feasibility of using atmospheric plasma treatment

240
Abstract TYNER, DAVID WADE. Evaluation of Repellent Finishes Applied by Atmospheric Plasma. (Under the direction of Dr. Peter J. Hauser.) The conventional pad-dry-cure method to impart a water repellent fluoropolymer finish onto a textile has been used effectively for many years. Although this process has been very successful and is the most common method of repellent finishing, it does have disadvantages. The largest draw back to this method is that it is a wet process requiring high levels of thermal energy to evaporate the water and cure the fluoropolymer. Plasma processing can also impart a repellent finish on a textile and does not require high levels of thermal energy because there is no water to evaporate and the fluoropolymer polymerizes in the plasma therefore it does not need to be cured. Until recently, plasmas for industrial processing were only available under reduced pressure. This limited manufacturing because of the high cost of the vacuum equipment and the limitations of batch processing. Plasma processing is now available at atmospheric pressure resulting in the ability to polymerize a water repellent fluoropolymer onto the surface of a textile in a continuous full width process. This process has been successful in research labs although there has been very little research conducted on fabrics treated with industrial machinery. This research studied the repellency, durability, and cost associated with Dow Corning Plasma Solution’s (DCPS) Atmospheric Pressure Plasma Liquid Deposition (APPLD) technology and the conventional pad-dry-cure method. The core objective of this project was to determine if the APPLD process could be a viable replacement for the conventional pad-dry-cure method at this current state of technology for the cotton, nylon, polyester, and polyester/cotton fabrics

Upload: others

Post on 11-Feb-2022

4 views

Category:

Documents


0 download

TRANSCRIPT

Abstract

TYNER, DAVID WADE. Evaluation of Repellent Finishes Applied by Atmospheric Plasma. (Under the direction of Dr. Peter J. Hauser.)

The conventional pad-dry-cure method to impart a water repellent fluoropolymer

finish onto a textile has been used effectively for many years. Although this process has

been very successful and is the most common method of repellent finishing, it does have

disadvantages. The largest draw back to this method is that it is a wet process requiring high

levels of thermal energy to evaporate the water and cure the fluoropolymer.

Plasma processing can also impart a repellent finish on a textile and does not require

high levels of thermal energy because there is no water to evaporate and the fluoropolymer

polymerizes in the plasma therefore it does not need to be cured. Until recently, plasmas for

industrial processing were only available under reduced pressure. This limited

manufacturing because of the high cost of the vacuum equipment and the limitations of batch

processing.

Plasma processing is now available at atmospheric pressure resulting in the ability to

polymerize a water repellent fluoropolymer onto the surface of a textile in a continuous full

width process. This process has been successful in research labs although there has been

very little research conducted on fabrics treated with industrial machinery. This research

studied the repellency, durability, and cost associated with Dow Corning Plasma Solution’s

(DCPS) Atmospheric Pressure Plasma Liquid Deposition (APPLD) technology and the

conventional pad-dry-cure method. The core objective of this project was to determine if the

APPLD process could be a viable replacement for the conventional pad-dry-cure method at

this current state of technology for the cotton, nylon, polyester, and polyester/cotton fabrics

tested in this research. It should be noted that the fluoropolymers used in the conventional

and plasma treatments are not the same and the environmental impact of the plasma

treatment is not known at this time.

Spray, impact, water/alcohol, oil, and contact angle tests suggested that all fabrics

treated by the atmospheric plasma process exhibited equal levels of water repellency as a

commercial product finished by the conventional pad-dry-cure method. Only the cotton and

polyester/cotton fabrics treated by atmospheric plasma showed a decrease in repellency after

multiple wash cycles when compared to the conventional finishes under identical washings.

This research has also taken an in depth look at the costs associated with both the

atmospheric plasma and the conventional processing methods. It has been determined that

the atmospheric plasma cost associated with the fabric used in this research was $1.13 per

square yard. It was also calculated that the cost to finish a square yard of the fabric by the

conventional method was $0.20. Although this is a large discrepancy, a theoretical cost

projection for the DCPS APPLD process in a fully engineered industrial scenario was

estimated at $0.15 per square yard.

The results of this research have lead to two main recommendations for future

research. First, additional fabric should be run by Dow Corning at settings from which the

theoretical cost calculation was based, which more accurately portrays an industrial scenario

in order to determine if comparable results will be observed. Secondly, a company named

APJeT should be investigated because they also have a continuous full width atmospheric

plasma machine and have the following differences from Dow Corning: APJeT can recycle

the helium gas used in the process, can coat different finishes on each side of the fabric, and

has the ability to run faster because of a higher plasma density, leading to a projected cost per

square yard of fabric of $0.10.

EVALUATION OF REPELLENT FINISHES APPLIED BY ATMOSPHERIC

PLASMA

by

DAVID WADE TYNER

A thesis submitted to the Graduate Faculty of

North Carolina State University

in partial fulfillment of the

Degree of Master of Science

TEXTILE ENGINEERING

Raleigh, NC

2007

APPROVED BY:

____________________________

Dr. Peter J. Hauser

Chair of Advisory Committee

____________________________

Dr. Stephen Michielsen

Member of Advisory Committee

____________________________

Dr. Henry Boyter Jr.

Member of Advisory Committee

____________________________

Dr. Jeffrey A. Joines

Member of Advisory Committee

ii

Dedication

This work is dedicated to my wife Jaclyn who supported and encouraged me to attend

graduate school. During my time at NCSU, she has given me a beautiful daughter who has

put my studies in perspective and to which I am deeply grateful.

iii

Biography

Wade Tyner was born and raised just outside of Athens, Ga. After graduating from

Madison County High school, Wade accepted an athletic scholarship to attend West Virginia

University where he studied Electrical Engineering. He graduated in May of 2003 with cum

laude honors while obtaining All-American status all four years while shooting for WVU’s

renowned rifle team. Wade accepted a position in plant engineering at Milliken &

Company’s Excelsior Union Finishing plant in Union, SC in July of the same year. His wife,

Jaclyn, has a master’s degree in counseling and was working as a counselor at Mount Olive

College at Research Triangle Park until the birth of Aubrey Gale Tyner on June 14, 2006.

After graduation from NCSU, Wade will be returning to Milliken & Company to pursue a

career in nonwovens.

iv

Acknowledgements

This work could not be completed without the help of many people. First, I would

like to thank Milliken & Company along with the Institute of Textile Technology for giving

me the opportunity to return to school to earn my masters degree. Secondly, I would like to

thank all of my committee members for sharing with me their knowledge of my subject and

giving me direction along with constructive criticism. Thirdly, I would like to thank the

following individuals that also have contributed to my research:

Alex Padilla, APJeT

Allen White, Milliken & Co.

Angie Brantley, NCSU

Mary Ann Ankeny, Cotton Inc.

Bob Adams, Milliken & Co.

Chris Desoiza, Milliken & Co.

David Wenstrup, Milliken & Co.

Fred Stevie, NCSU

Gary Lord, Dow Corning

Caroline O’Sullivan, Dow Corning

Jan Pegram, NCSU

Jeff Krauss, NCSU

Jack Daniels, AATCC

Paul Pruitt, Milliken & Co.

David Beard, Milliken & Co.

Joe Waddell, Milliken & Co.

Joel White, IT3

Judy Elson, NCSU

Hoonjoo Lee, NCSU

Manfred Young, ITG

Nathan Miller, Cotton Inc.

Shelly Benjamin, Milliken & Co.

Steve Middlebrook, Milliken & Co.

Suzanne Holmes, AATCC

Svetlana Verenich, NCSU

Patrice Hill, ITT

Chris Moses, ITT

Suzanne Matthews, Whitford

v

Table of Contents List of Figures ....................................................................................................................................... ix List of Tables.......................................................................................................................................... x List of Equations .................................................................................................................................xiii

1. Background .................................................................................................................................... 1 2. Literature Review ........................................................................................................................... 3

2.1 Introduction ............................................................................................................................ 3 2.2 Water Repellency ................................................................................................................... 3

2.2.1 Concepts ......................................................................................................................... 4 2.2.2 Wetting ........................................................................................................................... 4 2.2.3 Contact Angles ............................................................................................................... 7 2.2.4 Critical Surface Tension ................................................................................................. 9 2.2.5 Fabric Construction ...................................................................................................... 12

2.3 Water Repellents .................................................................................................................. 14 2.3.1.1 Non Silicone and Non Fluorocarbon Finishes.......................................................... 14 2.3.1.2 Silicone Finishes....................................................................................................... 16 2.3.1.3 Fluorochemical Finishes........................................................................................... 19

2.4 Test Methods ........................................................................................................................ 22 2.4.1 Spray Test..................................................................................................................... 22 2.4.2 Impact Test ................................................................................................................... 23 2.4.3 Rain Test....................................................................................................................... 23 2.4.4 Hydrostatic Pressure Test ............................................................................................. 23 2.4.5 Sorption Tests............................................................................................................... 24

2.5 Repellent Finishing............................................................................................................... 24 2.5.1 Conventional Methods.................................................................................................. 25

2.5.1.1 Exhaustion ................................................................................................................ 25 2.5.1.2 Padding..................................................................................................................... 25 2.5.1.3 Spraying.................................................................................................................... 27 2.5.1.4 Foaming.................................................................................................................... 27 2.5.1.5 Drying....................................................................................................................... 28

vi

2.5.1.6 Curing....................................................................................................................... 28 2.5.2 Plasma Processes .......................................................................................................... 29

2.5.2.1 Vacuum Plasmas ...................................................................................................... 32 2.5.2.2 Atmospheric ............................................................................................................. 34

2.6 Conclusion............................................................................................................................ 38 3. Procedures & Methodology.......................................................................................................... 39

3.1 Introduction .......................................................................................................................... 39 3.2 Fabrics Tested....................................................................................................................... 40

3.2.1 Cotton ........................................................................................................................... 40 3.2.2 65/35 Polyester/Cotton ................................................................................................. 41 3.2.3 Polyester ....................................................................................................................... 43 3.2.4 Nylon ............................................................................................................................ 44 3.2.5 Nonwovens ................................................................................................................... 45

3.3 Repellency Tests................................................................................................................... 46 3.3.1 Spray............................................................................................................................. 46 3.3.2 Impact ........................................................................................................................... 48 3.3.3 Water/Alcohol .............................................................................................................. 48 3.3.4 Oil ................................................................................................................................. 50 3.3.5 Contact Angle............................................................................................................... 51 3.3.6 Additional Tests............................................................................................................ 52

3.3.6.1 Hydrostatic Pressure ................................................................................................. 52 3.3.6.2 Wash Shrinkage........................................................................................................ 52 3.3.6.3 Air Permeability ....................................................................................................... 53 3.3.6.4 Tensile ...................................................................................................................... 53

3.4 Durability Tests .................................................................................................................... 53 3.4.1 X-ray Photoelectron Spectroscopy ............................................................................... 54 3.4.2 Wash............................................................................................................................. 54

4. Results and Discussions ............................................................................................................... 58 4.1 Atmospheric Plasma Treatment ........................................................................................... 58 4.2 Repellency & Durability....................................................................................................... 61

4.2.1 Cotton ........................................................................................................................... 61

vii

4.2.1.1 XPS Analysis............................................................................................................ 61 4.2.1.2 Spray......................................................................................................................... 62 4.2.1.3 Impact ....................................................................................................................... 63 4.2.1.4 Water/Alcohol .......................................................................................................... 64 4.2.1.5 Oil ............................................................................................................................. 64 4.2.1.6 Water Contact Angle ................................................................................................ 65

4.2.2 Polyester/Cotton ........................................................................................................... 66 4.2.2.1 XPS Analysis............................................................................................................ 67 4.2.2.2 Spray......................................................................................................................... 68 4.2.2.3 Impact ....................................................................................................................... 69 4.2.2.4 Water/Alcohol .......................................................................................................... 70 4.2.2.5 Oil ............................................................................................................................. 71 4.2.2.6 Water Contact Angle ................................................................................................ 71

4.2.3 Polyester ....................................................................................................................... 73 4.2.3.1 XPS Analysis............................................................................................................ 73 4.2.3.2 Spray......................................................................................................................... 74 4.2.3.3 Impact ....................................................................................................................... 75 4.2.3.4 Water/Alcohol .......................................................................................................... 76 4.2.3.5 Oil ............................................................................................................................. 76 4.2.3.6 Water Contact Angle ................................................................................................ 77 4.2.3.7 Additional Tests........................................................................................................ 78

4.2.4 Nylon ............................................................................................................................ 84 4.2.4.1 XPS Analysis............................................................................................................ 85 4.2.4.2 Spray......................................................................................................................... 86 4.2.4.3 Impact ....................................................................................................................... 86 4.2.4.4 Water/Alcohol .......................................................................................................... 87 4.2.4.5 Oil ............................................................................................................................. 88 4.2.4.6 Water Contact Angle ................................................................................................ 88

4.3 Cost Analysis........................................................................................................................ 90 4.3.1 Conventional Pad-Dry-Cure Finishing......................................................................... 90 4.3.2 Atmospheric Pressure Plasma Liquid Deposition Finishing ........................................ 91

viii

4.3.2.1 Theoretical Cost Projection ...................................................................................... 92 5. Conclusions & Recommendations ............................................................................................... 96

5.1 Repellency and Durability .................................................................................................... 96 5.2 Cost....................................................................................................................................... 97 5.3 Recommendations ................................................................................................................ 98 5.4 Summary ............................................................................................................................ 101

6. List of References....................................................................................................................... 102 7. Appendices ................................................................................................................................. 108

Appendix A : Dow Corning’s Atmospheric Pressure Plasma Liquid Deposition.............. 109 Appendix B : X-ray Photoelectron Spectroscopy (XPS) .................................................. 113

Appendix C : Cotton Additional Tables and Figures........................................................ 115

Appendix D : Polyester/Cotton Additional Tables and Figures........................................ 120

Appendix E : Polyester Additional Tables and Figures .................................................... 131

Appendix F : Nylon Additional Tables and Figures ......................................................... 173

Appendix G : Conventional Finish Cost Analysis Calculations ........................................ 184

Appendix H : APPLD Cost Analysis Calculations ............................................................ 189

Appendix I : Chemical Material Safety Data Sheets......................................................... 192

ix

List of Figures Figure 2.1. Equilibrium Contact Angle ................................................................................................. 7 Figure 2.2. Determination of Critical Surface Tension ....................................................................... 10 Figure 2.3. Three Possible Types of Behavior of a Liquid in Contact with a Surface ........................ 12 Figure 2.4. Polysiloxane Chemical Structure ...................................................................................... 16 Figure 2.5. Polymethylhydrogensiloxane (top) and Polydimethylsiloxane (bottom).......................... 17 Figure 2.6. Chemical Structures of Silanol (left) and Silane (right).................................................... 17 Figure 2.7. Schematic of Commercial Silicone Water Repellent........................................................ 18 Figure 3.1. Spray Test Ratings ............................................................................................................ 47 Figure 3.2. AATCC TM 193 Solution Grades .................................................................................... 49 Figure 4.1. Chemical Precursors Used for APPLD Treatment............................................................ 58 Figure 7.1. APPLD Precursor Injection Apparatus (Taken From WO Patent 28548) ...................... 109 Figure 7.2. Continuous APPLD Treatment (Taken from WO Patent 59809) ................................... 110 Figure 7.3. DCPS SE-1100 LabLine Machine .................................................................................. 111 Figure 7.4. DCPS SE-1000 AP4 Machine......................................................................................... 112

x

List of Tables Table 2.1. Critical Surface Tensions and Surface Free Energies of Polymers .................................... 11 Table 2.2. Surface Tension Values of Water, Critical Surface Energies of Selected Surfaces ........... 11 Table 2.3. Surface Tension Values of Surfaces Composed of Fluorocarbons .................................... 20 Table 2.4. Physicochemical Techniques ............................................................................................. 30 Table 3.1. Cotton Fabric Construction ................................................................................................ 40 Table 3.2. Cotton Fluorochemical Bath .............................................................................................. 41 Table 3.3. Polyester/Cotton Fabric Construction ................................................................................ 41 Table 3.4. Polyester/Cotton Repellency Requirements ....................................................................... 43 Table 3.5. Polyester Fabric Construction ............................................................................................ 43 Table 3.6. Polyester Additional Requirements.................................................................................... 44 Table 3.7. Nylon Fabric Construction ................................................................................................. 44 Table 3.8. Nylon Repellency Requirements........................................................................................ 45 Table 3.9. AATCC TM 193 Standard Test Liquids ............................................................................ 49 Table 3.10. AATCC TM 118 Standard Test Liquids .......................................................................... 51 Table 3.11. Number of Samples Required for Each Fabric................................................................. 55 Table 3.12. Wash Equipment .............................................................................................................. 55 Table 3.13. Washing Machine Settings ............................................................................................... 56 Table 3.14. Dryer Machine Settings.................................................................................................... 56 Table 4.1. DCPS APPLD DOE Operating Conditions........................................................................ 59 Table 4.2. DCPS LabLine Machine Settings....................................................................................... 59 Table 4.3. Optimal Parameters for Additional Nylon Treatment ........................................................ 60 Table 4.4. Cotton Fabric Nomenclature .............................................................................................. 61 Table 4.5. Fluorine Composition of Cotton Segments ........................................................................ 62 Table 4.6. Cotton Spray Results .......................................................................................................... 62 Table 4.7. Cotton Impact Penetration Results ..................................................................................... 63 Table 4.8. Cotton Water/Alcohol Results............................................................................................ 64 Table 4.9. Cotton Oil Results .............................................................................................................. 65 Table 4.10. Cotton Contact Angle Results .......................................................................................... 65 Table 4.11. Polyester/Cotton Fabric Nomenclature ............................................................................ 67 Table 4.12. Fluorine Composition of Polyester/Cotton Segments ...................................................... 67

xi

Table 4.13. Polyester/Cotton Spray Results ........................................................................................ 68 Table 4.14. Polyester/Cotton Impact Penetration Results ................................................................... 69 Table 4.15. Polyester/Cotton Water/Alcohol Results.......................................................................... 70 Table 4.16. Polyester/Cotton Oil Results ............................................................................................ 71 Table 4.17. Polyester/Cotton Contact Angle Results .......................................................................... 72 Table 4.18. Polyester Fabric Nomenclature ........................................................................................ 73 Table 4.19. Fluorine Composition of Polyester Segments .................................................................. 74 Table 4.20. Polyester Spray Results .................................................................................................... 75 Table 4.21. Polyester Impact Penetration Results ............................................................................... 75 Table 4.22. Polyester Water/Alcohol Results...................................................................................... 76 Table 4.23. Polyester Oil Results ........................................................................................................ 77 Table 4.24. Polyester Contact Angle Results ...................................................................................... 77 Table 4.25. Polyester Hydrostatic Pressure Results ............................................................................ 79 Table 4.26. Polyester 5 Wash Shrinkage Results ................................................................................ 80 Table 4.27. Polyester Air Permeability Results................................................................................... 81 Table 4.28. Polyester Tensile Test Results in the Warp Direction...................................................... 83 Table 4.29. Polyester Tensile Test Results in the Fill Direction ......................................................... 83 Table 4.30. Nylon Fabric Nomenclature ............................................................................................. 85 Table 4.31. Fluorine Composition of Nylon Segments ....................................................................... 85 Table 4.32. Nylon Spray Results ......................................................................................................... 86 Table 4.33. Nylon Impact Penetration Results .................................................................................... 87 Table 4.34. Nylon Water/Alcohol Results........................................................................................... 87 Table 4.35. Nylon Oil Results ............................................................................................................. 88 Table 4.36. Nylon Contact Angle Results ........................................................................................... 89 Table 4.37. Total Cost of Conventional Treatment ............................................................................. 90 Table 4.38. Total Cost of APPLD Treatment...................................................................................... 91 Table 4.39. Fluorine Analysis Test Results......................................................................................... 93 Table 4.40. Total Theoretical Cost of APPLD Treatment in an Industrial Scenario........................... 95 Table 5.1. Comparison of Dow Corning and APJeT Technologies .................................................. 101 Table 7.1. Conventional Chemical Cost per Pound........................................................................... 184 Table 7.2. Information Used by American Monforts ........................................................................ 187

xii

Table 7.3. Information Returned by American Monforts.................................................................. 187 Table 7.4. Price of Chemical Precursors ........................................................................................... 189

xiii

List of Equations Equation 2.1. Gibbs Equation................................................................................................................ 4 Equation 2.2. Spontaneous Wetting ...................................................................................................... 5 Equation 2.3. Work of Immersion and Penetration ............................................................................... 5 Equation 2.4. Dupré’s Equation ............................................................................................................ 6 Equation 2.5. Work of Spreading .......................................................................................................... 6 Equation 2.6. Young’s Equation ........................................................................................................... 7 Equation 2.7. Work of Adhesion........................................................................................................... 8 Equation 2.8. Hydrostatic Pressure ..................................................................................................... 13 Equation 2.9. Percent Wet Pick Up..................................................................................................... 25 Equation 4.1. Fluorine ppm Levels on Cotton (top) and Polyester (bottom) ...................................... 93 Equation 7.1. Weight of Conventional Bath Picked Up.................................................................... 184 Equation 7.2. Conventional Chemicals Picked Up............................................................................ 185 Equation 7.3. Conventional Chemical Cost....................................................................................... 186 Equation 7.4. Tenter Electricity Cost ................................................................................................ 188 Equation 7.5. Natural Gas Cost to Maintain Tenter at 350 °F........................................................... 188 Equation 7.6. Natural Gas Cost to Dry and Cure .............................................................................. 188 Equation 7.7. APPLD Electricity Cost .............................................................................................. 190 Equation 7.8. APPLD Helium Cost................................................................................................... 190 Equation 7.9. Mass of Precursor Injected into Plasma Region.......................................................... 191 Equation 7.10. Mass of Precursor on Fabric ..................................................................................... 191 Equation 7.11 . Cost of Chemical Precursors.................................................................................... 191

1

1. Background

Atmospheric plasma treatment of textile materials to obtain water repellency has

recently become available to industry in a full width continuous process. This project will

study the repellency, durability, and cost of fluoropolymer textiles treated with atmospheric

plasma in comparison to the conventional pad-dry-cure process. The core objective of this

study is to determine if the current pad-dry-cure process can be replaced with an atmospheric

plasma process having an equivalent or superior performance at a comparable cost.

Although there is evidence that an atmospheric plasma process can achieve

repellency in textiles, there is currently no cost projection available for this process on an

industrial scale. In order to determine if atmospheric plasma finishing is a practical

alternative to conventional pad-dry-cure finishing, the cost of the former must be identified.

A conventional pad-dry-cure process requires high levels of thermal energy to

evaporate water and cure the fluoropolymer. In an industrial process, the energy needed to

dry the fabric is extremely expensive. In addition, intermediate fluorochemicals that are used

to produce these fluoropolymers have recently been shown to be persistently present in the

environment. Concerns of danger to public health from these intermediates have prompted

extensive review of existing commercial repellent finishes and renewed interest in the search

for new chemicals and application methods for producing repellent textiles.

The atmospheric plasma process is a dry process at room temperature where neither

water nor drying energy is needed. Atmospheric plasma machines are relatively small and

2

can easily be placed as a step within an in-line continuous process. In addition, atmospheric

plasma applied repellent finishes can involve different hydrophobic reactants that have not

been shown to be environmentally hazardous. The fluorochemicals used in the atmospheric

plasma treatment for this research were different from the chemicals used in the conventional

pad-dry-cure method. In addition, it should be noted that the chemicals used in the

atmospheric plasma process in this research were not used to represent an environmentally

friendly fluorochemical replacement for conventional fluorochemical pad-dry-cure

processing.

