infrared and raman spectroscopy of polymers
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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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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.
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Report 18 Agricultural and Horticultural Applications ofPolymers, J.C. Garnaud, International Committee forPlastics in Agriculture.
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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.
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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.
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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.
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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.
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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.
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Report 59 Polyimides - Materials, Processing and Applications,A.J. Kirby, Du Pont (U.K.) Ltd.
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Report 63 Conductive Polymers II, R.H. Friend, University ofCambridge, Cavendish Laboratory.
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Report 66 Reinforced Thermoplastics - Composition, Processingand Applications, P.G. Kelleher, New Jersey PolymerExtension Center at Stevens Institute of Technology.
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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.
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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.
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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.
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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.
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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.
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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
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.
Infrared and Raman Spectroscopy of Polymers
12
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
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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-
Infrared and Raman Spectroscopy of Polymers
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
31
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
Infrared and Raman Spectroscopy of Polymers
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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).
Additional References
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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.
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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.
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a.16 M. Moskvits, Reviews in Modern Physics,1985, 57, 783.
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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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40
a.27 S. Bistac, M.F. Vallat and J. Schultz, AppliedSpectroscopy, 1997, 51, 1823.
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a.29 B. Jasse and J.L. Koenig, Journal ofMacromolecular Science: Reviews inMacromolecular Chemistry, 1997, C17, 1, 135.
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a.33 http://www.polymeradditives.com.
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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
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