLUENE, 133TOLUENE SULFONATE, 331TOPOCHEMICAL

POLYMERISATION, 315TOPOGRAPHY, 111TORQUE, 304TOUGHENING, 278TOUGHNESS, 278TRANS-POLYACETYLENE, 160TRANSESTERIFICATION, 348TRANSFORMATION, 151TRANSITION PHENOMENA, 31

216 309TRANSITION PROPERTIES, 216TRANSITION TEMPERATURE,

53 163TRANSMISSION ELECTRON

MICROSCOPY, 117 120 221TRANSMISSION FLUID, 154TRANSMISSION

SPECTROSCOPY, 4 104 146156 183 357

TRANSPARENCY, 247TRANSPORT COEFFICIENT,

230TRANSPORT NUMBER, 230TREAD, 341TRIAD, 155TRIBLOCK COPOLYMER, 85

344TRIMER, 302TRIMETHYLOLPROPANE

DIALLYL ETHERCOPOLYMER, 37 38

TRIMETHYLOLPROPANETRISTHIOL COPOLYMER,37 38

TUNGSTEN, 283TWISTON, 182TWO-DIMENSIONAL, 25 57 73

95 111 148 163 167 168 169174 218 235 254

TWO-LAYER, 194 245TWO-PART, 121TYRE, 139 341

UULTRA-THIN, 285ULTRADRAWN, 195 346ULTRAVIOLET CURING, 38 62

75 88 118ULTRAVIOLET IRRADIATION,

18 149 288 297ULTRAVIOLET

POLYMERISATION, 38 75 263

ULTRAVIOLETSPECTROSCOPY, 71

UNFILLED, 91 154UNIAXIAL, 79 235 243 253UNIAXIAL ORIENTATION, 1

251 359UNIAXIAL STRETCHING, 250UNIAXIALLY ORIENTED, 158UNIDIRECTIONAL, 223UNLOADING, 197UNSATURATED POLYESTER,

135 328 370UNSATURATION, 154 189UREA, 333URETHANE, 333URETHANE COPOLYMER, 96URETHANE DIACRYLATE

OLIGOMER, 161

VVANADIUM, 155VAPOUR, 150VARIATION COEFFICIENT, 176VINYL ACETATE, 72 130 141 226

272VINYL ACETATE COPOLYMER,

273VINYL ALCOHOL

COPOLYMER, 117 255VINYL CHLORIDE

COPOLYMER, 166VINYL CONTENT, 272 369VINYL CYANIDE, 154VINYL ESTER RESIN, 328VINYL GROUP, 272VINYL IMIDAZOLE

COPOLYMER, 142VINYL PHENOL COPOLYMER,

321VINYL PYRIDINE

COPOLYMER, 92 296VINYL SILANE, 142VINYL SILANE COPOLYMER,

142VINYL TOLUENE

COPOLYMER, 200VINYLIDENE FLUORIDE

COPOLYMER, 61VINYLPYRIDINE COPOLYMER,

92VINYLTRIMETHOXYSILANE

COPOLYMER, 142 327VIRGIN POLYMER, 247VISCOELASTIC PROPERTIES,

312VISCOELASTICITY, 312

Subject Index

© Copyright 2001 Rapra Technology Limited 143

VISCOSITY, 276 277 372VOLATILE, 189 302 325VOLUME CHANGE, 154VOLUME FRACTION, 165 192VULCANISATE, 304VULCANISATION, 154 304VULCANISATION TIME, 200VULCANISED, 264

WWATER, 17 36 93 140 146 150 154

185 196 232 246 258 287 293294 319 354

WATER ABSORPTION, 150 312WATER BINDING, 246WATER CONTENT, 185 246WATER PERMEABILITY, 150

300WATER RESISTANCE, 50WATER SOLUBLE, 297WAVE NUMBER, 154 189 264

WAVEGUIDE, 217 227WAVELENGTH, 135 141 247WEAR, 259WEATHER RESISTANCE, 76 149

153 189WEIGHT GAIN, 230WET SEPARATION, 175WIDE ANGLE, 94 114 116 173

180 186WIDTH, 161WINDOW FRAME, 176WOOL, 259

XX-RAY DIFFRACTION, 56 114

116 186 372X-RAY EMISSION

SPECTROMETRY, 341X-RAY FIBRE DIAGRAM, 195X-RAY PHOTOELECTRON

SPECTROSCOPY, 140 317

X-RAY SCATTERING, 10 56 94114 116 173 180 186

XENON ARC, 149XEROGEL, 2XYLENE, 133

YYARN, 320 337 372YIELD STRESS, 187YOUNG’S MODULUS, 10 79 187

216 237 312

ZZINC, 285ZINC OXIDE, 196 304ZINC SALT, 311ZINC SELENIDE, 194 215 245ZINC STEARATE, 33

Subject Index

144 © Copyright 2001 Rapra Technology Limited