The objective of this research problem is to determine if atmospheric plasma is a

practical alternative to conventional pad-dry-cure repellent finishing at this current state of

technology. In order to address this objective, this research will evaluate the effectiveness of

both processes relative to repellency and durability, and also associate a cost to both the pad-

dry-cure and atmospheric plasma processes.

3

2. Literature Review

2.1 Introduction

The purpose of this literature review is to establish what is already known about the

concepts of liquid repellency and the use of atmospheric plasma treatment on textiles. The

theory of liquid repellency will be investigated along with methods used to make textile

fabrics repellent. The physics of plasma processing will not be covered in depth although the

results from plasma treatments will be reviewed. For more information on the physics of

plasma processing, the reader is referred to a book by M. Lieberman and A. Lichtenburg

called Principles of Plasma Discharges and Materials Processing.1

The review is broken into two main sections. The first section will discuss repellency

including theory, chemicals, and test methods. The second section will discuss the methods

used in repellent textile finishing including the conventional processes, such as pad-dry-cure,

and plasma processes, both low pressure and atmospheric.

2.2 Water Repellency

This chapter will discuss the theory of water repellents, typical chemical finishes to

obtain water repellency, and tests that can be used in order to quantify liquid repellency.

Although this section will discuss water repellency, the concepts, chemicals, and test

methods can also apply to other liquids including oils.

Water repellent treatment of fabrics has been of great interest since at least the

1880s.2 By definition, fabrics with water repellent finishes will repel water. The repulsion of

4

water from the fabric surface is due to the resistance of wetting, absorption, or penetration of

the water or any combination of these. Many terms have been used for water repellent

fabrics, particularly in marketing2, that are often imprecise, such as the term “water proof”.

Water proofing of textile fabrics will provide a barrier not only to water, but to water

vapor as well. Water repellent textile fabrics provide a barrier to water in the form of a

liquid, such as a rain drop, but allow water vapor to escape the fabric. Such water repellent

“breathable” textiles provide a much greater value to the consumer than water proof textiles.

Care should be taken to make the distinction between water proof and water repellent

textiles. This review will focus only on water repellency.

2.2.1 Concepts

In order to understand the mechanisms of water repellency, the physical interactions

at the surface of the fiber must be understood. Once these mechanisms are understood, the

likelihood of a fabric being wetted by a liquid can be predicted and fabrics can be engineered

to meet water repellency specifications.

2.2.2 Wetting

Repellency can be defined as a circumstance of restricted wettability.3 Gibbs applied

thermodynamic theory to the issue and related a decrease of free energy to wetting.4 Gibbs’

equation, as given below in Equation 2.1, gives the sum of interfacial energies, F,

F = ASγSV + ALγLV + ASLγSL = ∑Aγ

Equation 2.1. Gibbs Equation

5

where A is the area of subscripts S, L, and V that represent solid, liquid, and gas respectively

while γ is the surface energy per unit area. Spontaneous wetting occurs when the change in

free energy, ΔF, becomes negative as the result of a liquid-solid contact. Gibbs presented

this in Equation 2.2 below as:

ΔF = F2-F1 = Σ(Aγ)2 - Σ(Aγ)1

Equation 2.2. Spontaneous Wetting

where F1 and F2 are the sum of the interfacial energies before and after the liquid-solid

contact respectively. As a liquid is introduced to a surface, the solid-vapor interface is

replaced by a liquid-vapor interface. The change of the surface interface by a liquid can be

achieved by work done on the surface by immersion, capillary sorption, adhesion, and

spreading.2, 3 The work of immersion, adhesion, and spreading is denoted as WI, WA, and

WS respectively, while the work of capillary sorption is commonly known as the work of

penetration (WP). Depending on the means of wetting, the free energy change when a liquid

is removed from a solid will yield WI if the solid was immersed in a liquid, or WP if the

liquid was absorbed into the solid, which in our case is a textile.3 This concept is given in

Equation 2.3 below.

WI = WP = γSV - γSL

Equation 2.3. Work of Immersion and Penetration

For a surface to be repellent, WI (or possibly WP) must be negative.3 In other words,

it is desirable for the interfacial energy between a solid and vapor (γSV) to be smaller than the

6

interfacial energy of the solid and liquid interface (γSL). From this, it can be concluded that a

surface with a very low interfacial energy relative to vapor (γSV) is desirable for repellency.

The work of adhesion (WA) is the energy of attraction between two surfaces in

contact2, which in this case is a solid and liquid. The work of adhesion is calculated as the

change in surface free energy when the liquid is removed from the surface while the liquid-

vapor interface remains constant. This is given by the Dupré equation below.3

WA = γSV + γLV- γSL

Equation 2.4. Dupré’s Equation

Spreading of a liquid over a solid surface requires the liquid to flow at least two

molecular layers thick.2 The work of spreading is calculated very similarly to the work of

adhesion, but during spreading, the liquid-vapor and the solid-liquid interfaces are increasing.

The work of spreading should be negative for the surface to be repellent to the liquid

introduced on the surface. This work of spreading is also commonly known as the

“spreading coefficient”2 and is given in Equation 2.5 below.

WS = γSV - (γLV + γSL)

Equation 2.5. Work of Spreading

It is important to state that the equations above are valid only under ideal conditions.

Ideally, the surface must be smooth, homogeneous, impermeable, and non-deformable.3 As a

result, the use of these equations on textile fabrics should be performed with great care. Even

if a textile fabric were an ideal surface, these equations would be of little use unless γSV can

be easily measured and thus far, there is no direct method of doing so.

7

2.2.3 Contact Angles

If a liquid is neither immediately absorbed nor spread along the surface of a solid, the

drop will take a definite shape as the liquid, vapor, and solid interfaces reach equilibrium.

The angle from the solid-liquid interface to the liquid-vapor tangent is defined as the contact

angle θ and shown below in Figure 2.1.

Figure 2.1. Equilibrium Contact Angle

In the middle of the nineteenth century, Young related the contact angle to

wettability.5 High values of the contact angle θ indicate repellency, or more technically poor

wettability.2 Young proposed that a drop similar to that in Figure 2.1 would be subject to the

equilibrium forces given in Equation 2.6 below.

γSV = γSL + γLV cos θ

Equation 2.6. Young’s Equation

Young’s equation brings us closer to being able to measure the work performed on a

surface in order to determine repellency. When Equation 2.6 is combined with Equation 2.4,

Equation 2.7 below is derived.

8

WA = (γSL + γLV cos θ)+ γLV - γSL = γLV cos θ

Equation 2.7. Work of Adhesion

Equation 2.7 is practical for use because both γLV and cos θ are measurable.2

Although relative wettability can be determined from a measured contact angle, caution

should be used because Young’s equation, Equation 2.6, is only valid for an equilibrium

contact angle. In a real system, the liquid will typically recede or advance.

In order to explore receding and advancing contact angles, assume that a rain drop

falls on the surface of a water repellent fabric. The initial force of the drop hitting the fabric

will cause the drop to deform and temporarily spread on the fabric. The drop will then

recede from the fabric and form a droplet with a measurable contact angle. The measured

contact angle would be lower than that of a droplet that was gently placed on the fabric. This

is because during the initial spreading of the water, the surface absorbed some of the liquid

and thereby changed the surface tension upon recession of the droplet.6

The difference between advancing and receding contact angles is expressed by

contact angle hysteresis.3 Contact angle hysteresis is also dependent on surface

inconsistencies7 or surface roughness.8 The works of Adam, Fowks, and Wenzel show that

water repellent surfaces must be prepared with great care before the application of a water

repellent finish so that surface homogeneity and smoothness can be achieved.3 This is a

major challenge for textiles, and explains why there is such variability in repellency

performance results with fabrics.2

9

2.2.4 Critical Surface Tension

In order to predict the wettability of a surface, scientists knew that they would have to

find a way to calculate the surface free energy of a solid. Zisman developed a critical surface

tension (γC) where only liquids having surface tensions above this value will be repelled by

the surface.9 Zisman came to this conclusion by taking low energy surfaces and measured

the advancing contact angles (θ) of a series of homologous liquids. Furthermore, he

concluded that the critical surface tension is the maximum surface tension for a liquid that

has an advancing contact angle equal to zero. When the cos θ values are plotted against the

surface tension of the liquids, a relatively straight line was observed. The surface tension

when the contact angle is zero can be determined by extrapolation of the measured cos θ

against the surface tension of the liquids to where cos θ is equal to 1. This is shown

graphically in Figure 2.2 on the following page.

10

x y

γC = γx

Surface Tension of Liquid [dynes/cm]

Cos

ine θ

1.0

0

measured

extrapolation

x y

γC = γx

Surface Tension of Liquid [dynes/cm]

Cos

ine θ

1.0

0

measured

extrapolation

x y

γC = γx

Surface Tension of Liquid [dynes/cm]

Cos

ine θ

1.0

0

measured

extrapolation

Figure 2.2. Determination of Critical Surface Tension

Zisman concluded that the nature and packing of the exposed surface atoms of the

solid determine the critical surface tension and, therefore, the wettability of a surface.

Zisman and Fox stressed that γC varies between liquid types and thus is not a measure of the

surface energy of the solid.3, 10 The Zisman method has limitations because multiple

measurements are required in order to determine γC.3

Girifalco and Good11, Wu12, and Fowkes13 contributed to Owens and Wendt14

developing a method to measure the total surface free energy γS. By measuring θ of two

different liquids against a solid and solving equations postulated by Fowkes to determine the

contributions made by intermolecular forces at the surface, the surface free energy can be

calculated. Owens and Wendt found agreement between γS and γC as shown below in Table

2.1.9, 14

11

Table 2.1. Critical Surface Tensions and Surface Free Energies of Polymers

Polymer Zisman γC Owens γS

Poly(tetrafluoroethylene) 18 19 Poly(trifluoroethylene) 22 24 Poly(vinylidene fluoride) 25 30 Poly(vinyl fluoride) 28 37 Polyethylene 31 33 Poly(chlorotrifluoroethylene) 31 30 Polystyrene 33 42 Poly(vinyl alcohol) 37 Poly(vinyl chloride) 39 42 Poly(methyl methacrylate) 39 40 Poly(vinylidene chloride) 40 45 Poly(ethylene terephthalate) 43 41 Poly(hexamethylene adipamide) 46 47

In the discussion of water repellents with respect to γC, it should be noted that water

has a surface tension (γLV) of 72.75 dynes/cm at 20 ˚C.15 This means, in theory, that a surface

with a γC less than 72.75 dynes/cm will repel water. For a practical water repellent surface, it

has been established that a γC value of about 30 dynes/cm will give very good repellency.2, 3

Another important point to address is that the addition of a surfactant, impurities, or the

raising of the temperature of water, will decrease the surface tension of water. Typical

surface tension values of water and the γC of textile surfaces are given below in Table 2.2.2, 16

Table 2.2. Surface Tension Values of Water, Critical Surface Energies of Selected Surfaces

Water γLV (dynes/cm) Textile Surface γC (dynes/cm) @ 20 °C 72.75 Nylon 6,6 46

@ 100 °C 58.9 Wool 45 with Surfactant 25-35 Cotton 44

Polyester 43 Polypropylene 29

12

2.2.5 Fabric Construction

Fabric construction plays an important role in the wettability of textiles. When a drop

of water comes in contact with a solid, there are three types of behavior possible:17, 18

Region III: (γSV – γSL) ≥ γLV the drop is completely spherical,

Region II: γLV > (γSV – γSL) > -γLV the drop has a finite contact angle, or

Region I: (γSV – γSL) ≥ γLV the drop spreads, thus wetting occurs.

The regions above are illustrated in Figure 2.3 below.

0

Region IRegion IIRegion III

-γLV(γSV – γSL)

γLV0

Region IRegion IIRegion III

-γLV(γSV – γSL)

γLV

Figure 2.3. Three Possible Types of Behavior of a Liquid in Contact with a Surface

The repellency of a textile fabric depends on resistance to wetting and penetration by

the liquid.3 Holme2 gives three main parameters that determine the resistance of a textile to

wetting:

1. the chemical nature of the fiber surface;

2. the geometry and roughness of the fiber surface;

3. and the nature of the capillary spacing in the fabric.

The chemical nature of the fiber surface refers, for example, to the polar or nonpolar

bonds at the surface that will interact with water. Also, the geometry and roughness of a

13

fiber surface may promote or deter wicking of the water into the bulk. According to

Wenzel8, if the apparent contact angle is less than 90 degrees, the contact angle will be

decreased by increased surface roughness therefore promoting wicking into the bulk. But, if

the apparent contact angle is greater than 90 degrees and the surface roughness is increased,

the contact angle will increase. In addition, Baxter and Cassie18 proposed that if the apparent

contact angle is greater than 90 degrees and the capillary spacing in the fabric decreases, the

pressure needed for the liquid to penetrate the fabric increases. This suggests that the

geometry of the fabric should be tightly woven to decrease capillary spaces.

Baxter and Cassie expressed the resistance to the penetration of water into a textile

fabric in terms of the pressure difference between the two sides of a curved liquid surface

with a surface tension γLV.18 The pressure difference is the hydrostatic pressure, ΔP, that is

required to force the liquid through the fabric and is given in Equation 2.8 below

ΔP = 2(γSV – γSL)/R

Equation 2.8. Hydrostatic Pressure

where R is the largest opening in the textile structure. Baxter and Cassie stated that for a

fabric to be repellent to a liquid and thus resist penetration, ΔP must be negative and large in

value. In order for ΔP to fulfill this requirement, γSV – γSL must be negative and R must be

very small.

In summary, a water repellent fabric must: be free of any impurities, especially

surfactants, have a uniform finish where γC < γLV, and be engineered where ΔP is a negative

and large value.

14

2.3 Water Repellents

The use of chemicals or auxiliaries to lower the surface energy of textiles to achieve

water repellency is a common practice. This section will give a brief history of the

developments of water repellent fabrics. Silicone and fluorocarbon finishes are the most

commonly used finishes today from which there is extensive literature. The following

review of water repellents is broken into three parts: non silicone and non fluorocarbon,

silicone, and fluorocarbon finishes.

2.3.1.1 Non Silicone and Non Fluorocarbon Finishes

Soap/Metal Salt Finishes

One of the oldest methods of making a water repellent fabric dating back to 1882 was

to take a tightly woven cotton canvas and impregnate it in an aluminum acetate solution

followed by a padding then careful drying.3, 19 Padding and drying will be discussed in

Section 2.5.1. The result was a water repellent fabric with harsh handle, poor adhesion, very

limited durability to washing, and prone to dusting.2, 3 By applying an aluminum water

soluble soap and precipitating it with an aluminum salt, the water repellent properties were

improved, but they still lacked washfastness. Zirconium soaps, introduced in 1925, replaced

aluminum soaps because they are more resistant to alkali detergents and thus they have a

better washfastness than aluminum soaps.19

Wax Finishes

One of the easiest and most economical ways to produce a water repellent fabric is to

coat it with a hydrophobic wax substance such as paraffin. Waxes are easily applied because

15

they can be padded on the surface and then heated up for a uniform coating. They can be

applied from aqueous emulsions or solutions in organic solvents.3 Waxes have poor

durability to washing, but when they are combined with a zirconium salt emulsion, they have

the potential to have a considerable durability to laundering.20 These emulsions are usually

compatible with most other kinds of finishes, but they do increase flammability and offer low

vapor permeability.21

Pyridinium-based Finishes

Pyridinium-based finishes were extensively reviewed by Harding in 1951.19

Research by Hydrierwerke in 1931 led to patents in the manufacture of quaternary

ammonium salts. It was discovered that impregnation of cotton fabrics with aqueous

solutions of quaternary ammonium compounds, such as octadecyloxymethyl pyridinium

chloride, resulted in a durable water repellent finish after drying. From this work Velan PF

was commercialized in 1937, but in the US it was known as Zelan.2, 19 A synergistic effect

was later observed in 1960 by coapplication with fluorochemical repellents resulting in good

durability to laundering and long lasting repellency.22 This finish was named Quarpel.

Because of toxicological considerations, pyridinium-based repellents are no longer in

production.3

Stearic Acid-Melamine Finishes

Stearic acid contains hydrophobic groups that will provide water repellency when it is

added to formaldehyde and reacted with melamine. The N-methylol groups that are formed

react with cotton or cross-link with themselves to yield an increased durability to

16

laundering.21 Although this class of repellents has desirable durability, they have decreased

tear strength and abrasion resistance in addition to a change of shade when applied to dyed

fabrics.21

2.3.1.2 Silicone Finishes

The application of silicone, based upon polysiloxanes, to provide water repellency for

textiles was first discovered by Kipping in 1901 but not commercialized until 50 years

later.23 Today, silicones are exceeded only in volume by fluorochemicals to achieve water

repellency in textiles.20 Silicones were widely used between 1970 and 1990 because they can

be applied at a relatively low add-on, have a soft handle compared to other alternatives, can

easily be applied and even easily be combined with other chemicals, have a wide

applicability to many textile materials, and their cost is lower compared to fluorochemicals.2

The most common silicone repellents are polydimethylsiloxane products.20 Silicones

used for water repellents have a -O-Si-O- backbone with a structure given in Figure 2.4.

These polymers are called polysiloxanes.

Si

R

R

O

n

Si

R

R

ROSi

R

R

O

Figure 2.4. Polysiloxane Chemical Structure

For textile applications, R is typically either a methyl or hydrogen yielding

polydimethylsiloxane or polymethylhydrogensiloxane respectively and both are shown in

Figure 2.5.2, 3

17

O

Si

O

Si

O

Si

O

Si

O

Si

O

CH3 CH3CH3 CH3CH3CH3CH3CH3 CH3 CH3

FABRIC SURFACE

FABRIC SURFACEO

Si

O

Si

O

Si

O

Si

O

Si

O

H CH3 H CH3CH3HCH3H H 3CH

Figure 2.5. Polymethylhydrogensiloxane (top) and Polydimethylsiloxane (bottom)

Polymethylhydrogensiloxanes polymerize during heating leaving a hard brittle

surface film with a harsh handle. For this reason, polydimethylsiloxane is commonly used

because they form a flexible surface film resulting in a soft hand.2 In the case of

polydimethylsiloxanes, water repellency is achieved by the outward oriented methyl groups

while hydrogen bonds adhere the polydimethylsiloxane to the fibers at the surface of the

fabric.21 Polydimethylsiloxane usually has a silanol and silane component as shown in

Figure 2.6.

Figure 2.6. Chemical Structures of Silanol (left) and Silane (right)

18

During the curing step after padding and drying as discussed in Sections 2.5.1.2 and

2.5.1.5, the silanol and silane components react forming a fully cross linked silicone polymer

film on the fiber surface resulting in excellent water repellency and durability.2, 21 This can

be further enhanced by using adjuvants, which are also known as catalysts, that accelerate

cross-linking, and ensure proper orientation on the fiber as well as improved bonding at the

fiber.3

Crosslinking is essential to durability. It is the Si-H groups of the silane that are the

reactive links that generate crosslinking. They can be oxidized by air or hydrolysed by water

forming hydroxyl groups that can also promote crosslinking. Although the hydroxyl groups

can promote crosslinking, if too many of them do not react, their hydrophilicity will decrease

repellency.21

Madaras states that silicones are intermediate in character between inorganic and

organic materials, and possess hybrid properties.23 The commercial silicone structure that

water repellent textiles are based on is given in Figure 2.7.

SiO O Si

CH3

O Si

CH3

CH3

CH3Si

CH3

CH3

H3C

CH3

CH3 Hx y

Figure 2.7. Schematic of Commercial Silicone Water Repellent

The chemical manufacturing of silicones is highly modifiable; therefore, silicone

finishes can be engineered to meet performance and repellent specifications. This can be

19

accomplished by chain forming or termination along with crosslinking functional groups or

modifying the molecular weight distribution.23

Synthetic fabrics have been found to have a high durability to laundering and dry

cleaning although hydrophobic impurities from dry cleaning solvents in addition to the

possible dissolution of the polysiloxanes in the organic solvent may eventually reduce water

repellency.2, 24 Natural fibers such as cotton can rupture the polysiloxanes sheath around the

fibers upon swelling under aqueous laundering conditions.3, 25 The polysiloxane film will not

flow and fill in the cracks that are ruptured by the application of heat. As a result,

deterioration in the performance of the water repellent finish on natural fibers is expected

after multiple aqueous laundering.2

2.3.1.3 Fluorochemical Finishes

Fluorochemical finishes, commonly referred to as fluorocarbon finishes, are the most

widely used repellent finish in the textile industry and both natural and synthetic fibers can

be treated.2, 20 Fluorocarbons are unique in that they can repel not only water, but oils as well

because they have a very low surface energy (γC ~ 15 dynes/cm or less).2, 3 Excellent

chemical and thermal stability of fluorocarbons allow them to have great durability during

laundering, drycleaning, and tumble-drying.2 In addition, fluorocarbon finishes can be

applied at a lower add-on (< 1% owf) than any other repellent finishes.2, 21 Surface tension

values containing different fluorochemicals are given below in Table 2.3.2

20

Table 2.3. Surface Tension Values of Surfaces Composed of Fluorocarbons

Surface Constitution γC at 20 ˚C (dynes/cm)

–CF3 6.0 –CF2H 15.0 –CF3 and –CF2 17.0 –CF2– 18.0 –CF2–CFH 20.0

Fluorocarbons are organic chemicals that are synthetically produced by incorporating

perfluoro alkyl groups into acrylic or urethane monomers that can then be polymerized to

form fabric finishes.2, 21 The two main techniques used to manufacture fluorocarbons are

electrochemical fluorination and telomerisation.2, 17

Electrochemical fluorination was discovered at Pennsylvania State University when a

researcher passed a direct current through an organic hydrocarbon that was dissolved in

anhydrous hydrogen fluoride and realized that a fluorocarbon could be produced.26 This

concept was later used by 3M to develop their common Scotchgard Protector® range of

products.2 The electrochemical process results in both linear and branched chains of

fluoropolymers.27 Although electrochemical fluorination is very effective, 3M phased this

process out in March of 2001 due to environmental concerns.2, 28

Telomerization was developed by the DuPont Company in the early 1960s and is now

the most common method to produce fluorochemicals.3, 21 Due to the radical nature of the

reaction, only linear chains are formed unlike electrochemical fluorination that also forms

branched chains. This process produces a mixture of telomers differing in the length of their

21

linear carbon chain resulting in a distribution from C6F13 up to C12F25 at C2F4 intervals. For a

water repellent textile, a high content of C8F17 is advantageous.2, 3, 29

Water repellency is achieved by the perfluorinated side chains that provide a dense

CF3 barrier on the fabric as suggested in Table 2.3.21 Most scientists agrees that the length of

the repellent side chain should contain about eight to ten carbon segments.2, 3, 21

A new development in fluoropolymer finishing is the use of blocked isocyanates,

commonly called boosters.21 With the use of boosters, it is possible to regenerate the correct

orientation of the perfluorinated side chains at room temperature without the need of ironing

or tumble drying as compared to conventional fluoropolymer finishes. Products where air

drying is sufficient are called laundry-air-dry or LAD products.21 It has been found that the

use of boosters increase repellency by improving film formation and orientation of the

perfluorinated side chains.30 Although boosters may increase repellency, they can adversely

affect fabric hand.21

Flurorcarbon finishes are currently the best repellent finishes available but they are

also the most expensive. In order to lower the cost of these finishes, they are commonly

mixed with other repellents, such as wax or melamines, in order to reduce cost and in some

cases result in improved durability or hand. Fluorocarbons are not used with silicones

because it would diminish the oil repellency of the fluorochemical due to phase separation

resulting from a chemical incompatibility causing the formation of inhomogeneous island

structures on the coated surface.17 In addition to the high cost of fluorocarbon finishes, they

can tend to cause graying during laundering, in the manufacturing process have potentially

22

dangerous aerosols, and commonly need special treatment for the waste water that is

generated from the application process.21 Also, intermediate fluorochemicals that are used in

the process have been shown to be persistently present in the environment.31

2.4 Test Methods

There have been many test methods developed over the years to test the repellency of

textile fabrics, this section will discuss the most widely accepted methods. There are three

main classes of test methods for water repellency:2, 3

Class I: spray tests;

Class II: hydrostatic pressure test;

Class III: sorption of water by the fabric immersed in water tests.

2.4.1 Spray Test

This first class of test methods simulates a fabric’s exposure to rain. The spray test,

AATCC Test Method 22, measures the resistance of fabrics to wetting by water.32 In this

method, a taunt fabric sample lies 155 mm below a spray nozzle at the 45˚ angle and 250 mL

of water is poured onto the fabric through the spray nozzle. After the fabric is “smartly”

tapped, the wetting pattern is compared with a standard rating chart given in Figure 3.1 on

page 47. Complete wetting results in a score of 0 while no wetting pattern will result in a

score of 100. Because of the portability and simplicity of the instrument used along with

how quickly results can be obtained, this test method is useful in textile production control

work. Although the spray test can obtain quick results, they are very subjective. Other tests

are available that are more objective because they can be measured.

23

2.4.2 Impact Test

The impact penetration test, AATCC TM 42, is also used to simulate a fabric’s

exposure to rain.32 Unlike the spray test, this test method measures the resistance of fabrics

to the penetration of water by impact, thus it can be used to predict the resistance of fabrics to

rain penetration. In this test, a weighed paper blotter is placed under the fabric sample that is

clamped on the top end at an angle of 45˚ and 500 mL of water is sprayed from a nozzle onto

the fabric sample from 0.6 m above. Immediately after spraying, the blotter is weighed and

the difference in weight indicates the amount of penetration by water.

2.4.3 Rain Test

The rain test, AATCC TM 35, is very similar to AATCC TM 42 because it also

measures the resistance of fabrics to the penetration of water by impact, but the rain test can

vary the intensity of the water impacting the fabric.32 The fabric sample, with a weighed

paper blotter behind it, is placed vertically across from a spray nozzle 30.5 cm away and is

exposed to a water spray for 5 minutes. The pressure head can be varied in the rain tester

apparatus to give the full range of a fabric sample’s performance. The pressure head can be

changed to determine the points where no penetration occurs. The test can be used to

determine the amount of water absorbed by a given pressure head over 5 minutes, or the

minimum pressure head required for the paper blotter to absorb 5g of water over 5 minutes.

2.4.4 Hydrostatic Pressure Test

The hydrostatic pressure test, AATCC TM 127, measures the resistance of a fabric to

the penetration of water under hydrostatic pressure, but the test results do not correlate with

24

resistance to penetration by rain.3, 32 A fabric sample is placed in a hydrostatic tester and

hydrostatic pressure is increased at a constant rate. The pressure at which water penetrates

through the fabric in three locations is the penetration pressure and is measured in

centimeters of water guage. There is also a variation in this test method where a fabric

sample is held at a constant hydrostatic pressure and the time until penetration is recorded.

2.4.5 Sorption Tests

The sorption test, AATCC TM 70, is a dynamic absorption test that measures the

absorption of water into, but not through, the fabric.32 The results of this test depend on the

resistance to wetting of the fibers and yarns in the fabric, and not upon the construction of the

fabric. Fabric samples are weighed and then tumbled in water for 20 minutes. The samples

are then removed and passed through a wringer at 2.5 cm/s. The sample is then placed

between two paper blotters and passed through the wringer again. The specimen is then

weighed to the nearest 0.1 gram. The percentage increase in mass of the fabric sample is the

measure of dynamic absorption.

2.5 Repellent Finishing

The final step of a textile process is finishing. The finishing of a textile is commonly

referred to as either a chemical or mechanical finish.21 Mechanical finishing is a dry process,

such as calendaring, that usually alters the appearance of the textile while chemical finishing,

discussed below, is a wet process and generally does not change the appearance of the

textile.21 Because chemical finishing involves imparting a chemical into a textile, the

chemicals used are nearly always incorporated in water. Because chemical finishing is an

25

aqueous process, the water must be removed from the fabric (drying) and if necessary, the

fabric temperature must raised to a temperature that activates the chemical (curing).21, 33 This

section will discuss the methods used to create a repellent finish on a textile.

2.5.1 Conventional Methods

2.5.1.1 Exhaustion

Exhaustion is a term commonly used in the dyeing industry. If a chemical has a

strong affinity to a fiber surface, it can be “exhausted” to the surface of the fiber in a bath.

This would usually be accomplished in a jet dyeing machine because it can provide the

specific temperature and agitation required for exhaustion.21 Silicone emulsions and

fluorocarbons can be applied by exhaustion to achieve water repellency, but the residual

emulsifiers can impair repellency.3, 20

2.5.1.2 Padding

The most effective method to achieve water repellency is through padding.20 In this

process, the textile is passed through a trough with a chemical bath and then ran through two

nip rolls that squeeze out the excess bath so the exiting textile will have a certain percentage

of chemical in it. The percentage of chemical imparted to the fabric is referred to as the “wet

pick up”, or wpu, and is expressed below in Equation 2.9.21

% wpu = (wt of soln applied/ wt dry fabric)*100

Equation 2.9. Percent Wet Pick Up

26

In order for there to be a uniform coating of chemical to the textile, the temperature

and concentration of the bath, the nip pressure, and the speed at which the textile passes

through the nip must remain constant.34 It is common to dry a fabric before padding that has

been dyed; this is a wet on dry process.21 Because this requires an additional drying step, a

wet on wet process is sometimes used where a wet textile is passed through a chemical bath

and then padded.21 This process is more complicated than the wet on dry process because the

water that is in the textile will mix with the chemical bath and dilute it causing a “tailing”

effect on the finish.21 In order for this problem to be alleviated, a chemical feed must be used

that is more concentrated than the bath. In addition, the wet pickup of the exiting fabric must

be at least 15-20% higher than that of the incoming fabric.21

As previously stressed, a textile going through a chemical finishing process will

contain water that must be removed. Typical wet pickups for pad applications are 70-100%21

and the evaporation of this large amount of water during drying can lead to an uneven finish

resulting from the migration of the finish to the fabric surface.35 For this reason, low wet

pickup application methods are used.

One obvious method to decrease the amount of water on the fabric is to increase the

concentration of the chemical. Although this is possible, it is many times impractical

because of both uniformity problems and chemical concentration constraints. Instead of

increasing the chemical concentration of the bath, the water can be recovered from the fabric

downstream by vacuum extraction. By vacuum extraction, the wet pick up can be reduced to

27

40%.33 In addition to vacuum extraction, spraying and foaming can be used to lower the wet

pick up of a finish.

2.5.1.3 Spraying

It is possible for some repellent chemicals to be sprayed directly onto the fabric

surface. Spraying is commonly used for silicone based chemistry but it is only used with

fluorocarbons if a low level of repellency is required.20 Spray bars deliver a set amount of

chemical to the textile that can be adjusted by controlling the flow rate.21 Overlapping spray

patterns can result in an uneven finish and caution should also be taken when using

fluorocarbon aerosols because they can be potentially dangerous when inhaled.21, 36

2.5.1.4 Foaming

Because wet processing requires expensive processing steps to dry the textile after the

application of a chemical, methods to reduce the amount of water added to the textile are

desirable. Foams are sometimes used to apply a finish on a fabric because they replace water

in the chemical formulation with air.21 Foam generators produce foam according to the

“blow ratio” that describes foam density, which is typically about 0.1 g cm-3.21, 33 A knife

blade or a squeeze roll can be used to ensure a uniform application of foam.21, 33 Because of

the application method of foam, it is possible to coat a textile with the same chemical on both

sides by a transfer or squeeze roll, or apply two different finishes on each side simultaneously

by using a foam slot applicator.21 Similar to spraying, a foam application of a fluorocarbons

are used only when low levels of water repellency are required.20

28

2.5.1.5 Drying

The majority of the water on a wet textile can be removed by squeezing or vacuum

extraction, but the remaining water in the fibers and inter yarn capillaries must be removed

thermally. This can be accomplished by conduction, convection, or radiation.21 Conduction

involves direct contact of the textile material with a hot surface such as a steam heated drum.

By vertically stacking these dry cans, a large heated area can be obtained with minimal floor

space.33 The most common drying method is through convection where hot air is put in

contact with the textile, such as in a tenter. With the use of a tenter frame, the textile can be

dried while tensions in both the length and width can be controlled, unlike conduction

methods.21 The factors affecting the drying in a tenter frame are the air temperature, air flow,

and the humidity of the drying air.33 Radiation dryers use infrared and radio frequencies to

vaporize the water in the textile.21 It should be noted that with all of these methods, the

temperature of the fabric cannot exceed 100 ˚C until all of the water is removed from the

fabric because the fabric will only get as hot as the boiling point of the water in it.33 After all

of the water is removed from the fabric, curing can occur at a set temperature.

2.5.1.6 Curing

All of the previous methods used to dry a textile can also be used for curing providing

the equipment is capable of reaching curing temperatures.33 For this reason, the drying and

curing stages are sometimes referred to synonymously because wet fabric will enter the dryer

and a cured fabric will exit. Drying and curing may occur on the same machine, but they are

two different processes. The drying process removes all the water from the textile and it is at

29

this point that curing begins.21, 33 For this reason it is important to know where and when all

of the moisture is evaporated from the textile and curing begins because it is possible to over-

or under-cure.37 For this reason, a pyrometer can be used to measure the temperature of the

fabric to determine the needed dwell time in the dryer for curing to be optimized.21 Chemical

manufactures will typically provide the temperature and dwell time that is needed for their

chemicals to cure in order to produce the desired effect.

2.5.2 Plasma Processes

In an effort to modify textile properties without a wet chemical process,

physicochemical techniques have become commercially available that involve alteration of

the textile surface by high energy.37 There are multiple high-energy treatments available, but

many of them are not suitable for textiles. Brief descriptions of some high-energy treatments

along with reasons they are not commonly used in the textile industry are given in Table 2.4

on the following page.

30

Table 2.4. Physicochemical Techniques

Method Description Disadvantage

Corona

Discharge Generates electrons and ions to bombard

textile38

Non-uniformity, creation of “pinholes”,

hard to control38

Flame

Treatment Oxidizes polymer/fiber surface39 Difficult to control38

UV Irradiation UV exposure promotes cross linking and

fragmentation39 Deterioration of physical properties40

Electron Beam

Bombardment High energy electrons initiate

polymerization and cross-linking39

Degradation of polymer surface, change

in bulk property41

Gamma Ray

Treatment Induces cross-linking and grafting39 Degradation of polymer surface, change

in bulk property42

Ion-Beam

Bombardment Ions with high momentum and low mean

path result in extensive modification39

Unfeasible for on-line use, safety

requirements for accelerator42

Another method to incorporate compounds to the surface of a textile is through a

plasma process. Plasmas are generated by applying large amounts of energy to a gaseous

state where neutral atoms or molecules of the gas are broken up by energetic collisions to

produce electrons, positively or negatively charged ions and other species.43 This mixture of

charged particles is called a plasma and because all of these partials are charged, they can be

31

controlled by external magnetic fields. Unlike traditional processes, plasma processing will

not change the bulk properties of the textile.44

The activation methods and operating energy used to generate the plasma can result

in very high or low plasma temperatures and thus these are referred to correspondingly as

hot, sometimes called thermal, or cold plasmas. Hot plasmas are usually at a Local

Thermodynamic Equilibrium and therefore they are referred to as LTE plasmas; conversely,

cold plasmas are referred to as non-LTE because they are not at equilibrium.45 If a plasma is

at LTE, then each kind of collision in the plasma is balanced by its inverse. In other words, if

there is an ionization, there is instantly a recombination and the plasma is in a kinetic

balance.45 Because hot plasmas have a very high operating temperature, it has no

applicability to textiles, thus only cold, non-LTE, plasmas are used in textile treatment.

It is important to distinguish between plasma treatment and the plasma

polymerization that is found extensively in literature. As explained by Iriyama46, plasma

polymerization results from a compound that polymerizes when in a plasma state and thus a

thin film is formed on the surface of the textile. Plasma treatment occurs when compounds

do not form polymers in a plasma state, but react with and are incorporated into substrate

polymers. During plasma treatment, the textile surface itself is modified, not covered by a

thin film. Plasma treatment is distinguished from plasma polymerization by the nature of

gases used. Most organic compounds polymerize under plasma resulting in plasma

polymerization, while inert gases result in plasma treatment.46 Iriyama was successful in

using both plasma treatment and polymerization to impart a hydrophobic finish on nylon

32

fabrics although he found that fabrics were more durable by plasma treatment then by plasma

polymerization.

Typical process parameters of plasmas include input power, feed gas ratio, gas flow,

and operating pressure.47, 48 The input power required to generate an electric field required

for plasma generation can come from either a direct current (DC) or alternating current (AC)

power source.49 To date, the most limiting factor that has prevented plasma processing from

being successful on the industrial scale is the operating pressure.47, 50-52 There are two

accepted plasma types: low pressure (vacuum) and atmospheric pressure plasmas.

2.5.2.1 Vacuum Plasmas

Vacuum plasmas are well documented and are proven methods for surface

modification.42, 53 Typical vacuum operating pressures are in the range between 10 mTorr

and 10 Torr.1 Both DC and AC power supplies produce what is called glow discharge

plasmas; under vacuum conditions this is referred to as a low pressure glow discharge

(LPGD). Direct current glow discharges have little applicability to textile processing

because they are a rather inefficient plasma generator and they are difficult to control.49

When using an AC power supply, an additional variable of frequency is introduced.

Many commercial processes are designed to work at the Federal Communication

Commission’s (FCC) assigned frequencies of 13.56 MHz and 2.45 GHz.49 Plasmas are

generally classified by the frequency they operate at as well. Because 13.56 MHz is in the

radio frequency spectrum, plasmas generated at this frequency are commonly called radio

frequency (RF) plasmas while plasmas operating at 2.45 GHz are called microwave (MW)

33

plasmas. At 13.56 MHz, large ions with a high inertia will not be able to respond to the

changing electric field between electrodes, but the lighter electrons will.49 When operating

an AC power source at 2.45 GHz, the need for electrodes is eliminated. Radio frequency

plasmas can be generated both inductively and capacitively.

An inductively coupled plasma (ICP) source is maintained by a magnetic field created

by a primary inductor coil. An electric field is induced and coupled to the magnetic field

resulting in a discharge voltage equal to the rate of change in the magnetic flux inside the

current loop.54 The discharge power output is typically from a few watts to a few kilowatts.

Additionally, the frequency is typically operated within tens of kilohertz or tens of

megahertz.54 Because of the nature of electromagnetic induction, impedances between the

power supply and the plasma load must be matched in order to maximize forward power

transfer and minimize reflected power. Under low pressure, ICPs are in non-equilibrium, but

have a very high density and have been used for ion particle accelerators and ion thrusters for

space propulsion.42, 54 Inductively coupled plasma discharges have been known for over a

century, but there has been little specific research involving textile modification. One recent

study on hydrophobicity improvements of silk found that ICP sources become unstable at a

RF power above 50 watts and a pressure above 5 mTorr.55

The most widely used plasma sources are generated from capacitively coupled

devices.42 Capacitively coupled devices consist of an RF voltage applied across two

electrodes. The randomization of kinetic energy from the RF electric fields results in power

transfer to the plasma.56 The electrodes can be symmetric or asymmetric and can also be

34

insulated creating what is called an electrodeless discharge.57 Unlike ICPs, capacitive plasma

sources have a limited density of 1016 m-3 and this density is not easily controllable.42, 58

Despite this drawback, capacitively coupled plasma devices work well for many applications,

specifically in textiles, and their use commercially continues to increase.58

Even with the success of surface modification to achieve water repellency, the textile

industry has been reluctant to adopt this technology because a vacuum process requires batch

processing and expenses involved with vacuum equipment.46, 59, 60 In order for industry to be

able to use plasma processing commercially, it has to be conducted at atmospheric pressure

in order for it to be a continuous process.

2.5.2.2 Atmospheric

The use of atmospheric plasmas has the potential to offer the textile industry a full

width, continuous, and cost effective solution to vacuum plasma systems and possibly even

conventional wet processing techniques. It is accepted that atmospheric plasma sources are

classified according to their excitation mode, similar to vacuum plasmas. There are three

methods of excitation: low frequency, radio frequency, and microwave discharges.45 All of

these forms have been industrialized in some form, mostly in the microelectronics industry.

For specific information on industrialized atmospheric plasma sources, the reader is referred

to a review recently published by Tendero.45

Dielectric Barrier Discharge (DBD) and Corona Discharges generate atmospheric

plasmas and were discovered in 19th century.61 As mentioned in Table 2.4, the main

disadvantage of these processes are a non uniform treatment due to the nature of the plasma

35

generation.61 In 1988, Kanazawa published a paper reporting a uniform, homogeneous, and

stable glow discharge plasma at atmospheric pressure: atmospheric pressure glow discharge

(APGD).62 Kanazawa discovered that a stable glow discharge is possible when using helium

to dilute the process gasses while using a high frequency source.62, 63 In addition, the APGD

has been found to deposit coatings of the same quality of the extensively researched LPGD.61

These results suggest that the extensive literature on low pressure plasma treatments are

pertinent to atmospheric pressure treatment.

This APGD technology gave rise to plasma processing at atmospheric pressure

allowing for the development of continuous and reliable full width plasma machinery.

Plasma Ireland Ltd. developed a series of wide area APGD systems that further advanced the

original APGD concept to become a leading plasma machinery manufacturer.64

Recently, scientists at North Carolina State University treated a nonwoven fabric by a

conventional pad-dry-cure and APGD plasma treatment as part of a study for antimicrobial

treatments for surgical gowns.44 The study showed that the conventional wet treatment

method resulted in a 27% loss of strength in the machine direction and a 21% loss of strength

in the cross direction while there was no significant decrease in strength for the plasma

treated sample. Additionally, comparing the conventional to plasma processes by the

hydrostatic pressure test, AATCC TM 127, showed that the plasma treated samples resulted

in the same water barrier characteristics. Modifications have also been made with APGD

plasmas to modify nylon and polypropylene fabrics.51

36

Another atmospheric glow discharge plasma was developed by EA Technology Ltd.

known as an atmospheric pressure nonequilibrium plasma (APNEP).65 This plasma system

is based on a commercial multimode microwave technology which is desirable because these

are readily available apparatuses.66 A comparison of APNEPs to vacuum plasma showed

that both processes result in near identical modifications in spite of the differences in

pressure, particle density, gas throughput, and thermal properties.66

All of the atmospheric plasmas mentioned above have overcome the poor

manufacturability hurdle of low pressure plasmas by offering a continuous process. In order

to use atmospheric plasma for complex surface finishes, complex chemicals must survive

transport through the plasma. Because of the highly aggressive nature of plasma, it is

difficult to introduce long chain molecule precursors ideal for repellency into a plasma

because they will likely be destroyed in the highly energized ionized gas. For this reason,

conventional plasma deposited coatings are comprised of low molecular weight species.

This places a limit on the functionality of surface coatings using the plasma process. There

are currently two companies with technology that they believe has overcome this secondary

hurdle in plasma processing, APJeT and Dow Corning.

Research from the Los Alamos National Laboratory in collaboration with the

University of California, Los Angeles has developed what is called an atmospheric pressure

plasma jet (APPJ).45 The device operates at 13.56 MHz and consists of two concentric

electrodes through which gases flow. When a voltage is applied across the electrodes, a gas

discharge is ignited and ionized gas exits through a nozzle at a velocity of about 12 m/s

37

where it is directed toward a substrate.67 The APPJ patent was awarded to Dr. Gary Selwyn,

a scientist at the Los Alamos National Laboratory who started APJeT Inc.68 In 2005,

Avondale Mills Inc. and APJeT Inc. signed a joint development agreement to commercialize

this plasma process for the treatment of cotton and cotton/polyester apparel fabrics for water

repellency along with other treatments.69

According to an APJeT patent70, the company uses what they call a downstream

operation to prevent their precursor gas from being fragmented by the plasma region. This is

accomplished by adding the precursors not into the plasma, but into what is called the

afterglow. Since no electrons are present in the afterglow, the precursor is not dissociated or

fragmented. Instead of the precursor reacting inside of the plasma, the reaction takes place

between the atomic and metastable species generated by the plasma and the undissociated

chemical precursor gas in the afterglow.

In 2001, with a proprietary coating technology developed with the University of

Durham in England and the acquisition of Plasma Ireland Ltd., Dow Corning is now

marketing Atmospheric Pressure Plasma Liquid Deposition (APPLD) technology to the

textile industry.52 According to scientists at Dow Corning Plasma Solutions, complex, long-

chain, and even fragile precursor molecules can be injected into a plasma without being

damaged or destroyed using their APPLD technology. Ultrasonic nozzles are used to inject

atomized liquid droplets that protect the precursor from the plasma and transport it intact to

the substrate resulting in plasma polymerization. The liquid precursors can be freely mixed

and matched with gas, solid, or liquid additives resulting in a large range of functional

38

coating potentials.71 With the use of APPLD treatment, water contact angles of 140˚ have

been recorded on cotton fabrics.52

2.6 Conclusion

In order to repel a liquid, a textile surface must have a lower surface energy than the

surface tension of the liquid that comes in contact with it. Fluorocarbons are the most widely

used chemicals today in the textile industry to drastically lower a textile’s surface energy

allowing it to repel both water and oil. Conventional methods to place the fluoropolymer

onto the textile surface require the use of water and therefore are known as wet processes.

Large amounts of energy must be placed into the textile to evaporate the water and cure the

chemical finish resulting in excessive energy costs. Also, intermediate fluorochemicals that

are used to produce the fluoropolymers have recently been shown to be persistently present

in the environment. Concerns of danger to public health from these intermediates have

prompted extensive review of existing commercial repellent finishes and renewed interest in

the search for new chemicals and application methods for producing repellent textiles.

Plasma processing has been proven in the laboratory to treat textiles with a repellent

finish comparable to conventional processing. This dry plasma method is now available

commercially in a reliable, full width, and continuous process that promises to alleviate

excessive energy costs associated with wet processing. In addition, atmospheric plasma

applied repellent finishes can involve different hydrophobic reactants that have not been

shown to be environmentally hazardous.

39

3. Procedures & Methodology

3.1 Introduction

Textile compaines were contacted and asked to participate in this research by

donating well prepared fabric from one of their commercial water and/or oil repellent

products. The companies were also asked to provide a head end of their commercial product

along with the tests and specifications used to verify their product’s functionality. The well

prepared samples were sent off for atmospheric plasma treatment by Dow Corning Plasma

Solutions (DCPS). DCPS has a patented Atmospheric Pressure Plasma Liquid Deposition

(APPLD) technology that has shown promising results and is currently available in a

commercial full width continuous process as discussed in Section 2.5.2.2 and also in

Appendix A.

For each fabric type that DCPS treated with their APPLD technology, they received a

sample of the well prepared control fabric with no finish, along with a sample of the

conventionally treated fluorochemical finish. DCPS was asked to do whatever was necessary

to match their APPLD finish to the conventional wet finish that was provided to them.

DCPS conducted a Design of Experiment (DOE) for each sample submitted in order to

determine the optimal settings for their APPLD machine. Because of cost restrictions, the

fabrics were not treated at full width, but on a reel to reel lab machine that is used to simulate

the results of a full width continuous process on a 12 inch wide roll. More details of the

APPLD machinery and process are given in Appendix A.

40

In order to determine the viability of using atmospheric plasma processing for water

and/or oil repellents in the commercial textile industry, conventional pad-dry-cure finishing

was compared to atmospheric plasma finishing, specifically the DCPS APPLD technology,

on the basis of repellency, durability, and cost.

3.2 Fabrics Tested

Textile companies responded to this research by providing well prepared fabrics of

nylon, polyester, a 65/35 polyester/cotton blend, and also a polypropylene and polyester

nonwoven to be treated with Dow’s APPLD technology. Cotton fabric was acquired from

Cotton Incorporated. Each fabric’s information is given below in the following sections.

3.2.1 Cotton

A one hundred percent cotton fabric was requested and received from Cotton

Incorporated in Cary, NC. Cotton Incorporated works to strengthen the US cotton industry

through research and promotion.72 A close up photograph of the fabric’s construction can be

found on page 115 and the physical properties are given below in Table 3.1.

Table 3.1. Cotton Fabric Construction

Weave Fiber Picks/inch Ends/inch Weight (oz/yd2) Twill Ring Spun 85 52 6.7

The well prepared cotton was split into three segments: control, conventional, and

atmospheric plasma. The control segment was a well prepared cotton with no finish, and the

atmospheric plasma segment was a prepared cotton with no finish that was sent to DCPS for

APPLD treatment. Because treated cotton could not be acquired commercially from a textile

41

company, the conventional segment was treated with a conventional fluorochemical finish

via the pad-dry-cure method. This process was completed at Cotton Incorporated in

Research Triangle Park, NC on their tenter range. The chemical bath given in Table 3.2 was

padded on with a wet-pick-up (wpu) of 75%, dried at 250 °F, and cured for 60 seconds at 350

°F. The material safety data sheets for each of the chemicals given below in Table 3.2 are

given in Appendix I.

Table 3.2. Cotton Fluorochemical Bath

g/L Company Chemical Name Description 70 Clarient Nuva HPU water and oil repellent fluorochemical 50 Huntsman Phobotex JVA stearated melamine wax extender 15 Huntsman Ultratex REP epoxy silicone polymer emulsion 20 Apollo Fluftone NPE polyethylene emulsion

The atmospheric plasma segment of the cotton was sent to DCPS for APPLD

treatment. After the return of the APPLD treated fabric, it was tested for repellency and

durability as discussed in Sections 3.3 and 3.4 and compared to the conventional method.

3.2.2 65/35 Polyester/Cotton

A commercial polyester/cotton blend was requested and received from a textile

company. The fabric received was a 65/35 blend of polyester to cotton. A close up

photograph of the fabric’s construction can be found on page 120 in Appendix D and the

physical properties are given below in Table 3.3.

Table 3.3. Polyester/Cotton Fabric Construction

Weave Fiber Picks/inch Ends/inch Weight (oz/yd2) Poplin Open-End 92 50 4.5

42

This is a new product that is being developed that has a water repellent finish on one

side and a soil release finish on the other. Because using APPLD to impart a separate finish

on each side of the fabric is beyond the scope of this research, the soil release side was

ignored. The polyester/cotton was broken into four different segments: control,

conventional, member conventional, and atmospheric plasma.

The control segment was a well prepared 65/35 polyester/cotton blend with no finish

and the atmospheric plasma segment was the same as the control except it was sent off to

DCPS for APPLD treatment. Because the company was not able to provide what was

considered to be an adequate amount of fabric for testing, some of the well prepared control

polyester/cotton segment with no finish was treated with a conventional fluorochemical

finish via the pad-dry-cure method. This segment is referred to as conventional and was

finished at Cotton Incorporated in Cary, NC on their tenter range. The same chemical bath

that was used to finish the cotton was also used to finish the polyester/cotton. The bath in

Table 3.2 was padded on with a wet-pick-up (wpu) of 75%, dried at 250 °F, and cured for 60

seconds at 350 °F.

The limited amount of fabric that was supplied by the company was referred to as

member conventional. After the return of the APPLD treated fabric, it was tested for

repellency and durability as discussed in Sections 3.3 and 3.4 and compared to the

conventional method. The repellency test requirements provided by the company for this

fabric are given below in Table 3.4.

43

Table 3.4. Polyester/Cotton Repellency Requirements

Washes Test 0 5 10 25

Spray - AATCC TM 22 90 70 70 70 Water/Alcohol - AATCC TM 193 5 5 5 5

Oil - AATCC TM 118 4 4 4 4

3.2.3 Polyester

A commercially available one hundred percent polyester fabric was requested and

received by a textile company. The polyester fabric is a calendered durable water repellent

(DWR) barrier fabric used in the medical profession. A close up photograph of the

calendered and non-calendered fabric’s construction can be found on page 131 and 132

respectively in Appendix E and the physical properties are given below in Table 3.5.

Table 3.5. Polyester Fabric Construction

Weave Fiber Picks/inch Ends/inch Weight (oz/yd2) Plain Multi-Filament 155 94 2.7

Because calendering is an additional finishing step, both calendered and non-

calendered well prepared polyester fabrics were requested from the company. When

received, the polyester was broken into five different segments: control calendered, control

non-calendered, conventional calendered, atmospheric plasma calendered, and atmospheric

plasma non-calendered. The control segments were both well prepared fabrics containing no

finish. Both atmospheric plasma sections were well prepared fabrics that were sent to DCPS

for APPLD treatment. After the return of the APPLD treated fabric, they were tested for

repellency and durability as discussed in Sections 3.3 and 3.4 and compared to the

conventional method.

44

The only repellency test required by the company for this fabric is that it scores a 90

in the spray test before washing. Because this is a barrier fabric, additional physical tests

were performed as requested by the company. Table 3.6 below gives the performance

specification requirements of the calendered polyester.

Table 3.6. Polyester Additional Requirements

Test Measurement Hydrostatic Pressure – AATCC TM 127 55 cm minimum 5 Wash Shrinkage 3% length & width maximumAir Permeability – ASTM D737 2.5 cfm maximumTensile – ASTM D5034 120 lbs Warp & 70 lbs Fill minimum

The calendered sections were compared in order to determine the feasibility of the

company replacing their conventional finishing with the APPLD technology. The non-

calendered sections were analyzed, but were not compared to the calendered sections.

3.2.4 Nylon

A commercially available one hundred percent nylon fabric was requested and

received from a textile company. The fabric supplied was an apparel outerwear jacket

material that has a durable water repellent (DWR) finish. A close up photograph of the

fabric’s construction can be found on page 173 in Appendix F and the physical properties are

given below in Table 3.7.

Table 3.7. Nylon Fabric Construction

Weave Fiber Picks/in Ends/in Weight (oz/yd2) 3-Ply Multi-Filament 160 66 3.8

45

The company submitted a head end of their conventionally treated nylon fabric along

with prepared only fabric. The prepared only fabric received for treatment was well prepared

but not dyed. These fabrics received from the company were split into three segments:

control, conventional, and atmospheric plasma. The atmospheric plasma segment was a

section of the well prepared fabric that was sent to DCPS for APPLD treatment. After the

return of the APPLD treated fabric, it was tested for repellency and durability as discussed in

Sections 3.3 and 3.4 and compared to the conventional method. The repellency test

requirements provided by the company for this fabric is given below in Table 3.8.

Table 3.8. Nylon Repellency Requirements

Washes Test 0 5 10 25

Spray - AATCC TM 22 90 90 90 90

3.2.5 Nonwovens

Commercially available one hundred percent polyester and a one hundred percent

polypropylene nonwoven fabrics were submitted and received from a textile company. Both

nonwovens were being used in the automotive industry as water repellent products. They

were submitted for this research in an effort to try to find an alternative to the current

fluorocarbon aerosol application method. Both nonwovens were submitted to DCPS for

APPLD treatment but both were returned because they would not fit between the electrodes

for processing. Both nonwoven samples had a thickness of 4 mm. After DCPS returned the

samples, APJeT was contacted to treat the samples but our request was turned down because

46

we could not be scheduled within the next six months. For this reason, neither of the

nonwoven samples will be discussed for the remainder of this document.

3.3 Repellency Tests

A variety of tests were chosen in order to evaluate the repellency of each treated

fabric. The spray, impact, oil, and water/alcohol resistance tests are mostly subjective and

used most often in the textile industry to test how repellent a surface is to a liquid, while the

contact angle test is more objective and used in research. All of these tests were conducted in

accordance with the American Association of Textile Chemist and Colorists (AATCC)

standard test methods. For all tests performed, the fabrics were conditioned at 65 ± 2%

relative humidity and 70 ± 2 °F for a minimum of four hours before testing. Because the

polyester fabric received was a barrier fabric, additional tests were performed as discussed in

Section 3.3.6. All fabrics were conditioned in a temperature and humidity controlled room at

NCSU except for the impact and hydrostatic pressure test fabrics that were conditioned in the

AATCC’s Parameter Generation and Control conditioning chamber, model number 9134-

3119 in Research Triangle Park, NC.

3.3.1 Spray

The spray test is standardized as AATCC Test Method 22.32 This test was used to

measure the resistance of fabrics to wetting by water. The fabric samples were laid 150 mm

under a spray nozzle at a 45˚ angle and 250 mL of water was poured onto the fabric through

the spray nozzle. After the fabric was “smartly” tapped, and the wetting pattern was

compared with a standard rating chart given in Figure 3.1 on the following page. Complete

47

wetting resulted in a score of 0 while no wetting pattern received a score of 100. All spray

tests were conducted on spray test equipment as specified by the AATCC and were

performed at NCSU.

Figure 3.1. Spray Test Ratings

48

3.3.2 Impact

The impact penetration test, standardized as AATCC TM 4232, was used to simulate a

fabric’s exposure to rain. Unlike the spray test, this test method measures the resistance of

fabrics to the penetration of water by impact, thus it can be used to predict the resistance of

fabrics to rain penetration. For each sample, a weighed paper blotter was placed under the

fabric that was clamped on the top end at an angle of 45˚ and 500 mL of water was sprayed

onto the fabric 0.6 m below the nozzle. Immediately after spraying, the blotter paper was

reweighed and the difference in weight indicated penetration of water. All impact

penetration tests were conducted on a Type I tester as specified in the test method and were

performed at the AATCC lab in Research Triangle Park, NC.

3.3.3 Water/Alcohol

The water/alcohol test is known as the “Aqueous Liquid Repellency: Water/Alcohol

Solution Resistance Test” and is standardized as AATCC TM 193.32 This test was

performed to measure the repellency of each sample’s surface to wetting. This was

accomplished by placing aqueous solutions with decreasing surface tensions on each of the

fabric samples. There are eight different aqueous solutions in this test as seen in Table 3.9 on

the following page.

49

Table 3.9. AATCC TM 193 Standard Test Liquids

AATCC Aqueous Solution Repellency

Grade Number Composition (vol:vol) Surface

Tension *N

0 None (fails Grade 1) 1 98:2 / Water : isopropyl alcohol 59.0 2 95:5 / Water : isopropyl alcohol 50.0 3 90:10 / Water : isopropyl alcohol 42.0 4 80:20 / Water : isopropyl alcohol 33.0 5 70:30 / Water : isopropyl alcohol 27.5 6 60:40 / Water : isopropyl alcohol 25.4 7 50:50 / Water : isopropyl alcohol 24.5 8 40:60 / Water : isopropyl alcohol 24.0

*N = dynes/cm at 25°C

Five drops of the first solution, grade number 1, were placed on the fabric in different

locations along the filling direction approximately 4 cm apart. The drops were observed for

approximately 10 seconds from a 45° angle. After each aqueous solution was observed, it

was given a grade as shown in Figure 3.2.

Figure 3.2. AATCC TM 193 Solution Grades

50

If no penetration, wetting, or wicking occurred, the process was repeated for the next

solution’s aqueous grade number up to grade 8. If the three out of five solution drops of

grade 8 showed no sign of wetting or wicking and had a well-rounded drop, the fabric

received a grade of 8. If the grade was a borderline pass (a rating of B in Figure 3.2), the

grade was expressed to the nearest 0.5 value by subtracting one-half from the number of the

borderline test liquid. The best grade and therefore the highest repellency that can be

received by the water/alcohol test is an 8. All water/alcohol tests were performed at NCSU

using a ratio of 99.9% isopropyl alcohol to deionized water.

3.3.4 Oil

The oil test is also known as the “Oil Repellency Hydrocarbon Resistance Test” and

is standardized as AATCC TM 118.32 This test is the same as the water/alcohol test in every

way except for the test solutions used. The lowest liquid surface tension used in the

water/alcohol test is 24.0 dynes/cm but for the oil test it is 19.8 dynes/cm as shown in Table

3.10 on the following page.

51

Table 3.10. AATCC TM 118 Standard Test Liquids

AATCC Aqueous Solution Repellency

Grade Number Composition Surface

Tension *N

0 None (fails Grade 1) 1 Kaydol 31.5 2 65:35 Kaydol : n-hexadecane (vol:vol) 28.9 3 n-hexadecane 27.3 4 n-tetradecane 26.4 5 n-dodecane 24.7 6 n-decane 23.5 7 n-octane 21.4 8 n-heptane 19.8

*N = dynes/cm at 25°C

All oil tests were performed at NCSU using the chemicals listed above in Table 3.10.

All chemicals were at least 99.5% pure.

3.3.5 Contact Angle

Contact angle measurements were measured with a NCSU built microscopic

apparatus to view a water droplet on a surface. The microscope was positioned so that when

looking through it, the water droplet will appear similar to Figure 2.1.

The eyepiece contained a straight horizontal reference line that was placed between

the water droplet and the surface of the fabric and a second vertical line was adjusted to

represent the contact angle. When the reference and measurement lines were positioned as

shown in Figure 2.1 by the bold arrows, the contact angle θ was measured by the eyepiece’s

internal protractor. Each fabric finish was measured five times at different locations

52

throughout the roll. The contact angle measurements give an objective comparison of the

conventional and atmospheric plasma treatments.

3.3.6 Additional Tests

Because the polyester fabric received is a barrier fabric, the additional tests below

were performed.

3.3.6.1 Hydrostatic Pressure

The hydrostatic pressure test, standardized as AATCC TM 12732, was used to

measure the resistance of a fabric to the penetration of water under hydrostatic pressure. A

fabric sample was placed in a hydrostatic tester and the hydrostatic pressure was increased at

a constant rate. The pressure at which water penetrated through the fabric in three locations

was the penetration pressure and was measured in centimeters of water. All hydrostatic

pressure tests were performed at the AATCC lab in Research Triangle Park, NC.

3.3.6.2 Wash Shrinkage

The wash shrinkage test was performed by measuring and marking a ten inch by ten

inch square on six fabric samples from each finish. After five washes, as described in

Section 3.4.2, the squares were measured again. From knowing the dimensions of the box

before and after five washes, the percentage that the sample shrank was calculated in both the

warp and filling directions.

53

3.3.6.3 Air Permeability

Because the current facilities at NCSU do not have an air permeability machine that

can accurately calculate very low air flow due to a calendered product, the finished samples

were sent back to the company after treatment for internal testing. The results were shared

for this research.

3.3.6.4 Tensile

The tensile test performed on the polyester was the grab test standardized as ASTM D

503473. This test is also known as the “Standard Test Method for Breaking Strength and

Elongation of Textile Fabrics.” For this test, four inch wide by eight inch long fabric

specimens were mounted centrally in the clamps of a Sintech 1/S tensile testing machine at

NCSU. The clamps slowly separated until the fabric failed. Three samples were tested for

each finish in both the warp and filling directions. The Sintech testing machine is computer

controlled assuring that all settings adhere to the ASTM D 5034 procedure. The computer

calculated the breaking force in pounds and provided a printout for each finish tested.

3.4 Durability Tests

Durability testing was performed in order to determine if the atmospheric plasma

treatment can perform as well as conventional wet finishing after multiple launderings. The

repellency tests in Section 3.3 were performed at 0, 5, 10, and 25 washes. Each wash cycle

of 0, 5, 10 and 25 washes were mutually exclusive relative to repellency testing. For

example, a spray test was not performed at five washes and then again on the same sample at

10 washes; each test had a specific fabric sample for that test at a specific wash cycle only.

54

3.4.1 X-ray Photoelectron Spectroscopy

X-ray Photoelectron Spectroscopy (XPS) was used on all of the as received fabric

samples before any testing. XPS is a surface analysis technique used to determine the

concentration of different elements at the fabric surface. A more detailed explanation of XPS

can be found in Appendix B. The machine used in this research was a Riber LAS-3000 using

MgKα x-ray excitation. Energy calibration was established by referencing to the

adventitious carbon (C1s at 284.5 eV).

Using XPS analysis, an approximate amount of fluorine on the surface was

determined. This was necessary because it was possible that the atmospheric plasma

treatment could have placed a significantly higher or lower amount of fluorine on the surface

than the conventional treatment resulting in a bias. In order to determine if the durability

testing was biased, each finished fabric sample that was compared was tested by XPS in

order to determine if they had approximately the same percentage of fluorine on the surface.

Because each finish was applied to the same base fabric, the percentage of other elements

besides fluorine remained constant. Therefore, the percent of fluorine on the surface gave a

good indication of the actual amount of fluorine across each finish.

3.4.2 Wash

The washing procedure used adhered to AATCC TM 130 Section 8 and the

AATCC’s “Standardization of Home Laundry Test Conditions”. AATCC TM 130 Section 8

pertains to how the wash load is prepared and the latter for the settings used on the washer

and dryer. There were two small deviations away from AATCC 130 Section 8. The first

55

deviation was the sample size. The procedure calls for each sample to be washed to be 15

inches square. Because the fabric returned from DCPS was on a 12 inch reel, the sample size

was changed to be 12 by 15. Secondly, the procedure calls for no more than 30 specimens to

be placed in a washer although each fabric to be washed contained more than 30 specimens.

Table 3.11 below shows how many samples were needed for each fabric in order to complete

the tests in Section 3.3 for each wash cycle. Because of the large number of fabric samples,

the 30 specimen limit per wash was ignored. For each wash, more than 30 specimens were

loaded into the washer.

Table 3.11. Number of Samples Required for Each Fabric

Fabric SamplesPolyester 120 Nylon 48 Cotton 32 Polyester/Cotton 64

Because of the amount of samples that were to be washed, they were split up between

two washers and dryers. All samples washed in washer A were dried in dryer A and samples

washed in washer B were dried in dryer B. The equipment used is given in Table 3.12

below.

Table 3.12. Wash Equipment

Make Model Washer A Kenmore 110.26712693 Washer B Kenmore 92596100 Dryer A Kenmore 110.6493220 Dryer B Kenmore 110.60932990

56

The nylon and polyester samples were washed in washer A while the cotton and

polyester/cotton samples were washed in washer B. Thirty six inch square 100 percent

polyester ballasts were added to the nylon and polyester set while 36 inch square 100 percent

cotton ballasts were added to the cotton and polyester/cotton set to reach 4.0 lbs of fabric to

be washed in each machine. One hundred grams of AATCC 1993 Standard Reference

Detergent was added to each wash load. The detergent was measured on a scale to within

one tenth of a gram. The washing machine settings for both the nylon-polyester and the

cotton-polyester/cotton sets are given in Table 3.13 below.

Table 3.13. Washing Machine Settings

Wash Temp Rinse Temp Cycle Wash Time Warm: 105 ± 5°F < 85 °F Normal 10 min

After a load of fabric samples were washed, they were immediately placed in the

dryer. The machine settings for the dryer are given in Table 3.14 below.

Table 3.14. Dryer Machine Settings

Technique Cycle Dry Time Tumble Normal 45 min

After five washes, the samples labeled for testing at five washes as described in

Section 3.4 were removed. More ballast was added to get the next wash load up to 4.0

pounds and the process was repeated. After ten washes the samples marked for testing at ten

washes were removed leaving only the samples for testing at twenty five washes.

57

By comparing the results of the repellency tests discussed in Section 3.3 for 0, 5, 10,

and 25 washes, a comparison of durability to washing between a conventional and

atmospheric plasma treatment was made.

58

4. Results and Discussions

4.1 Atmospheric Plasma Treatment

Dow Corning Plasma Solutions (DCPS) conducted a Design of Experiment (DOE) in

order to determine the optimum settings for their LabLine Atmospheric Pressure Plasma

Liquid Deposition (APPLD) machine. The chemical precursor chosen by DCPS for the

fabric treatment was a 50:50 volume to volume mix of heptadecafluorodecyl acrylate

(HDFDA) CAS number 27905-45-9 and heptadecafluoro-1-decene (HDFD) CAS number

21652-58-4. The material safety data sheets (MSDS) for these chemicals are available in

Appendix I. It should be noted that the chemical vendor that DCPS used is unknown and the

MSDS listed for each chemical in Appendix I is not necessarily from the DCPS chemical

vendor used in this research. The chemical structures of these chemical precursors and the

final copolymer formed are given in Figure 4.1 below.

C F 3 ( CF2)7CH CH2HDFD :

C F 3(CF2)7CH2CH2OCCHO

CH2HDFDA :

(CHCH2)n (CHCH 2 ) m (CF2)7CF3

C O

OCH2

CH2(CF2)7 CF3

HDFD/HDFDA Copolymer:

Figure 4.1. Chemical Precursors Used for APPLD Treatment

59

The DOE performed by DCPS is given below in Table 4.1.

Table 4.1. DCPS APPLD DOE Operating Conditions

Run 1 2 3 4 5 6 7 8 Line Speed

(m/min) 5 10 5 10 5 10 10 5

Precursor Flow Rate (μl/min) 1000 1500 1500 1000 1000 1000 1500 1500

Power (W) 1800 1800 2000 1800 2000 2000 2000 1800

Number of Passes 1 1 1 3 3 1 3 3

The machine settings found by DCPS to be optimum for repellency were determined

to be the settings used at run number eight. These settings along with the constant settings

used for each run is given below in Table 4.2.

Table 4.2. DCPS LabLine Machine Settings

Optimal Parameters Constant Settings Precursor Flow Rate 1.5 mL/min Gas Helium Power 1.8 kW Gas pressure to nozzle 50 psi Line Speed 5 m/min Gas flow rate to top box 10 L/min Passes 3 Gas flow rate to shower seals 15 L/min

Twenty meters of APPLD treated fabric were returned for each fabric sent with the

exception of both nonwoven samples. They were not analyzed or treated because with a

thickness of 4mm, they were “too thick” to pass through the LabLine’s electrode gap.

Upon inspection of the returned fabrics, they all contained tiny holes on a significant

area of the twenty meters returned. When referring back to the accompanying report, DCPS

stated the following:

“All fabric substrates were seen to exhibit some micro-discharges during the plasma treatment, as a result, pinholes were observed in

60

the 20 m plasma treated fabrics. The reasons for this highly undesirable phenomenon are qualitatively understood and steps are underway to eliminate the cause.”

Because of the excessive pinholes, extreme care was taken preparing samples for

each test. All fabrics were placed on a light box and pinholes were marked clearly with a

black marker. Samples for testing were cut around the pinholes severely limiting the sample

size for each test. Although the sample size was limited, there were enough pinhole free

samples to successfully complete all testing.

DCPS offered to rerun the trial again at no cost and stated that the pinholes were due

to operator error. Because of this offer, more nylon was sent to DCPS except they were

asked to modify their DOE. This time they were asked not only to optimize repellency, but

to also optimize durability. The same chemical precursors were used although some

parameters for the LabLine machine changed. The optimal parameters found by DCPS are

given below in Table 4.3.

Table 4.3. Optimal Parameters for Additional Nylon Treatment

Optimal Parameters Gas He with 1.4% Ar Precursor Flow Rate 750 μL/min Power 1500 W Line Speed 5 m/min Passes 6

The nylon sample returned did not contain any pinholes. A more in-depth look at the

APPLD technology and machinery is given in Appendix A.

61

4.2 Repellency & Durability

Repellency tests discussed in Section 3.3 were performed at each wash cycle of 0, 5,

10, and 25 as discussed in Section 3.4. All graphs and statistical conclusions were produced

and calculated by JMP® 6 statistical software available by SAS© at www.jmp.com. Results

are considered to be statistically significant if p-values are less than 0.05. Data collected in

this research is assumed to be of the normal distribution.

4.2.1 Cotton

The cotton fabric contained three segments: control, conventional, and atmospheric

plasma as discussed in Section 3.2.1. The nomenclature used throughout the remainder of

the document is given in Table 4.4 on the following page. Tabular results of all cotton as

received repellency tests along with tests at 5 and 10 washes can be found on page 117 in

Appendix C.

Table 4.4. Cotton Fabric Nomenclature

Abbreviation Segment Description CTRL control cotton fabric with no finish (prepared only)

W conventional cotton fabric with conventional wet pad-dry-cure finish P atmospheric plasma cotton fabric treated with APPLD

4.2.1.1 XPS Analysis

An XPS analysis was performed as discussed in Section 3.4.1 on all three cotton

segments. Table 4.5 shows the percent fluorine composition of each segment. The complete

elemental composition can be found on page 117 in Appendix C.

62

Table 4.5. Fluorine Composition of Cotton Segments

Segment CompositionCTRL 0%

W 62% P 63%

As expected, the CTRL segment does not have a repellent finish, therefore no

fluorine was detected on the surface with only carbon and oxygen present from the cotton

molecules. For both the W and P finishes, fluorine was found to represent 62 and 63 percent

of the surface respectively. Also, the binding energies for both the W and P finish are

extremely similar, given on page 116, suggesting that both the W and P finishes have not

only the same amount of fluorine on the surface, but both surfaces have an analogous

chemical composition. Therefore, it can be expected that no initial bias in repellency or

durability exists between the W or P finishes.

4.2.1.2 Spray

Spray tests were preformed as discussed in Section 3.3.1 on all as received samples

along with samples washed 5 and 10 times. The results of the spray test shown in Table 4.6

are the score as given by Figure 3.1 on page 47. The average of two tests was used to

determine the results. The results for each individual test can be found on page 117 in

Appendix C.

Table 4.6. Cotton Spray Results

Washes Finish 0 5 10

W 100 95 88 P 100 55 0

63

The CTRL segment is not included in the results of Table 4.6 because it scored a 0.

For this reason, the CTRL segment will not be included in any of the proceeding tests

discussed in this section. In addition, at 10 washes, the P finish sample was completely

saturated by the water from the spray test also resulting in a score of 0. Therefore, the cotton

was not tested at 25 washes for this or any other proceeding test. After 5 washes, as shown

in Table 4.6, the P finish showed a dramatic drop in repellency relative to the W finish.

4.2.1.3 Impact

Impact tests were performed as discussed in Section 3.3.2 on all as received samples

along with samples washed 5 and 10 times. The results of the test shown below in Table 4.7

are in grams (g) of water penetrated through the fabric. The average of three tests was used

to calculate the results. In accordance with AATCC TM 42, if more than five grams of water

penetrates through the fabric, it is recorded as “>5 g”. Results for each individual test can be

found on page 117 in Appendix C.

Table 4.7. Cotton Impact Penetration Results

Washes Finish 0 5 10

W 1.2 g 0.1 g 0.0 g P 0.4 g > 5 g > 5 g

Table 4.7 shows that the P finish initially outperformed the W finish. Although this is

true for the samples before washing, the W finish improved slightly through ten washes

while the P finish failed after just five. The W finish performance is most likely due to the

fabric shrinking and therefore decreasing the capillary pores of the fabric surface. With a

64

tighter construction of the fabric in addition to the repellent finish still left on the surface, the

amount of water that penetrated through the W finish decreased after 5 and 10 washes. The P

finish also had some shrinkage observed after 5 and 10 washes, but by the results of the spray

test, most of the repellent finish was removed after 5 washes.

4.2.1.4 Water/Alcohol

Water/alcohol tests were performed as discussed in Section 3.3.3 before washing

along with samples washed 5 and 10 times. The results of the water/alcohol test shown in

Table 4.8 on the following page were determined by Table 3.9 and Figure 3.2 as described in

Section 3.3.3.

Table 4.8. Cotton Water/Alcohol Results

Washes Finish 0 5 10

W 7.5 8 8 P 7.5 0.5 0

Table 4.8 shows that both the W and P finishes are comparable before washing.

Although the W finish slightly improved through 5 and 10 washes, the P finish showed a

dramatic decrease in repellency after just 5 and 10 washes.

4.2.1.5 Oil

Oil tests were performed as discussed in Section 3.3.4 on all as received samples

along with samples washed 5 and 10 times. The results of the oil test shown in Table 4.9

were determined by Table 3.10 and Figure 3.2 as described in Section 3.3.4.

65

Table 4.9. Cotton Oil Results

Washes Finish 0 5 10

W 6.5 6 6 P 6.5 5 2

Table 4.9 shows that both the W and P finishes are comparable before washing. The

W finish is consistent around a grade of 6 although the P finish shows a significant decrease

in repellency after 10 washes down to a grade of 2 from 6.5.

4.2.1.6 Water Contact Angle

Contact angle measurements were taken as discussed in Section 3.3.5 for all as

received samples along with samples washed 5 and 10 times. The results of the contact angle

tests shown in Table 4.10 are the average of five different measurements and are given in

degrees. The results for each individual test can be found on page 117 in Appendix C.

Table 4.10. Cotton Contact Angle Results

Washes Finish 0 5 10

W 157° 145° 143° P 152° 0° 0°

Analysis of Variance (ANOVA) tests in Appendix C were conducted on the data used

to generate Table 4.10 in order to compare the repellency and durability of the finishes. An

ANOVA was conducted between and within each finish. When testing the P finish samples

at 5 and 10 washes, no measurement could be taken because by the time the apparatus was

adjusted and ready for measurement, the water had absorbed into the fabric resulting in a

contact angle of 0°.

66

The ANOVA between finishes determines if there is a statistically significant

difference in the water contact angle between each finish at each wash cycle. In this case,

only the as received samples could be compared. The results of this ANOVA on page 118

in Appendix C shows that with the given data, there is no statistical difference in the water

contact angle between the W and P finishes before washing.

The ANOVA within each finish determines the statistical significance of how much,

or even if, each specific repellent finish deteriorates after each wash cycle. In this case, only

the W finish could be analyzed. The results of this ANOVA on page 119 in Appendix C

shows that the water contact angle drops by about 10° after 5 washes for the W finish. Also,

there is no statistical difference between 5 and 10 washes.

4.2.2 Polyester/Cotton

The polyester/cotton fabric contained four segments: control, conventional, member

conventional, and atmospheric plasma as discussed in Section 3.2.2. As discussed on page

42, the member conventional segment had a limited amount of fabric for testing. Because of

the pinholes as discussed on page 59, the amount of fabric for the atmospheric plasma

segment was also limited. Therefore, both the member conventional and conventional

segments could be compared to the atmospheric plasma segment. The nomenclature used

throughout the remainder of the document is given in Table 4.11 on the following page.

67

Table 4.11. Polyester/Cotton Fabric Nomenclature

Abbreviation Segment Description

CTRL control polyester/cotton fabric with no finish (prepared only)

W conventional polyester/cotton fabric with conventional wet pad-dry-cure finish

WM member conventional commercially available polyester/cotton fabric with conventional finish

P atmospheric plasma polyester/cotton fabric with APPLD

4.2.2.1 XPS Analysis

An XPS analysis was performed as discussed in 3.4.1 on all four polyester/cotton

segments. Table 4.12 shows the percent fluorine composition of each segment. The full

elemental compositions can be found on page 122 in Appendix D.

Table 4.12. Fluorine Composition of Polyester/Cotton Segments

Segment CompositionCTRL 0%

W 65% WM 60%

P 64%

As expected, the CTRL segment does not have a repellent finish therefore no fluorine

was detected on the surface. For both the W and P finishes, the fluorine was found to

represent 65 and 64 percent of the surface respectively. The WM finish contained slightly

less fluorine as a percentage on the surface because of a small presence of nitrogen. The

presence of nitrogen was most likely contamination due to the soil release finish on the

opposite side of the fabric. Also, the binding energies for the W, WM, and P finishes, shown

on page 121, are all extremely similar suggesting that all three finishes have the same amount

68

of fluorine on the surface and both surfaces have an analogous chemical composition.

Therefore, it can be expected that there is no initial bias in repellency or durability among the

W, WM, or P finishes.

4.2.2.2 Spray

Spray tests were performed as discussed in Section 3.3.1 on all as received samples

along with samples washed 5, 10, and 25 times. The results of the spray test shown in Table

4.13 are the scores as given by Figure 3.1 on page 47. The average of three tests was used to

determine the results. The results for each individual test can be found on page 122 in

Appendix D.

Table 4.13. Polyester/Cotton Spray Results

Washes Finish 0 5 10 25

W 100 100 100 98 WM 100 100 98 92

P 97 80 70 53

The CTRL segment is not included in the results of Table 4.13 because it scored a 0.

For this reason, the CTRL segment will not be included in any of the proceeding tests

discussed in this section. As shown in Table 4.13, the W and WM conventional finishes

score quite well at 5, 10, and even 25 washes while the P finish slowly decreased in

repellency at each wash cycle. Referring back to Table 3.4, the P-finish fails the company’s

requirement of a minimum spray score of 70 at 25 washes.

69

4.2.2.3 Impact

Impact tests were performed as discussed in Section 3.3.2 on all as received samples

along with samples washed 5, 10, and 25 times. The results of the tests are shown below in

Table 4.14 in grams (g) of water penetrated through the fabric. The average of three tests

was used to calculate the results. In accordance with AATCC TM 42, if more than five

grams of water penetrates through the fabric, it is recorded as “>5g”. The results for each

individual test can be found on page 122 in Appendix D.

Table 4.14. Polyester/Cotton Impact Penetration Results

Washes Finish 0 5 10 25

W > 5 g 3.6 g 3.5 g 1.4 g WM > 5 g > 5 g 4.7 g 3.9 g

P > 5 g > 5 g > 5 g > 5 g

Table 4.14 shows that all finishes absorbed more than 5 grams of water before

washing. After washing, the W finish was dramatically improved after 25 washes while the

WM finish improved after 5 and 10 washes but deteriorated after 25. The P finish absorbed

more than 5 grams of water for each wash cycle. It should be noted that the P finish allowed

over 15 grams of water to penetrate the fabric for nearly every test. A fully saturated paper

blotter varied in weight between 16 and 18 grams. This suggests that the P finish had a

minimal protection of impact resistance. This may be because the polymerized water

repellent film failed allowing water to pass easily into the bulk of the fabric.

The interesting results observed between the W and WC finishes can be explained by

both the fabric’s construction and the durability of the repellent finish after each wash cycle.

70

The polyester/cotton fabric tested in this research was very porous as shown on page 120.

Because the fabric contained large capillary spaces within the fabric, it was expected that it

would not perform well in the impact test. After each wash cycle, the fabric shrank

decreasing the pore size. This can explain the improved performance over each wash cycle

for both the W and WM finishes. The spray test suggested that the W finish is more repellent

than the WM finish after 10 and 25 washes. This can help explain how the W finish allowed

less water to penetrate the fabric than the WC finish.

4.2.2.4 Water/Alcohol

Water/alcohol tests were performed as discussed in Section 3.3.3 on all as received

samples along with samples washed 5, 10, and 25 times. The results of the water/alcohol

tests shown in Table 4.15 were determined by Table 3.9 and Figure 3.2 as described in

Section 3.3.3.

Table 4.15. Polyester/Cotton Water/Alcohol Results

Washes Finish 0 5 10 25

W 8 8 8 8 WM 8 8 8 6.5

P 8 6.5 5.5 3

Table 4.15 shows that all unwashed finishes received the highest grade of 8. Both

conventional W and WM finishes are comparable with WM having a small decrease in

repellency after 25 washes. The P finish’s repellency slowly decreased as washes increased

down to a grade of 3 after 25 washes. Referring back to Table 3.4, the P finish fails the

company’s requirement of a minimum grade of 5 at 25 washes.

71

4.2.2.5 Oil

Oil tests were performed as discussed in Section 3.3.4 on all as received samples

along with samples washed 5, 10, and 25 times. The results of the oil test shown in Table

4.16 were determined by Table 3.10 and Figure 3.2 as described in Section 3.3.4.

Table 4.16. Polyester/Cotton Oil Results

Washes Finish 0 5 10 25

W 6.5 6.5 6.5 6.5 WM 7.5 6.5 6.5 6.5

P 7.5 6.5 5.5 5

Table 4.16 shows that each finish is comparable before washing. Both conventional

finishes remained mostly constant through 25 washes although the P finish decreases slowly

in repellency after each wash cycle. Referring back to Table 3.4, the P finish just passes the

company’s requirement of a minimum grade of 5 after 25 washes.

4.2.2.6 Water Contact Angle

Contact angle measurements were taken as discussed in Section 3.3.5 for all as

received samples along with samples washed 5, 10, and 25 times. The results of the contact

angle tests shown in Table 4.17 on the following page are the average of five different

measurements and are given in degrees. The results for each individual water contact angle

test can be found on page 123 in Appendix D.

72

Table 4.17. Polyester/Cotton Contact Angle Results

Washes Finish 0 5 10 25

W 150° 155° 153° 151° WM 156° 155° 154° 152°

P 150° 146° 142° 138°

Analysis of Variance (ANOVA) tests in Appendix D were conducted on the data used

to generate Table 4.17 in order to compare the repellency and durability of the finishes. An

ANOVA was conducted both between and within each finish.

The ANOVA between finishes determines if there is a statistically significant

difference in water contact angles between each finish at each wash cycle. The results of

these ANOVAs on pages 124 through 127 show that before washing there is no difference

between the W and P finishes although there is a borderline statistical significance of the

WM finish having a water contact angle approximately 5 degrees greater then the W and P

finishes. At 5 washes the conventional W and WM finishes had a statistically higher water

contact angle by 5 degrees over the P finish. This is also true at 10 and 25 washes except the

angle increased from 5 degrees to 10 and 12 degrees respectively.

The ANOVA within each finish determines the statistical significance of how much,

or even if, each specific repellent finish deteriorates after each wash cycle. The results of

these ANOVAs on pages 128 though 130 show that from the data collected, no significant

difference in repellency can be determined for the conventional finishes, although a

difference is observed for the P finish. The P finish shows a slow descending progression in

73

the water contact angle where there is a statistical difference in the contact angle between 0

and 25 washes by about 12°.

4.2.3 Polyester

The polyester fabric contained five segments: control calendered, control non-

calendered, conventional calendered, atmospheric plasma calendered, and atmospheric

plasma non-calendered as discussed in Section 3.2.3. The nomenclature used throughout the

remainder of the document is given below in Table 4.18.

Table 4.18. Polyester Fabric Nomenclature

Abbreviation Segment Description

C-CTRL control calendered calendered PET with no finish (prepared only)

NC-CTRL control non-calendered non-calendered PET with no finish (prepared only)

C-W conventional calendered commercially available calendered PET with conventional finish

C-P atmospheric plasma calendered calendered PET with APPLD finish

NC-P atmospheric plasma non-calendered non-calendered PET with APPLD finish

4.2.3.1 XPS Analysis

An XPS analysis was performed as discussed in 3.4.1 on all five polyester segments.

Table 4.19 on the following page shows the percent fluorine composition of each nylon

segment. The full elemental compositions can be found on page 134 in Appendix E.

74

Table 4.19. Fluorine Composition of Polyester Segments

Segment Composition C-CTRL 0%

NC-CTRL 0% C-W 63% C-P 64%

NC-P 65%

As expected, the CTRL segments do not have a repellent finish therefore no fluorine

was detected on the surface. For the C-W, C-P, and NC-P finishes, fluorine was found to

represent 63, 64, and 65 percent of the surface respectively. Also, the binding energies for

the C-W, C-P, and NC-P finishes are all extremely similar suggesting that all three finishes

have the same amount of fluorine on the surface and all of the surfaces have an analogous

chemical composition. Therefore, it can be expected that there is no initial bias in repellency

or durability between the C-W, C-P, or the NC-P finish. The full scan of each polyester

segment can be found on page 133 in Appendix E.

4.2.3.2 Spray

Spray tests were performed as discussed in Section 3.3.1 on all as received samples

along with samples washed 5, 10, and 25 times. The results of the spray test shown in Table

4.20 on the following page are the score as given by Figure 3.1 on page 47. The average of

three tests was used to determine the results. The results for each individual test can be

found on page 134 in Appendix E.

75

Table 4.20. Polyester Spray Results

Washes Finish 0 5 10 25 C-W 100 100 100 100 C-P 100 100 100 100

NC-P 100 100 100 100

Neither of the CTRL segments are included in the results of Table 4.20 because they

both scored a 0. For this reason, the CTRL segments will not be included in any of the

proceeding tests discussed in this section. Table 4.20 shows that all three finishes scored a

perfect score of 100 before and after each wash cycle. Referring back to page 44, all finishes

pass the companies’ requirement for an as received score of at least 90.

4.2.3.3 Impact

Impact tests were performed as discussed in Section 3.3.2 on all as received samples

along with samples washed 5, 10, and 25 times. The results shown below in Table 4.21 are

in grams (g) of water penetrated through the fabric. The average of three tests was used to

calculate the results. The results for each individual test can be found on page 134 in

Appendix E.

Table 4.21. Polyester Impact Penetration Results

Washes Finish 0 5 10 25 C-W 0g 0g 0g 0g C-P 0g 0g 0g 0g

NC-P 0.1g 0.1g 0.1g 0.1g

Table 4.21 shows that the conventional C-W finish and the C-P finish allowed no

penetration of water through the fabric. The NC-P finish also performed well allowing only

76

a slight penetration of water through the fabric most likely due to the non-calendered fabric

having larger capillary spaces than the calendered fabrics.

4.2.3.4 Water/Alcohol

Water/alcohol tests were performed as discussed in 3.3.3 on all as received samples

along with samples washed 5, 10, and 25 times. The results of the water/alcohol test shown

in Table 4.22 were determined by Table 3.9 and Figure 3.2 as described in Section 3.3.3.

Table 4.22. Polyester Water/Alcohol Results

Washes Finish 0 5 10 25 C-W 7.5 7.5 6.5 6.5 C-P 8 8 8 8

NC-P 8 8 8 8

Table 4.22 shows that both the C-P and NC-P atmospheric plasma finishes scored the

highest score possible in the water/alcohol test both before and after each wash cycle. The

conventional C-W also performed well, but showed a slight decrease in repellency after 10

washes.

4.2.3.5 Oil

Oil tests were performed as discussed in Section 3.3.4 on all as received samples

along with samples washed 5, 10, and 25 times. The results of the oil tests shown in Table

4.23 on the following page were determined by Table 3.10 and Figure 3.2 as described in

3.3.4.

77

Table 4.23. Polyester Oil Results

Washes Finish 0 5 10 25 C-W 4.5 4 3 2 C-P 5.5 5 5 5.5

NC-P 5 5.5 5.5 5.5

Table 4.23 shows that the conventional C-W finish decreases in repellency after each

wash cycle while the atmospheric plasma finishes C-P and NC-P do not. The results of the

oil tests suggest that the atmospheric plasma finish is more repellent and more durable than

the conventional finish.

4.2.3.6 Water Contact Angle

Contact angle measurements were taken as discussed in Section 3.3.5 for all as

received samples along with samples washed 5, 10, and 25 times. The result of the contact

angle tests shown in Table 4.24 are the average of five different measurements and are given

in degrees. The results of each individual water contact angle test can be found on page 135

in Appendix E.

Table 4.24. Polyester Contact Angle Results

Washes Finish 0 5 10 25 C-W 131° 143° 144° 145° C-P 127° 142° 146° 145°

NC-P 155° 151° 153° 154°

Analysis of Variance (ANOVA) tests in Appendix E were conducted on the data used

to generate Table 4.24 in order to compare the repellency and durability of the finishes. An

ANOVA was conducted both between and within each finish.

78

The ANOVA between finishes determines if there is a statistically significant

difference in water contact angles between each finish at each wash cycle. The results of

these ANOVAs on pages 138 through 141 show that for each wash cycle the non-calendered

NC-P finish had a statistically greater contact angle than the calendered C-W and C-P

finishes. This is most likely explained by the non-calendered fabric having a slightly rougher

surface than the calendered fabrics. Although the NC-P finish had a greater contact angle

then the other finishes, the ANOVA shows that the C-W and C-P finishes do not have

statistically different water contact angles.

The ANOVA within each finish determines the statistical significance of how much,

or even if, each specific repellent finish deteriorates after each wash cycle. The results of

these ANOVAs on pages 142 though 144 show that for both calendered finishes C-W and C-

P, the contact angle before washing was lower then the angles measured after washing by

about 12°. This is most likely because of the smooth surface of the calendered fabric. After

washing the C-W and C-P finishes, the contact angles increased because the washing caused

the surface to become slightly rougher. At 5, 10, and 25 wash cycles, the C-W and C-P

finishes did not have a statistically different water contact angle. The NC-P finish does not

have a statistically different water contact angle at 0, 5, 10 or 25 washes.

4.2.3.7 Additional Tests

The polyester fabric is a barrier fabric; therefore, additional tests were performed to

ensure that the atmospheric plasma treatment would not negatively affect the physical

properties of the fabric. Because calendering changes the physical properties of the fabric,

79

the non-calendered NC-P finish was not compared to the calendered C-W and C-P finishes.

The non-calendered finish results are provided to show the effects of atmospheric plasma

treatment on non-calendered fabrics for academic purposes only.

Hydrostatic Pressure Test

The hydrostatic pressure test was performed as described in Section 3.3.6.1 for all as

received samples along with samples washed 5, 10, and 25 times. The results, shown below

in Table 4.25, are in centimeters (cm) of water. The higher the water reaches in centimeters,

the greater the pressure on the fabric before failure. The average of three tests was used to

calculate the results. The results for each individual test can be found on page 136 in

Appendix E.

Table 4.25. Polyester Hydrostatic Pressure Results

Washes Finish 0 5 10 25 C-W 67cm 80cm 71cm 67cm C-P 96cm 80cm 76cm 71cm

NC-P 42cm 41cm 42cm 43cm

As expected, Table 4.25 shows that the non-calendered finishes tend to fail at lower

pressures than the calendered finishes. An ANOVA between finishes given on pages 145

through 148 shows that at 0 and 10 washes there is a statistical difference between the

conventional C-W and atmospheric plasma C-P calendered finishes. Before washing, the C-

P finish can withstand a greater pressure than the C-W finish by about 25 cm but only by a

few cm after 10 washes.

80

An ANOVA within finishes given on pages 149 through 151 shows that for the

conventional C-W finish, there is no statistical difference between failure at 0, 10, and 25

washes but the pressure to fail at 5 washes was statistically higher by more than 5 cm. The

ANOVA also shows a steady decrease in the pressure needed to fail the C-P finish resulting

in a statistical difference between 0 and 5 washes, and then again between 5 and 25 washes.

There was no significant statistical difference found in the height of water needed to fail the

fabric for the non-calendered NC-P finish. Referring back to Table 3.6, both the

conventional C-W and the atmospheric plasma C-P finish are well within 55 cm minimum

specification of the product.

Wash Shrinkage

The wash shrinkage test was performed on samples that had been washed 5 times as

described in Sections 3.3.6.2 and 3.4.2. The results, shown below in Table 4.26, are in

percent of shrinkage. An average of six samples was used to calculate the results. The

results for each individual test can be found on page 136 in Appendix E.

Table 4.26. Polyester 5 Wash Shrinkage Results

Direction Finish Warp Fill

C-CTRL 1.5% 0.3% NC-CTRL 1.5% 0.3%

C-W 0.7% 0.1% C-P 2.1% 0.6%

NC-P 3.9% 0.1%

Table 4.26 shows that the conventional C-W finish does not shrink after five washes

as much as the atmospheric plasma C-P finishes. This can be explained because the C-W

81

finish has already been exposed to heat during the pad-dry-cure process. The C-P finish was

first subjected to heat during laundering and therefore shrank more than the C-P finish after 5

washes. Referring back to Table 3.6, both the conventional C-W and the atmospheric plasma

C-P finishes were well within the 3% shrinkage specification of the product.

Air Permeability

Air permeability testing was performed by the company that submitted the fabric as

discussed in Section 3.3.6.3 for all as received samples along with samples washed 5, 10, and

25 times. The results shown in Table 4.27 are in cubic feet per minute (cfm). The results for

each individual test can be found on page 136 in Appendix E.

Table 4.27. Polyester Air Permeability Results

Washes Finish 0 5 10 25 C-W 0.7cfm 0.7 cfm 0.8 cfm 0.8 cfm C-P 0.3 cfm 0.4 cfm 0.9 cfm 1.0 cfm

NC-P 7.9 cfm 10.2 cfm 9.8 cfm 10.0 cfm * C-CTRL = 0.4 cfm, NC-CTRL = 9.4 cfm

As expected, Table 4.27 shows that the non-calendered finish allows more air through

the fabric than the calendered finishes. ANOVAs performed between the C-W and C-P

finishes on pages 152 through 155 shows that each cfm difference given in Table 4.27 is

statistically significant. The C-P finish initially allowed less air to pass through it although

at 10 washes the performance of the C-W finish overcomes it. This could possibly be

explained by the C-P finish having an additional polymerized thin film that contributed to

preventing air from passing though the fabric, but after 25 washes, the film was not as

82

effective. This hypothesis is backed up by the ANOVA within the C-P finish discussed in

the following paragraph.

ANOVAs were also performed within the C-W and C-P finish to determine if the air

permeability was affected by washing for each finish. These ANOVAs on pages 156 through

158 show that the C-W finish was very consistent through each wash cycle although the C-P

finish was not. For each wash cycle, the amount of air passed through the C-P finish became

greater and greater. The NC-P finish showed a large increase in air permeability after

washing. The NC-P wash results of 5, 10, and 25 washes were not statistically different.

Referring back to Table 3.6, both the conventional C-W and the atmospheric plasma C-P

finish are well within the 2.5 cfm maximum specification of the product.

Tensile

The tensile tests were performed as described in Section 3.3.6.4 for all as received

samples along with samples washed 5, 10, and 25 times. The results shown on the following

page in Table 4.28 and Table 4.29 are in pounds (lb) of breaking force in the warp and filling

direction respectively. The average of five tests was used to calculate the results. The results

for each individual test can be found on page 137 in Appendix E.

83

Table 4.28. Polyester Tensile Test Results in the Warp Direction

Washes Finish 0 5 10 25 C-W 177 lb 175 lb 175 lb 170 lb C-P 169 lb 173 lb 175 lb 173 lb

NC-P 177 lb 171 lb 175 lb 170 lb * C-CTRL = 184 lb, NC-CTRL = 181 lb

ANOVAs on pages 159 through 162 were conducted on the data used to generate

Table 4.28 to determine if there is a statistical difference in breaking strength in the warp

direction between the finishes across each wash cycle. It suggests that the C-W finish has a

higher breaking strength than the C-P finish by about 7 pounds although there is no statistical

difference in warp breaking strength between the two finishes after 5 or more washes.

ANOVAs were also conducted within each finish on pages 163 through 165 and found there

to be no statistical difference between washes within each finish. Referring back to Table

3.6, the warp breaking strength is well above the 120 pound minimum for each finish.

Table 4.29. Polyester Tensile Test Results in the Fill Direction

Washes Finish 0 5 10 25 C-W 100 lb 90 lb 100 lb 104 lb C-P 107 lb 103 lb 107 lb 99 lb

NC-P 108 lb 110 lb 108 lb 108 lb * C-CTRL = 104 lb, NC-CTRL = 108 lb

ANOVAs on pages 166 through 169 were conducted on the data used to generate

Table 4.29 to determine if there is a statistical difference in breaking strength in the fill

direction between the finishes across each wash cycle. The ANOVA shows that for 0, 5, and

10 washes, the C-P finish has a higher breaking strength than the C-W finish by about 7, 13,

84

and 7 pounds respectively. After 25 washes, the breaking strength of the C-W finish is

slightly greater than the C-P finish by 5 pounds.

ANOVAs were also conducted on pages 170 through 172 within each finish to

determine if each finish’s breaking strength changed after each wash cycle. The ANOVA

shows no statistical difference in the breaking strength in the filling direction of the NC-P

finish, but it does show a statistical difference in both the conventional C-W and atmospheric

plasma C-P finish. The conventional C-W finish had a lower breaking strength at 5 washes

than it did at 0, 10, and 25 washes by about 10 pounds. The atmospheric plasma C-P finish

had a lower breaking strength at 25 washes than at 0 and 10 washes by about 5 pounds.

Referring back to Table 3.6, the warp breaking strength is well above the 70 pound minimum

for each finish.

4.2.4 Nylon

The nylon fabric contained three segments: control, conventional, and atmospheric

plasma as discussed in 3.2.4. Because DCPS treated an additional 20 meters of nylon as

discussed in Section 4.1, an additional atmospheric plasma segment was added. The

nomenclature used throughout the remainder of the document is given on the following page

in Table 4.30.

85

Table 4.30. Nylon Fabric Nomenclature

Abbreviation Segment Description

CTRL control nylon fabric finished with no finish (prepared only)

W conventional nylon fabric finished with conventional wet pad-dry-cure finish

PA atmospheric plasma nylon fabric finished with APPLD from Table 4.2

PB atmospheric plasma nylon fabric finished with APPLD from Table 4.3

4.2.4.1 XPS Analysis

An XPS analysis was performed as discussed in 3.4.1 on all four nylon segments.

Table 4.31 shows the percent fluorine composition of each nylon segment. The full

elemental compositions can be found on page 175 in Appendix F.

Table 4.31. Fluorine Composition of Nylon Segments

Segment CompositionCTRL 0%

W 62% PA 63% PB 62%

As expected, the CTRL segment does not have a repellent finish therefore no fluorine

was detected on the surface. For the W, PA, and PB finishes, fluorine was found to represent

62, 63, and 62 percent of the fabric surface respectively. Also, the binding energies for the

W, PA, and PB finishes are all extremely similar suggesting that all three finishes have the

same amount of fluorine on the surface and both surfaces have an analogous chemical

composition. Therefore, it can be expected that there is no initial bias in repellency or

86

durability between the W, PA, or PB finishes. The full scan of the nylon surface’s elemental

binding energies can be found on page 174 in Appendix F.

4.2.4.2 Spray

Spray tests were performed as discussed in Section 3.3.1 on all as received samples

along with samples washed 5, 10, and 25 times. The results of the spray test shown in Table

4.32 are the score as given by Figure 3.1 on page 47. The average of three tests was used to

determine the results. The results for each individual test can be found on page 175 in

Appendix F.

Table 4.32. Nylon Spray Results

Washes Finish 0 5 10 25

W 100 100 98 98 PA 100 100 100 100 PB 100 100 100 100

The CTRL segment is not included in the results of Table 4.32 because it scored a 0.

For this reason, the CTRL segment will not be included in any of the proceeding tests

discussed in this section. As shown in Table 4.32, all finishes scored well on the spray test

both before and after washing. Referring back to Table 3.8, all nylon finishes scored the

companies’ minimum requirement of 90 for all wash cycles.

4.2.4.3 Impact

Impact tests were performed as discussed in Section 3.3.2 on all as received samples

along with samples washed 5, 10, and 25 times. The results are shown below in Table 4.33

in grams (g) of water penetrated through the fabric. The average of three tests was used to

87

calculate the results. The results for each individual test can be found on page 175 in

Appendix F.

Table 4.33. Nylon Impact Penetration Results

Washes Finish 0 5 10 25

W 0.4 g 0.2 g 0.1 g 0.1 g PA 0 g 0.1 g 0 g 0.1 g PB 0 g 0 g 0 g 0 g

Table 4.33 shows that all finishes performed very well in the impact penetration test.

This result is expected because the product is made specifically as outerwear jacket material.

Both atmospheric plasma finishes performed exceptionally well. The conventional W finish

allowed a slight penetration of water through the fabric before washing, but after washing it

was comparable to both PA and PB atmospheric plasma finishes.

4.2.4.4 Water/Alcohol

Water/alcohol tests were performed as discussed in Section 3.3.3 on all as received

samples along with samples washed 5, 10, and 25 times. The results of the water/alcohol

tests shown in Table 4.34 where determined by Table 3.9 and Figure 3.2 as described in

Section 3.3.3.

Table 4.34. Nylon Water/Alcohol Results

Washes Finish 0 5 10 25

W 8 8 8 8 PA 8 8 8 8 PB 8 8 8 8

88

Table 4.34 shows that all finishes, both the conventional W and the atmospheric

plasma PA and PB finishes, scored a grade of 8. This is the highest score possible for the

water/alcohol test.

4.2.4.5 Oil

Oil tests were performed as discussed in Section 3.3.4 on all as received samples

along with samples washed 5, 10, and 25 times. The results of the oil test shown in Table

4.35 were determined by Table 3.10 and Figure 3.2 as described in Section 3.3.4

Table 4.35. Nylon Oil Results

Washes Finish 0 5 10 25

W 7.5 7.5 6.5 6.5 PA 6.5 6.5 5.5 5.5 PB 6 6 5.5 5.5

Table 4.35 shows that the conventional W finish slightly outperformed both

atmospheric plasma finishes although not significantly. All finishes showed about the same

rate of repellency lost due to washing.

4.2.4.6 Water Contact Angle

Contact angle measurements were taken as discussed in Section 3.3.5 for all as

received samples along with samples washed 5, 10, and 25 times. The result of the contact

angle tests shown in Table 4.36 are the average of five different measurements and are given

in degrees. The results of each individual water contact angle test can be found on page 176

in Appendix F.

89

Table 4.36. Nylon Contact Angle Results

Washes Finish 0 5 10 25

W 151° 144° 145° 144° PA 147° 147° 150° 142° PB 144° 151° 151° 144°

ANOVAs in Appendix F were conducted on the data used to generate Table 4.36 in

order to compare the repellency and durability of the finishes. An ANOVA was conducted

both between and within each finish.

The ANOVA between finishes determines if there is a statistically significant

difference in water contact angles between each finish at each wash cycle. The results of

these ANOVAs on pages 177 through 180 show that from the data collected, only at 0 and 5

washes there was a difference in water contact angles among the finishes. The PA and PB

finishes had no difference in both cases although the W finish had a contact angle greater

than the PB finish by about 8° at 0 washes and at 5 washes the PB finish had a higher water

contact angle than the W finish by about 7°.

The ANOVA within each finish determines the statistical significance of how much,

or even if, each specific repellent finish deteriorates after each wash cycle. The results of

these ANOVAs on pages 181 though 183 show that from the data collected, the repellency of

each finish does not deteriorate over each wash cycle. The PB finish actually has a greater

water contact angle at 5 and 10 washes than it does at 0 and 25 washes by about 7°.

90

4.3 Cost Analysis

The final element that was studied in order to determine the viability of a commercial

atmospheric plasma process was the total cost to produce the product. In this section, the

chemical and energy cost of conventional pad-dry-cure finishing will be compared to the cost

of the APPLD finish that the fabrics in this study were treated with.

4.3.1 Conventional Pad-Dry-Cure Finishing

Because chemical and energy costs used to produce commercial textile products are

kept confidential by textile companies, conventional finishing costs were estimated.

Estimates were based on the cotton fabric that was finished at Cotton Incorporated in Cary,

NC as discussed in Section 3.2.1. The cotton was chosen because it is a heavier weight

fabric that would pick up more chemical and take more energy to dry and cure resulting in a

conservative estimate. The specific calculations used to determine the conventional pad-dry-

cure chemical and energy costs are located in Appendix G. A breakdown of the calculations

provided in Appendix G is given below in Table 4.37.

Table 4.37. Total Cost of Conventional Treatment

$ per sq ydChemicals 0.18 Electricity 0.011

Gas 0.0077 Total 0.20

These calculations suggest that an approximate cost, including chemicals and energy,

to conventionally apply a repellent finish onto a fabric is $0.20 per square yard. This

estimate was confirmed as “reasonable” by a textile company cooperating with this research.

91

4.3.2 Atmospheric Pressure Plasma Liquid Deposition Finishing

Dow Corning Plasma Solutions (DCPS) did not disclose the exact cost associated

with the fabric treated in this research because they said the following stipulations have the

potential to drastically reduce the cost per square yard.

1. The project did not explore the limits of the processing window, so the costs associated are the maximum which would be incurred.

2. In an industrial scenario, the processing speed could be between 5 and 10 times faster with the same usage of electricity and helium. Also, a professional procurement manager could negotiate better pricing for the precursor.

3. Process development could allow the amount of precursor used to be decreased, perhaps dramatically.

With these provisions stated, DCPS stated that the cost of the APPLD treatment of

this research was less than $2.00 per square yard. Although an exact dollar figure could not

be provided by DCPS, an estimate was calculated in Appendix H resulting in a total cost

including energy, process gas, and chemicals to be about $1.13 per square yard. This

breakdown is given below in Table 4.38.

Table 4.38. Total Cost of APPLD Treatment

$ per sq ydElectricity 0.0062

Helium 0.81 Chemicals 0.31

Total 1.13

92

4.3.2.1 Theoretical Cost Projection

In order for APPLD to be a viable replacement for conventional finishing, the total

cost must be drastically lowered. As a result, ways that the total cost could be lowered were

explored.

In order to lower the cost of the APPLD treatment on an industrial scale, the

efficiency of the process must be determined. For this reason, the efficiency of the

polymerization process was investigated. As calculated in Equation 7.9 in Appendix H, there

is about 1.25 grams of each precursor that is injected into the plasma region every minute.

Of these 1.25 grams, Equation 7.10 shows that about 2 grams of each precursor polymerizes

on each square yard of the fabric surface. This equation assumes that the polymerization

process is 100 percent efficient.

Because DCPS was told to do whatever was necessary to match the repellency of the

conventional repellent finishes they were provided, they very likely over engineered their

process. To determine just how much fluorine was present on the fabric, samples from the

one hundred percent cotton and one hundred percent polyester atmospheric pressure plasma

as received segments were sent to Galbraith for fluorine analysis. By calculating the

theoretical ppm of fluorine from Equation 7.10 and comparing this with the actual ppm of

fluorine as tested by Galbraith, the efficiency of polymerization was determined.

The theoretical amount of fluorine due to each precursor on each surface of each

fabric was calculated by dividing the milligrams of fluorine by a kilogram of fabric. With

the mass of each precursor on a square yard of fabric calculated in Equation 7.10, the weight

93

of each fabric as shown in Table 3.1 and Table 3.5, and the known molecular structure of

each chemical precursor given in Figure 4.1, the theoretical parts per million (ppm) of

fluorine for each fabric was calculated below in Equation 4.1.

HDFD F HDFDA F F

2 HDFD 2 HDFDA 2

cotton cotton

2 2

2.06 323 2.02 323 1000 2750446.12 518.19 1

14600 F6.65 0.189

35.27

g mw g mw mg mgyd mw yd mw g yd ppm

oz kg kgyd oz yd

⎡ ⎤⎛ ⎞ ⎛ ⎞⋅ + ⋅ ⋅⎢ ⎥⎜ ⎟ ⎜ ⎟

⎝ ⎠ ⎝ ⎠⎣ ⎦ = =⋅

HDFD F HDFDA F F

2 HDFD 2 HDFDA 2

PET PET

2 2

2.06 323 2.02 323 1000 2750446.12 518.19 1

36100 F2.69 0.0763

35.27

g mw g mw mg mgyd mw yd mw g yd ppm

oz kg kgyd oz yd

⎡ ⎤⎛ ⎞ ⎛ ⎞⋅ + ⋅ ⋅⎢ ⎥⎜ ⎟ ⎜ ⎟

⎝ ⎠ ⎝ ⎠⎣ ⎦ = =⋅

Equation 4.1. Fluorine ppm Levels on Cotton (top) and Polyester (bottom)

Table 4.39 below gives the amount of fluorine as determined by Galbraith and the

theoretical ppm fluorine levels for each fabric.

Table 4.39. Fluorine Analysis Test Results

Cotton Polyester Theoretical Actual Theoretical Actual

ppm F 14600 6200 36100 17900

Table 4.39 shows that the actual amount of fluorine on the surface of both the cotton

and polyester fabrics is much lower than the theoretical amount as determined by Equation

7.10. The amount of fluorine on the cotton and polyester are 42 and 50 percent respectively

of the theoretical value calculated in Equation 7.9. This shows that half of the chemical

precursors that are injected into the plasma region do not polymerize on the surface. This

can possibly be explained by a combination of the following:

94

1. the chemical precursors are not polymerizing;

2. there are more precursors injected into the plasma than can polymerize; or

3. the precursor is polymerizing on surfaces other than the fabric.

Most likely, only half of the chemical precursors polymerize on the surface due to a

combination of the latter two items above. These results suggest that the APPLD process

used in this research was over engineered in order to guarantee that it would be comparable

to the repellency of the conventional repellent finishes. Therefore, it may be possible to

either decrease the amount of precursors injected into the plasma or to increase the speed of

the process with comparable results. Since the APPLD process used in this research was not

up to conventional textile speeds, an increase in processing speed will be explored.

Because DCPS suggested that in an industrial scenario the speed of the process could

increase 5 to 10 times, and because only half of the chemical precursors injected into the

plasma were actually polymerized, a processing speed of 25 yards per minute is not

unreasonable for a theoretical calculation. In addition to an increase in processing speed, the

theoretical calculation below will assume that DCPS can recycle 90 percent of the helium

used in the process. By substituting a line speed of 25 yards per minute into Equation 7.10,

using Equation 7.11 to calculate the cost of the precursors, and taking ten percent of the

helium used in Equation 7.8, all in Appendix H, Table 4.40 shows the total theoretical cost of

the APPLD process in an industrial scenario assuming that all of the precursors injected into

the plasma polymerize on the fabric surface.

95

Table 4.40. Total Theoretical Cost of APPLD Treatment in an Industrial Scenario

$ per sq ydElectricity 0.0062

Helium 0.081 Chemicals 0.067

Total 0.15

96

5. Conclusions & Recommendations

5.1 Repellency and Durability

Results given from the spray, impact, water/alcohol, oil, and contact angle tests for

both the cotton and polyester/cotton fabrics suggest that the atmospheric plasma treatment is

comparable to the conventional finish on the basis of repellency before washing, but it is not

as durable as the conventional finish.

Cotton fabrics are difficult to impart a durable repellent finish on because of the

swelling of the fibers during washing. This research shows that the conventional repellent

finish is more durable than a commercial atmospheric plasma treatment. Because both

conventional and atmospheric plasma treated cotton and polyester/cotton fabrics had the

same amount of fluorine on the surface before washing, the explanation of the conventional

finish’s superior durability to that of the atmospheric plasma finish most likely lies in the

cross-linking on the conventional finish’s surface.

The repellency and durability tests performed on the nylon fabric show that

atmospheric plasma treatment is comparable on the basis of both repellency and durability to

the conventional pad-dry-cure method. Dow Corning’s second nylon APPLD treatment, the

PB finish, that was optimized for durability had a statistically greater water contact angle

after five washes, but only by a few degrees. No other repellency tests conducted with the

second APPLD finish suggest that it is in any way superior to the original APPLD finish.

Comparing the machine settings of Table 4.2 and Table 4.3 shows that reducing the precursor

flow rate by half and doubling the number of passes does not result in a significant change in

97

repellency or durability. Both conventional and atmospheric plasma finishes were well

within the repellency and durability specifications provided by the company.

For the polyester tested in this research, the conventional finish was just as repellent

as the atmospheric plasma treatment but in the oil test it was not as durable. After 25 washes,

the conventional finish dropped from a grade of 4.5 to a 2 in the oil test and the atmospheric

plasma finish remained constant with a grade of 5.5 through each wash cycle. The water

contact angle test gave slightly different results. When testing the contact angle of water on

the polyester after each wash cycle, there was no statistical difference between the contact

angles of the conventional or atmospheric plasma finish. The oil test suggests the surface

energy of the conventionally finished polyester fabric does increase after washing more than

the atmospheric plasma finish; however, the contact angle test could not measure this

because water was being used as the test liquid. The additional physical tests performed

concluded that the atmospheric plasma treatment did not negatively affect the fabric’s burst

pressure, air permeability, or tensile strength, although it did slightly increase the shrinkage

of the fabric. Both conventional and atmospheric plasma finishes were well within the

physical specifications as given by the company that submitted the fabric.

5.2 Cost

In order for the atmospheric plasma treatment to be a viable replacement for

conventional pad-dry-cure finishing, it must not only be comparable in repellency and

durability, but also in cost. Although the APPLD technology works, it currently costs a

significant amount more than conventional finishing. As discussed in Section 4.3,

98

conventional treatment costs about $0.20 per square yard while the atmospheric plasma

treatment used in this research costs approximately $1.13 per square yard. The theoretical

proposed cost of running the DCPS APPLD machine in an industrial scenario at 25 yards per

minute with a helium recycling system costs $0.15 per square yard.

At this point, Dow Corning’s APPLD technology as used in this research is too

expensive to be a viable replacement for conventional processing. Although the treatment

used in this research was too expensive, DCPS did show that their APPLD technology does

work, and if they could recycle their helium and show comparable results at around 25 yards

per minute, APPLD could possibly be a viable replacement for conventional finishing.

5.3 Recommendations

Because the atmospheric plasma treated samples that contained cotton had poor

durability characteristics, the addition of cross-linking monomers into the plasma region

should be investigated. Also, the precursor used by DCPS in this research has only one

reactive group, although monomers can be used that would have two reactive groups

resulting in more cross-linking and therefore a more durable finish.

Additional chemicals should be explored for use with the APPLD technology. One of

the key aspects of the technology as compared with other atmospheric plasma coating

technologies is that the chemicals injected into the plasma can be monomers that are

immiscible or in different phases. For this reason, some chemicals that are used in

conventional finishing could possibly be used for APPLD. If it is determined that this is not

99

feasible, silicone chemistry should be explored because it is much more inexpensive than

fluorochemistry.

The proposed theoretical cost of the APPLD process as calculated in this research

assumes that the helium process gas can be recycled although this is currently not the case.

Because the helium gas was calculated to cost approximately $0.81 per square yard and the

total conventional finishing cost was only $0.20 per square yard, a way to recycle the helium

must be accomplished or it doesn’t matter what kind of chemistry is used in the APPLD

process.

The speed at which the APPLD process ran at in this research was 5 meters per

minute (about 5.5 yards per minute) which is much slower than a typical 25 yard per minute

tenter. Although the data given in Section 4.3.2.1 suggests that a faster processing speed is

possible and on page 91 DCPS states that they would expect the processing speed to increase

by 5 to 10 times in an industrial scenario, it must be determined if the APPLD process is

even capable of providing a comparable repellent finish at upwards of 25 yards per minute or

greater.

Current slow speeds and excessive helium gas costs naturally result in looking at

other technologies that can possibly overcome this hurdle. A company in Santa Fe, NM

USA, named APJeT Inc., discussed on page 37, has a full width atmospheric plasma

industrial machine called the TexJet that can run at 40 yards per minute. APJeT has a

method to recycle the helium gas used in the process, but unlike Dow Corning’s APPLD

technology, they can only use gas chemical precursors for fabric treatments. Although they

100

can use only gas, APJeT uses a downstream technology as discussed on page 37 so the

complex gas precursors are not dissociated in the plasma region. Because APJeT relies

heavily on process gasses, they have partnered with Air Products and Chemicals out of

Allentown, PA USA, which may result in very low process gas prices.

The current preliminary cost of a fully configured TexJet capable of running 40 yards

per minute is $1.75 million USD. A recycling unit that can recycle 90% of the helium used

in the process is an additional $0.5 million for a total of $2.25 million USD. APJeT provided

a proposed cost per linear yard estimated for a 72 inch wide roll at $0.20. This calculates to

$0.10 per square yard.

NCSU is currently working to acquire an APPR model 300-13 lab scale atmospheric

plasma treatment device from APJeT. This device can be used to develop a repellent finish

that is both as repellent and durable as a commercial finish. If the proposed cost per square

yard of fabric from APJeT is correct, it could very well be a viable replacement for

conventional pad-dry-cure repellent finishing.

A comparison of the two technologies is given in Table 5.1 on the following page.

101

Table 5.1. Comparison of Dow Corning and APJeT Technologies

DCPS AP4 APJeT TexJet Capital Cost (Million USD) 2.5 - 4 2.25 He recycled? N Y Different finish on each side? N Y Dimensions (h x w x d) ft 10.8 x 6.6 x 12.5 8 x 8 x 3 Power (KW) ~0 - 20 20 - 120 Max Speed (ypm) 75 80 Max Fabric Width (in) 98 72 Cost per square yard *$0.15 **$0.10 * Theoretically calculated in Section 4.3.2.1, see Section 4.3.2 for actual ** Proposed cost from APJeT

5.4 Summary

For all fabrics tested in this research before washing, the atmospheric plasma treated

fabrics were equally as repellent as the fabrics treated with the conventional pad-dry-cure

method. Also, all fabrics treated with the atmospheric plasma treatment, except for the

fabrics containing natural fibers, were also equally as durable as the conventionally treated

fabrics. Currently, the only hurdle making this technology a viable replacement for

conventional pad-dry-cure finishing is the cost associated with the process, at least for the

DCPS APPLD process used in this research. Currently there are two major commercial

players that have the ability to treat a full width fabric at more than 25 yards per minute.

These two companies are Dow Corning Plasma Solutions with their AP4 machine and APJeT

with their TexJet machine. This research study was conducted solely on the technology

available from Dow Corning. A future research study should be conducted in a similar

manner with the APJeT technology.

102

6. List of References

(1) Lieberman, M.; Lichtenberg, A. In Principles of Plasma Discharges and Materials Processing; Wiley-Interscience: Hoboken, N. J., 2005.

(2) Holme, I. In Water Repellency and Waterproofing; Heywood, D., Ed.; Textile Finishing; Society of Dyers and Colourists: West Yorkshire, UK, 2003; pp 137-213.

(3) Kissa, E. In Handbook of Fiber Science and Technology; Lewin, M., Sello, S., Eds.; Marcel Dekker: New York, NY, 1984; Vol. II Chemical Processing of Fibers and Fabrics Part B.

(4) Gibbs, J. In Trans. Connecticut Acad. 3, (1876-1878); Collecte Works; Longmas: New York, NY, 1928; Vol. I.

(5) Young, T. An Essay on the Cohesion of Fluids. Phil. Trans. Roy. Soc. 1805, 95, 65-87.

(6) Adam, N. In The Chemical Structure of Solid Surfaces as Deduced from Contact Angles; Gould, R., Ed.; Contact Angle, Wettability and Adhesion; Amer. Chem. Soc.: Washington, DC, 1964; Vol. 43.

(7) Fowkes, F.; Harkins, W. The State of Monolayers Adsorbed at the Interface Solid-Aqueous Solution. J. Am. Chem. Soc. 1940, 43, 3377-3386.

(8) Wenzel, R. Resistance of Solid Surfaces to Wetting by Water. Ind. Eng. Chem. 1936, 28, 988-994.

(9) Zisman, W. In Relation of the Equilibrium Contact Angle to Liquid and Solid Constitution; Good, R., Ed.; Contact Angle, Wettability, and Adhesion; Amer. Chem. Soc.: Washington, DC, 1964; Vol. 43.

(10) Fox, H.; Zisman, W. The Spreading of Liquids on Low-Energy Surfaces. II. Modified Tetrafluoroethylene Polymers. J. Colloid Sci. 1956, 7, 109-121.

(11) Good, R.; Girifalko, L. A Theory for Estimation of Surface and Interfacial Energies. III. Estimation of Surface Energies of Solids from Contact Angle Data. J. Phys. Chem. 1960, 64, 561-565.

103

(12) Wu, S. Surface Tension of Solids: An Equation of State Analysis. J. Colloid Interface Sci. 1979, 71, 605-609.

(13) Fowkes, F. Active Forces at Interfaces. Ind. Eng. Chem. 1964, 56, 40-52.

(14) Owens, D.; Wendt, R. Estimation of the Surface Free Energy of Polymers. J. Appl. Polym. Sci. 1969, 13, 1741-1747.

(15) Osipow, L. In Surface Chemistry Theory and Industrial Applications; ACS Monograph 153; Reinhold: New York, 1962.

(16) Weast, R. In Surface Tensions of Common Liquids; Handbook of Chemistry and Physics; CRC Press Inc.: Boca Raton, FL, 2007; Vol. 87, pp 6.127-6.130.

(17) Audenaert, F.; Lens, H.; Rolly, D.; Van der Elst, P. Fluorochemical Textile Repellents - Synthesis and Applications: A 3M Perspective. J. Text. Inst. 1999, 90, 76-94.

(18) Baxter, S.; Cassie, A. The Water Repellency of Fabrics and a New Water Repellency Test. J. Text. Inst. 1945, 36, T67-T90.

(19) Harding, T. Water Repellency of Textiles - Past Developments and Future Prospects. J. Text. Inst. 1951, 42, P691-P702.

(20) Howells, R. Water, Waterproofing and Water/Oil Repellency. Kirk-Othmer 2000March 8, 2006.

(21) Schindler, W.; Hauser, P. In Chemical Finishing of Textiles; Woodhead Publishing Limited: Cambridge, England, 2004.

(22) De Marco, C.; McQuade, A.; Kennedy, S. For Rainwear, A New Durable Water-Repellent Finish. Mod. Text. Mag 1960, 41, 50-56.

(23) Madaras, G. Water-Repellent Finishes - Modern Use of Silicones. J. Soc. Dyers Colourists 1958, 74, 835-841.

(24) Cray, S.; Budden, G. It Looks Good, But Does It Feel Good? Int. Dyer 1997, 182, 19-23.

(25) Fortess, F. Silicon Resins in Textiles. Ind. Eng. Chem. 1954, 46, 2325-2334.

(26) Simons, J. In Fluorine chemistry; Academic Press: New York, NY, 1950; Vol. I.

(27) Nuyttens, R. Fluorochemicals: High Performance Finishes for Textile Protection. Text. Tech. Int. 1995, 167-169.

104

(28) Wilson, A. Scotchgard to be Pulled by 3M. Text. Month. Jun 2000, 4.

(29) Grottenmüller, R. Fluorocarbons - An Innovative Aid to the Finishing of Textiles. Melliand Textilber 1998, 79, E195-E197.

(30) Thumm, S. LAD-Fluorocarbon Technology for High-Tech Sports-Wear. Int. Text. Bulletin 2000, 46, 56-61.

(31) U.S. Environmental Protection Agency Perfluorooctanoic Acid (PFOA) and Fluorinated Telomers. http://www.epa.gov/opptintr/pfoa/index.htm (accessed January, 2007).

(32) American Association of Textile Chemists and Colorists In AATCC Technical Manual; Chehna, A., Agrawal, N., Ricard, L., Smith, G. and Varley, A., Eds.; Amerian Association of Textile Chemists and Colorists: Raleigh, NC, 2006; Vol. 81.

(33) Tomasino, C. In Chemistry & Technology of Fabric Preparation & Finishing. Department of Tex. Engr., Chem. & Sci. Col. of Textiles: Raleigh, North Carolina, 1992.

(34) Interox In A Bleachers Handbook; Interox America: Houston, TX, 1983.

(35) Preston, J.; Bennett, A. Some Aspects of the Drying and Heating of Textiles V - Migration in Relation to Moisture Content. J. Soc. Dyers Colourists 1951, 67, 101-102.

(36) Wallace, G.; Brown, P. Horse Rug Lung: Toxic Pneumonitis Due to Fluorocarbon Inhalation. Occup Environ Med 2005, 62, 414-416.

(37) Vigo, T. In Textile Processing and Properties: Preparation, Dyeing, Finishing, and Performance; Textile Science and Technology; Elsevier: New York, NY, 1994; Vol. 11.

(38) Chan, C. In Polymer Surface Modification and Characterization; SPE Books; Hanser/Gardner Publications, Inc.: New York, NY, 1994.

(39) Garbassi, F.; Morra, M.; Occhiello, E. In Polymer Surfaces; Wiley: Chichester, England, 1998.

(40) Waddell, W.; Evans, L.; Gilick, J.; Shuttleworth, D. Polymer Surface Modification. Rubber Chem. and Technol. 1992, 65, 687-696.

(41) Reichmanis, E.; Frank, C.; O'Donnell, J. In Irradiation of Polymeric Materials: Processes, Mechanisms, and Applications. ACS Symposium Series; American Chemical Society: Washington, DC, 1993; Vol. 527.

(42) Matthews, S. Plasma Aided Finishing of Textile Materials, North Carolina State University, Raleigh, NC, 2005.

105

(43) Goodwin, A.; Leadley, S.; Swallow, F.; Dobbyn, P. An Atmospheric Pressure Plasma Assembly. Country Cork, Ireland. WO Patent 086031. October 16, 2003.

(44) Virk, R.; Ramaswamy, G.; Bourham, M.; Bures, B. Plasma and Antimicrobial Treatment of Nonwoven Fabrics for Surgical Gowns. Text. Res. J. 2004, 74, 1073-1079.

(45) Tendero, C.; Tixier, C.; Tristant, P.; et.al. Atmospheric Pressure Plasmas: A Review. Spect. Acta P. B: Atomic Spect. 2006, 61, 2-30.

(46) Iriyama, Y.; Yasuda, T.; Cho, D.; Yasuda, H. Plasma Surface Treatment on Nylon Fabrics by Fluorocarbon Compounds. J. Appl. Polym. Sci. 1990, 39, 249-264.

(47) Wolf, R.; Sparavigna, A. The Plasma Advantage. http://www.textileworld.com/News.htm?CD=3232&ID=10308 (accessed February 2, 2006).

(48) Hynes, A. Pulsed Plasma Polymerization of Perfluorocyclohexane. Macromolecules 1996, 29, 4220-4225.

(49) Cecchi, J. In Introduction to Plasma Concepts and Discharge Configurations; Rossnagel, S., Cuomo, J. and Westwood, W., Eds.; Handbook of Plasma Processing Technology - Fundamentals, Etching, Deposition, and Surface Interactions; Noyes Publications: Park Ridge, NJ, 1990; pp 14-69.

(50) "Europlasma: Plasma Treatment" Tech. Text. March 2003, 46, E21-E22.

(51) McCord, M.; Hwang, Y.; Hauser, P.; et al. Modifying Nylon and Polypropylene Fabrics with Atmospheric Pressure Plasmas Text. Res. J. 2002, 72, 491-498.

(52) Herbert, T. Atmospheric Pressure Plasma Liquid Deposition - a New Route to High-Performance Textiles Int. Dyer 2003, 188, 11-13.

(53) Shenton, M.; Stevens, G.; Wright, N.; Duan, X. Chemical-Surface Modification of Polymers Using Atmospheric Pressure Nonequilibrium Plasmas and Comparisons with Vacuum Plasmas. J. Polym. Sci. Part A: Polym. Chem. 2001, 40, 95-109.

(54) Godyak, V. Plasma Phenomena in Inductive Discharges. Plasma Phys. Control. Fusion 2003, 45, A399-A424.

(55) Chaivan, P.; Pasaja, N.; Boonyawan, D.; et. al. Low-Temperature Plasma Treatment for Hydrophobicity Improvement of Silk. Surf. Coat. Technol. 2005, 193, 356-360.

(56) Roth, J. In Industrial Plasma Engineering; Institute of Physics Pub.: Philadelphia, PA, 1995; Vol. 2.

106

(57) Raizer, Y.; Shneider, M.; Yatsenko, N. In Radio-Frequency Capacitive Discharges; CRC Press: Boca Raton, FL, 1995.

(58) Shul, R.; Pearton, S. In Handbook of Advanced Plasma Processing Techniques; Springer: New York, NY, 2000.

(59) Wang, H.; Rembold, M.; Wang, J. Characterization of Surface-Properties of Plasma-Polymerized Fluorinated Hydrocarbon Layers - Surface Stability as a Requirement for Permanent Water Repellency. J. Appl. Polym. Sci. 1993, 49, 701-710.

(60) Hocker, H. Plasma Treatment of Textile Fibers Pure Appl. Chem. 2002, 74, 423-427.

(61) Herbert, P.; Bourdin, E. New Generation Atmospheric Pressure Plasma Technology for Industrial On-Line Processing. J. Coated Fabrics 1999, 28, 170-182.

(62) Kanazawa, S.; Kogoma, M.; Moriwaki, T.; Okazaki, S. Stable Glow Plasma at Atmospheric Pressure. J. Phys. D: Appl. Phys. 1988, 21, 838-840.

(63) Yokoyama, T.; Kogoma, M.; Moriwaki, T.; Okazakit, S. The Mechanism of the Stabilization of Glow Plasma at Atmospheric Pressure. J. Phys. D: Appl. Phys. 1990, 23, 1125-1128.

(64) Herbert A.; O'Reilly F.; Braddell J.; Dobbyn P. An Atmospheric Pressure Plasma System. Midleton County Cork, Ireland. WO Patent 59809. August 16, 2001.

(65) Duan, X. Method Of and Apparatus for Microwave-Plasma Production. Cheshire, GB. US Patent 5874705. April 8, 1997.

(66) Shenton, M. Surface Modification of Polymer Surfaces: Atmospheric Plasma versus Vacuum Plasma Treatments. J. Phys. D: Appl. Phys. 2001, 34, 2761-2768.

(67) Schutze, A.; Jeong, J.; Babayan, S.; et. al. The Atmospheric-Pressure Plasma Jet: A Review and Comparison to Other Plasma Sources. IEEE Trans. Plasma Sci. 1998, 26, 1685-1693.

(68) Selwyn, G. Atmospheric-Pressure Plasma Jet. New Mexico, US. US Patent 5961772. October 5, 1999.

(69) Avondale, APJet To Promote Plasma Treatment of Fabrics Textile World 2005, January, 49.

(70) Selwyn, G.; Henins, I.; Babayan, S.; Hicks, R. Large Area Atmospheric-Pressure Plasma Jet. New Mexico, US. US Patent 6262523. April 21, 1999.

107

(71) Goodwin, A.; Merlin, P.; Badyal, J.; Ward, L. Method and Apparatus for Forming a Coating. Michigan, USA. WO Patent 28548. September 25, 2001.

(72) Cotton Incorporated. http://www.cottoninc.com/AboutCotton/ (accessed January 15, 2007).

(73) ASTM International Standard Test Method for Breaking Strength and Elongation of Textile Fabrics (Grab Test). www.ihs.com (accessed January 15, 2007).

(74) Dow Corning Large-Area APPLD Equipment Platform from Dow Corning Plasma Solutions. http://www.dowcorning.com/content/plasma/large_area_APPLD.asp (accessed February, 3, 2007).

(75) Dow Corning Brochure Atmospheric Pressure Plasma Liquid Deposition: A Portfolio of Equipment Platforms. http://www.dowcorning.com/content/publishedlit/01-3096-01.pdf (accessed February 3, 2007).

(76) Moulder, J.; Stickle, W.; Sobol, P.; Bombem, K. In Handbook of X-ray Photoelectron Spectroscopy; Chastain, J., King, R. J., Eds.; Physical Electronics, Inc.: Eden Prairie, MN, 1995.

108

7. Appendices

109

Appendix A: Dow Corning’s Atmospheric Pressure Plasma Liquid Deposition

Dow Corning Plasma Solution’s (DCPS) Atmospheric Pressure Plasma Liquid

Deposition (APPLD) technology is unique by the way chemical precursors, called coating-

forming materials in the patent, are introduced into a plasma region. Figure 7.1 below is the

precursor injection apparatus referred to as an atomizer in a DCPS patent.71

Figure 7.1. APPLD Precursor Injection Apparatus (Taken From WO Patent 28548)

According to the patent, the atomizer consisted of a Sonoteck 8700-120 ultrasonic

nozzle (30) connected to a Sono-tek 06-05108 broadband ultrasonic generator (32). The

patent states that the optimal drop size for the coating-forming material ejected from the

atomizer should have a drop size from 10 to 50 microns. Because DCPS uses an atomizer to

110

inject the precursor into the plasma region, precursor monomers can be immiscible or in

different phases unlike other atmospheric plasma processes. Also, these precursors do not

have to be introduced into the plasma by a carrier gas such as helium; it can be directly

injected.

DCPS also has a patent where they took their technology purchased from Plasma

Ireland and combined it with their APPLD technology.64 A figure depicting the APPLD

treatment being used in a continuous process is given below in Figure 7.2 below.

Figure 7.2. Continuous APPLD Treatment (Taken from WO Patent 59809)

Figure 7.2 shows one APPLD treatment module. The fabric travels into plasma

region 25 where it is cleaned, then moves into the treatment region (60). Note that the

ultrasonic nozzle (74) is the same device given in Figure 7.1.

111

The machine that was used in this research was the SE-1100 LabLine platform,

shown in Figure 7.374 below, that is a stand alone, reel-to-reel surface engineering system for

flexible web materials up to 12.5 inches wide. The web is handled by an unwind/rewind

system with a maximum reel mass of 100 kilograms and a maximum line speed of 20 meters

per minute. This machine is used to simulate the results which would be possible on their

full width SE-1000 AP4 machine.

Figure 7.3. DCPS SE-1100 LabLine Machine

The SE-1000 AP4 machine from DCPS, shown in Figure 7.475, is capable of treating

fabrics up to 2.5 meters (98 inches) wide. Individual modules can be purchased for multiple

treatments or multiple passes. It can be configured for either in-line production or as a stand

alone system with the addition of web handling equipment. The foot print of the SE-1000

AP4 machine is 2 meters wide by 3.8 meters long and is 3.3 meters high. DCPS has

provided an approximate cost of a 3 station SE-1000 AP4 machine that will allow three

112

passes as performed in this research to be between 2.5 and 4 million US dollars depending on

the need for web handling equipment, and the amount of integration into the current

production line. The SE-1000 AP4 requires one operator.

Figure 7.4. DCPS SE-1000 AP4 Machine

113

Appendix B: X-ray Photoelectron Spectroscopy (XPS)

All information in this appendix has been taken from the book Handbook of X-ray

Photoelectron Spectroscopy.76

XPS is a surface analysis technique that irradiates a sample with monoenergetic soft

x-rays and analyzes the energy of the electrons that are emitted from the surface. There are

three different types of x-rays that can be used. In this study Mg Kα (1486.7 eV) x-rays were

used exclusively. These photons interact with atoms only 1-10 microns into the surface

because they have limited penetrating power. The photons cause electrons on the surface to

be emitted by the photoelectric effect. These electrons have a kinetic energy which can be

measured. From this kinetic energy, the binding energy of the atomic orbital from which the

electron originated can be determined by subtracting out the energy of the photon and the

spectrometer work function.

The measured binding energies of electrons are the key to XPS. Binding energies can

be defined as the difference between the initial and final states after the photoelectron has left

the atom that was bombarded by the x-rays. Electron binding energies are unique to each

element in the periodic table. Because XPS can measure these binding energies, it can be

used to both identify and determine the concentration of elements on the surface.

In order to produce the binding energy spectra, electrons leaving the surface are

detected by an electron spectrometer according to their kinetic energy. The analyzer can

only accept electrons at a specific kinetic energy. A variable electrostatic field is placed

114

before the analyzer in order to determine the different energies of the electrons. The

electrons are detected as discrete events. The number of electrons detected in a given time is

given on the y-axis and the binding energy of the electron is displayed on the x-axis.

The electrons that leave the surface without energy loss produce peaks in the spectra.

There is usually multiple spikes due to one element. This is because roughly 10-14 seconds

after the photoelectric event, excited ions emit Auger electrons. Software packages are used

to analyze the XPS spectrum to determine what elements are present on the surface and in

what quantities.

115

Appendix C: Cotton Additional Tables and Figures

Photograph of Cotton Fabric Used in This Research

116

Appendix C: XPS Binding Energy Scan of Cotton

Fl 1

s

Fl A

uger

Pea

ks

O 1

s

C 1

s

Fl 1

s

Fl A

uger

Pea

ks

O 1

s

C 1

s

117

Appendix C: Individual Repellency Tests for Cotton

Washes Finish Water Absorbed (g) Washes Finish Contact Angle0 P 0.4 0 P 1520 P 0.4 0 P 1530 P 0.4 0 P 1580 W 1.3 0 P 1450 W 1 0 P 1500 W 1.3 0 W 1595 P 12.3 0 W 1605 P 7.5 0 W 1605 P 10.3 0 W 1525 W 0.1 0 W 1525 W 0.1 5 P 05 W 0.1 5 P 010 P 14 5 P 010 P 15.5 5 P 010 P 17.1 5 P 010 W 0.1 5 W 13510 W 0 5 W 14310 W 0 5 W 150

5 W 1535 W 14310 P 010 P 0

Washes Finish Rating 10 P 00 CTRL 0 10 P 00 CTRL 0 10 P 00 P 100 10 W 1430 P 100 10 W 1430 W 100 10 W 1350 W 100 10 W 1455 P 60 10 W 1485 P 505 W 955 W 9510 P 010 P 0 Finish Element Composition10 W 85 CTRL C 63%10 W 90 CTRL O 37%

CTRL Fl 0%W C 33%W O 5%W Fl 62%P C 5%P O 32%P Fl 63%

XPS

Impact Test Contact Angle Test

Spray Test

118

Appendix C: Contact Angle ANOVA between Finishes (Cotton) As Received

130

135

140

145

150

155

160

165C

onta

ct A

ngle

P W

Finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.2803950.1904444.477723

154.110

Summary of Fit

W-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

5.0002.832

11.531-1.531

0.95

t RatioDFProb > |t|Prob > tProb < t

1.7655618

0.11550.05770.9423 -10 -5 0 5 10

t Test

FinishErrorC. Total

Source189

DF62.50000

160.40000222.90000

Sum of Squares62.500020.0500

Mean Square3.1172F Ratio

0.1155Prob > F

Analysis of Variance

PW

Level55

Number151.600156.600

Mean2.00252.0025

Std Error146.98151.98

Lower 95%156.22161.22

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Contact Angle By Finish Washes=0

119

Appendix C: Contact Angle ANOVA Within W-Finish (Cotton)

130

135

140

145

150

155

160

165C

onta

ct A

ngle

0 5 10

Washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.6065140.5409345.483308148.0667

15

Summary of Fit

WashesErrorC. Total

Source2

1214

DF556.13333360.80000916.93333

Sum of Squares278.06730.067

Mean Square9.2483F Ratio

0.0037*Prob > F

Analysis of Variance

0510

Level555

Number156.600144.800142.800

Mean2.45222.45222.4522

Std Error151.26139.46137.46

Lower 95%161.94150.14148.14

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Contact Angle By Washes Finish=W

120

Appendix D: Polyester/Cotton Additional Tables and Figures

Photograph of Polyester/Cotton Fabric Used in This Research

121

Appendix D: XPS Binding Energy Scan of Polyester/Cotton

Fl 1

s

Fl A

uger

Pea

ks

O 1

s

C 1

s

Fl 1

s

Fl A

uger

Pea

ks

O 1

s

C 1

s

122

Appendix D: Individual Repellency Tests for Polyester/Cotton

Washes Finish Rating Washes Finish Water Absorbed (g) Finish Element Composition0 CTRL 0 0 P 15.2 CTRL C 65%0 CTRL 0 0 P 14.9 CTRL O 35%0 CTRL 0 0 P 15.9 W C 31%0 P 95 0 W 5.3 W O 4%0 P 95 0 W 6.6 W F 65%0 P 100 0 W 4.9 WM C 33%0 W 100 0 WM 8.9 WM O 5%0 W 100 0 WM 9.3 WM F 60%0 W 100 5 P 11.8 WM N 2%0 WM 100 5 P 16.9 P C 32%0 WM 100 5 P 16.9 P O 4%0 WM 100 5 W 2.4 P F 64%5 P 80 5 W 4.35 P 80 5 W 4.15 P 80 5 WM 85 W 100 5 WM 75 W 100 5 WM 7.65 W 100 10 P 15.45 WM 100 10 P 16.15 WM 100 10 P 17.15 WM 100 10 W 3.710 P 70 10 W 3.810 P 70 10 W 2.910 P 70 10 WM 7.510 W 100 10 WM 4.710 W 100 10 WM 210 W 100 25 P 17.410 WM 95 25 P 16.910 WM 100 25 P 16.610 WM 100 25 W 1.825 P 50 25 W 1.625 P 50 25 W 0.825 P 60 25 WM 3.825 W 95 25 WM 4.125 W 100 25 WM 3.825 W 10025 WM 9025 WM 9025 WM 95

Spray Test Impact Test XPS Test

123

Appendix D: Individual Repellency Tests for Polyester/Cotton (cont.)

Contact Angle Test Washes Finish Contact Angle Washes Finish Contact Angle

0 P 155 10 P 138 0 P 156 10 P 140 0 P 148 10 P 143 0 P 145 10 P 140 0 P 148 10 P 147 0 W 153 10 W 148 0 W 151 10 W 156 0 W 145 10 W 153 0 W 148 10 W 157 0 W 152 10 W 150 0 WM 163 10 WM 158 0 WM 154 10 WM 148 0 WM 153 10 WM 158 0 WM 158 10 WM 148 0 WM 151 10 WM 157 5 P 152 25 P 135 5 P 145 25 P 132 5 P 147 25 P 135 5 P 147 25 P 140 5 P 140 25 P 147 5 W 156 25 W 148 5 W 154 25 W 150 5 W 155 25 W 154 5 W 158 25 W 152 5 W 152 25 W 149 5 WM 154 25 WM 155 5 WM 162 25 WM 150 5 WM 155 25 WM 149 5 WM 159 25 WM 149 5 WM 146 25 WM 159

124

Appendix D: Contact Angle ANOVA between Finishes (Polyester/Cotton) As Received

130

135

140

145

150

155

160

165co

ntac

t ang

le

P W WM

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.3250.2125

4.34741315215

Summary of Fit

finishErrorC. Total

Source2

1214

DF109.20000226.80000336.00000

Sum of Squares54.600018.9000

Mean Square2.8889F Ratio

0.0946Prob > F

Analysis of Variance

PWWM

Level555

Number150.400149.800155.800

Mean1.94421.94421.9442

Std Error146.16145.56151.56

Lower 95%154.64154.04160.04

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=0

125

Appendix D: Contact Angle ANOVA between Finishes (Polyester/Cotton) at 5 Washes

130

135

140

145

150

155

160

165co

ntac

t ang

le

P W WM

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.5222780.4426584.487018152.1333

15

Summary of Fit

finishErrorC. Total

Source2

1214

DF264.13333241.60000505.73333

Sum of Squares132.06720.133

Mean Square6.5596F Ratio

0.0119*Prob > F

Analysis of Variance

PWWM

Level555

Number146.200155.000155.200

Mean2.00672.00672.0067

Std Error141.83150.63150.83

Lower 95%150.57159.37159.57

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=5

126

Appendix D: Contact Angle ANOVA between Finishes (Polyester/Cotton) at 10 Washes

130

135

140

145

150

155

160

165co

ntac

t ang

le

P W WM

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.6751030.6209544.289522

149.415

Summary of Fit

finishErrorC. Total

Source2

1214

DF458.80000220.80000679.60000

Sum of Squares229.40018.400

Mean Square12.4674F Ratio

0.0012*Prob > F

Analysis of Variance

PWWM

Level555

Number141.600152.800153.800

Mean1.91831.91831.9183

Std Error137.42148.62149.62

Lower 95%145.78156.98157.98

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=10

127

Appendix D: Contact Angle ANOVA between Finishes (Polyester/Cotton) at 25 Washes

130

135

140

145

150

155

160

165co

ntac

t ang

le

P W WM

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.7243220.6783754.483302146.9333

15

Summary of Fit

finishErrorC. Total

Source2

1214

DF633.73333241.20000874.93333

Sum of Squares316.86720.100

Mean Square15.7645F Ratio

0.0004*Prob > F

Analysis of Variance

PWWM

Level555

Number137.800150.600152.400

Mean2.00502.00502.0050

Std Error133.43146.23148.03

Lower 95%142.17154.97156.77

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=25

128

Appendix D: Contact Angle ANOVA within Finishes (Polyester/Cotton) W Finish

130

135

140

145

150

155

160

165co

ntac

t ang

le

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.3619740.2423443.008322

152.0520

Summary of Fit

washesErrorC. Total

Source3

1619

DF82.15000

144.80000226.95000

Sum of Squares27.38339.0500

Mean Square3.0258F Ratio

0.0602Prob > F

Analysis of Variance

051025

Level5555

Number149.800155.000152.800150.600

Mean1.34541.34541.34541.3454

Std Error146.95152.15149.95147.75

Lower 95%152.65157.85155.65153.45

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By washes finish=W

129

Appendix D: Contact Angle ANOVA within Finishes (Polyester/Cotton) WM Finish

130

135

140

145

150

155

160

165co

ntac

t ang

le

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.074537-0.098995.181699

154.320

Summary of Fit

washesErrorC. Total

Source3

1619

DF34.60000

429.60000464.20000

Sum of Squares11.533326.8500

Mean Square0.4295F Ratio

0.7346Prob > F

Analysis of Variance

051025

Level5555

Number155.800155.200153.800152.400

Mean2.31732.31732.31732.3173

Std Error150.89150.29148.89147.49

Lower 95%160.71160.11158.71157.31

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By washes finish=WM

130

Appendix D: Contact Angle ANOVA within Finishes (Polyester/Cotton) P Finish

130

135

140

145

150

155

160

165co

ntac

t ang

le

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.5583130.4754964.716991

14420

Summary of Fit

washesErrorC. Total

Source3

1619

DF450.00000356.00000806.00000

Sum of Squares150.00022.250

Mean Square6.7416F Ratio

0.0038*Prob > F

Analysis of Variance

051025

Level5555

Number150.400146.200141.600137.800

Mean2.10952.10952.10952.1095

Std Error145.93141.73137.13133.33

Lower 95%154.87150.67146.07142.27

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By washes finish=P

131

Appendix E: Polyester Additional Tables and Figures

Photograph of Calendered Polyester Fabric Used in This Research

132

Appendix E: Photograph of Non-Calendered Polyester Used in This Research

133

Appendix E: XPS Binding Energy Scan of Polyester

Fl 1

s

Fl A

uger

Pea

ks

O 1

s

C 1

s

Fl 1

s

Fl A

uger

Pea

ks

O 1

s

C 1

s

134

Appendix E: Individual Repellency Tests for Polyester

Washes Finish Rating Washes Finish Water Absorbed (g) Finish Element Composition0 C-CTRL 0 0 C-P 0.1 C-CTRL C 82%0 C-CTRL 0 0 C-P 0 C-CTRL O 18%0 C-CTRL 0 0 C-P 0 NC-CTRL C 80%0 NC-CTRL 0 0 C-W 0 NC-CTRL O 20%0 NC-CTRL 0 0 C-W 0 C-W C 33%0 NC-CTRL 0 0 C-W 0 C-W O 4%0 C-P 100 0 NC-P 0.1 C-W Fl 63%0 C-P 100 0 NC-P 0.1 C-P C 32%0 C-P 100 0 NC-P 0.1 C-P O 5%0 C-W 100 5 C-P 0 C-P Fl 64%0 C-W 100 5 C-P 0.1 NC-P C 30%0 C-W 100 5 C-P 0 NC-P O 5%0 NC-P 100 5 C-W 0 NC-P Fl 65%0 NC-P 100 5 C-W 00 NC-P 100 5 C-W 0.15 C-P 100 5 NC-P 0.15 C-P 100 5 NC-P 0.15 C-P 100 5 NC-P 0.15 C-W 100 10 C-P 05 C-W 100 10 C-P 0.15 C-W 100 10 C-P 05 NC-P 100 10 C-W 05 NC-P 100 10 C-W 0.15 NC-P 100 10 C-W 010 C-P 100 10 NC-P 0.110 C-P 100 10 NC-P 0.110 C-P 100 10 NC-P 0.110 C-W 100 25 C-P 0.110 C-W 100 25 C-P 010 C-W 100 25 C-P 010 NC-P 100 25 C-W 010 NC-P 100 25 C-W 0.110 NC-P 100 25 C-W 025 C-P 100 25 NC-P 025 C-P 100 25 NC-P 0.125 C-P 100 25 NC-P 0.125 C-W 10025 C-W 10025 C-W 10025 NC-P 10025 NC-P 10025 NC-P 100

Spray Test Impact Test XPS Test

135

Appendix E: Individual Repellency Tests for Polyester (cont.)

Contact Angle Test Washes Finish Contact Angle Washes Finish Contact Angle

0 C-P 124 10 C-P 143 0 C-P 132 10 C-P 150 0 C-P 131 10 C-P 153 0 C-P 124 10 C-P 143 0 C-P 125 10 C-P 140 0 C-W 140 10 C-W 141 0 C-W 126 10 C-W 145 0 C-W 122 10 C-W 143 0 C-W 131 10 C-W 146 0 C-W 135 10 C-W 143 0 NC-P 152 10 NC-P 151 0 NC-P 158 10 NC-P 151 0 NC-P 162 10 NC-P 156 0 NC-P 158 10 NC-P 151 0 NC-P 147 10 NC-P 156 5 C-P 142 25 C-P 150 5 C-P 146 25 C-P 152 5 C-P 148 25 C-P 148 5 C-P 133 25 C-P 135 5 C-P 140 25 C-P 140 5 C-W 145 25 C-W 138 5 C-W 142 25 C-W 148 5 C-W 140 25 C-W 146 5 C-W 143 25 C-W 148 5 C-W 143 25 C-W 144 5 NC-P 147 25 NC-P 153 5 NC-P 148 25 NC-P 153 5 NC-P 153 25 NC-P 149 5 NC-P 149 25 NC-P 158 5 NC-P 158 25 NC-P 156

136

Appendix E: Individual Additional Test Results for Polyester

Washes Finish Water Pressure (cm) Washes Finish Permeability (cfm) Finish Warp Fill0 C-P 91.0 0 C-CTRL 0.44 C-W 0.6% 0.0%0 C-P 98.7 0 NC-CTRL 9.40 C-W 0.6% 0.0%0 C-P 97.0 0 C-P 0.36 C-W 0.6% 0.0%0 C-W 67.5 0 C-P 0.28 C-W 0.6% 0.0%0 C-W 67.0 0 C-P 0.35 C-W 0.6% 0.0%0 C-W 66.8 0 C-W 0.75 C-W 1.3% 0.3%0 NC-P 41.2 0 C-W 0.74 NC-P 3.8% 0.0%0 NC-P 40.8 0 C-W 0.74 NC-P 3.8% 0.0%0 NC-P 43.0 0 NC-P 7.74 NC-P 4.4% 0.0%5 C-P 80.8 0 NC-P 7.91 NC-P 3.8% 0.0%5 C-P 79.9 0 NC-P 8.03 NC-P 3.8% 0.3%5 C-P 78.5 5 C-P 0.45 NC-P 3.8% 0.0%5 C-W 80.9 5 C-P 0.41 C-P 1.9% 0.6%5 C-W 77.7 5 C-P 0.40 C-P 2.5% 0.6%5 C-W 79.9 5 C-W 0.74 C-P 2.5% 0.6%5 NC-P 41.9 5 C-W 0.74 C-P 2.2% 0.6%5 NC-P 40.8 5 C-W 0.74 C-P 1.9% 0.6%5 NC-P 41.5 5 NC-P 9.96 C-P 1.9% 0.6%10 C-P 77.0 5 NC-P 10.4010 C-P 74.2 5 NC-P 10.3010 C-P 76.3 10 C-P 0.8610 C-W 71.5 10 C-P 0.8610 C-W 69.1 10 C-P 0.8610 C-W 72.3 10 C-W 0.7910 NC-P 44.1 10 C-W 0.7710 NC-P 39.0 10 C-W 0.7610 NC-P 42.3 10 NC-P 9.7825 C-P 70.0 10 NC-P 10.1025 C-P 73.8 10 NC-P 9.5325 C-P 68.6 25 C-P 1.0125 C-W 72.3 25 C-P 1.0425 C-W 66.8 25 C-P 1.0025 C-W 63.0 25 C-W 0.7825 NC-P 41.7 25 C-W 0.7725 NC-P 42.2 25 C-W 0.7825 NC-P 44.2 25 NC-P 9.86

25 NC-P 10.1025 NC-P 10.00

Air PermeabilityHydrostatic Pressure Test 5 Wash Shrinkage Test

137

Appendix E: Individual Additional Test Results for Polyester (cont.)

Tensile Test Washes Finish Warp (lb) Fill (lb) Washes Finish Warp (lb) Fill (lb)

0 C-CTRL 183.2 103.8 5 NC-P 177.9 107.7 0 C-CTRL 180.2 105.6 5 NC-P 169.6 111.3 0 C-CTRL 181.1 99.1 5 NC-P 164.8 109.3 0 C-CTRL 187 106.6 5 NC-P 170.3 111.4 0 C-CTRL 189.1 104.7 5 NC-P 174.1 108 0 NC-CTRL 180.2 109.7 10 C-P 174.9 110 0 NC-CTRL 181.7 110.1 10 C-P 175.6 105.7 0 NC-CTRL 180.4 105.5 10 C-P 171.1 103.6 0 NC-CTRL 184.2 104.6 10 C-P 180.4 104.7 0 NC-CTRL 180 111.1 10 C-P 173.6 108.6 0 C-P 173.4 105 10 C-W 172 100 0 C-P 163.5 110.2 10 C-W 179.1 104.2 0 C-P 167.7 102 10 C-W 174.5 102.6 0 C-P 169.2 105.7 10 C-W 172.6 92 0 C-P 171.1 113.2 10 C-W 175.8 99.7 0 C-W 177.9 97.3 10 NC-P 177.5 110.9 0 C-W 176.8 95.1 10 NC-P 176.4 111.1 0 C-W 174.5 105 10 NC-P 173.4 110.6 0 C-W 177 102.4 10 NC-P 178.7 109.2 0 C-W 177.7 99.3 10 NC-P 168.4 111.3 0 NC-P 180.4 109.5 25 C-P 170.3 98.9 0 NC-P 185.3 109.2 25 C-P 176.6 103.3 0 NC-P 168.5 108.3 25 C-P 174.1 102.4 0 NC-P 186.3 108.3 25 C-P 172.4 98.9 0 NC-P 163.4 102.5 25 C-P 172.6 93.9 5 C-P 177.2 99.4 25 C-W 171.7 104.9 5 C-P 172 103.8 25 C-W 171.5 107.8 5 C-P 176.4 103.8 25 C-W 177.2 103.1 5 C-P 167.6 103.8 25 C-W 165.2 100.8 5 C-P 169.8 101.9 25 C-W 163.5 101.2 5 C-W 179.6 91.2 25 NC-P 176.6 109.2 5 C-W 173.9 87.6 25 NC-P 170.3 103.9 5 C-W 176 90 25 NC-P 169.8 108.3 5 C-W 176.8 93.8 25 NC-P 167.7 108.5 5 C-W 167.8 86.9 25 NC-P 167.7 107.8

138

Appendix E: Contact Angle ANOVA between Finishes (Polyester) As Received

120

130

140

150

160

170co

ntac

t ang

le

C-P C-W NC-P

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.8533550.8289145.80804

137.815

Summary of Fit

finishErrorC. Total

Source2

1214

DF2355.6000404.8000

2760.4000

Sum of Squares1177.80

33.73

Mean Square34.9150F Ratio

<.0001*Prob > F

Analysis of Variance

C-PC-WNC-P

Level555

Number127.200130.800155.400

Mean2.59742.59742.5974

Std Error121.54125.14149.74

Lower 95%132.86136.46161.06

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=0

139

Appendix E: Contact Angle ANOVA between Finishes (Polyester) 5 Washes

120

130

140

150

160

170co

ntac

t ang

le

C-P C-W NC-P

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.52820.4495664.396969145.1333

15

Summary of Fit

finishErrorC. Total

Source2

1214

DF259.73333232.00000491.73333

Sum of Squares129.86719.333

Mean Square6.7172F Ratio

0.0110*Prob > F

Analysis of Variance

C-PC-WNC-P

Level555

Number141.800142.600151.000

Mean1.96641.96641.9664

Std Error137.52138.32146.72

Lower 95%146.08146.88155.28

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=5

140

Appendix E: Contact Angle ANOVA between Finishes (Polyester) 10 Washes

120

130

140

150

160

170co

ntac

t ang

le

C-P C-W NC-P

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.5957940.5284263.696846147.4667

15

Summary of Fit

finishErrorC. Total

Source2

1214

DF241.73333164.00000405.73333

Sum of Squares120.86713.667

Mean Square8.8439F Ratio

0.0044*Prob > F

Analysis of Variance

C-PC-WNC-P

Level555

Number145.800143.600153.000

Mean1.65331.65331.6533

Std Error142.20140.00149.40

Lower 95%149.40147.20156.60

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=10

141

Appendix E: Contact Angle ANOVA between Finishes (Polyester) 25 Washes

120

130

140

150

160

170co

ntac

t ang

le

C-P C-W NC-P

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.449410.3576455.192944147.8667

15

Summary of Fit

finishErrorC. Total

Source2

1214

DF264.13333323.60000587.73333

Sum of Squares132.06726.967

Mean Square4.8974F Ratio

0.0279*Prob > F

Analysis of Variance

C-PC-WNC-P

Level555

Number145.000144.800153.800

Mean2.32242.32242.3224

Std Error139.94139.74148.74

Lower 95%150.06149.86158.86

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=25

142

Appendix E: Contact Angle ANOVA Within Finishes (Polyester) Calendered Conventional (C-W) Finish

120

130

140

150

160

170co

ntac

t ang

le

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.6784390.6181474.330127

140.4520

Summary of Fit

washesErrorC. Total

Source3

1619

DF632.95000300.00000932.95000

Sum of Squares210.98318.750

Mean Square11.2524F Ratio

0.0003*Prob > F

Analysis of Variance

051025

Level5555

Number130.800142.600143.600144.800

Mean1.93651.93651.93651.9365

Std Error126.69138.49139.49140.69

Lower 95%134.91146.71147.71148.91

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By washes finish=C-W

143

Appendix E: Contact Angle ANOVA Within Finishes (Polyester) Calendered Plasma (C-P) Finish

120

130

140

150

160

170co

ntac

t ang

le

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.6819240.6222855.735852

139.9520

Summary of Fit

washesErrorC. Total

Source3

1619

DF1128.5500526.4000

1654.9500

Sum of Squares376.18332.900

Mean Square11.4341F Ratio

0.0003*Prob > F

Analysis of Variance

051025

Level5555

Number127.200141.800145.800145.000

Mean2.56522.56522.56522.5652

Std Error121.76136.36140.36139.56

Lower 95%132.64147.24151.24150.44

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By washes finish=C-P

144

Appendix E: Contact Angle ANOVA Within Finishes (Polyester) Non-Calendered Plasma (NC-P) Finish

120

130

140

150

160

170co

ntac

t ang

le

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.14417-0.0163

4.315669153.3

20

Summary of Fit

washesErrorC. Total

Source3

1619

DF50.20000

298.00000348.20000

Sum of Squares16.733318.6250

Mean Square0.8984F Ratio

0.4635Prob > F

Analysis of Variance

051025

Level5555

Number155.400151.000153.000153.800

Mean1.93001.93001.93001.9300

Std Error151.31146.91148.91149.71

Lower 95%159.49155.09157.09157.89

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By washes finish=NC-P

145

Appendix E: Hydrostatic Pressure ANOVA Between Finishes (Polyester) As Received

60

70

80

90

100cm

C-P C-W

finish

Excluded Rows 3

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.9735790.9669742.87170181.33333

6

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-28.4672.345

-21.957-34.977

0.95

t RatioDFProb > |t|Prob > tProb < t

-12.14074

0.0003*0.99990.0001* -30 -20 -10 0 10 20 30

t Test

finishErrorC. Total

Source145

DF1215.5267

32.98671248.5133

Sum of Squares1215.53

8.25

Mean Square147.3961

F Ratio0.0003*

Prob > F

Analysis of Variance

C-PC-W

Level33

Number95.566767.1000

Mean1.65801.6580

Std Error90.96362.497

Lower 95%100.17

71.70

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cm By finish washes=0

146

Appendix E: Hydrostatic Pressure ANOVA Between Finishes (Polyester) 5 Washes

60

70

80

90

100cm

C-P C-W

finish

Excluded Rows 3

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.010047-0.237441.41833279.61667

6

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-0.23331.15812.9820

-3.44860.95

t RatioDFProb > |t|Prob > tProb < t

-0.201494

0.85020.57490.4251 -4 -3 -2 -1 0 1 2 3 4

t Test

finishErrorC. Total

Source145

DF0.08166678.04666678.1283333

Sum of Squares0.081672.01167

Mean Square0.0406F Ratio

0.8502Prob > F

Analysis of Variance

C-PC-W

Level33

Number79.733379.5000

Mean0.818870.81887

Std Error77.46077.226

Lower 95%82.00781.774

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cm By finish washes=5

147

Appendix E: Hydrostatic Pressure ANOVA Between Finishes (Polyester) 10 Washes

60

70

80

90

100cm

C-P C-W

finish

Excluded Rows 3

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.7839070.7298841.564715

73.46

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-4.86671.2776

-1.3195-8.4138

0.95

t RatioDFProb > |t|Prob > tProb < t

-3.809274

0.0190 *0.99050.0095 * -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6

t Test

finishErrorC. Total

Source145

DF35.526667

9.79333345.320000

Sum of Squares35.5267

2.4483

Mean Square14.5106

F Ratio0.0190 *

Prob > F

Analysis of Variance

C-PC-W

Level33

Number75.833370.9667

Mean0.903390.90339

Std Error73.32568.458

Lower 95%78.34273.475

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cm By finish washes=10

148

Appendix E: Hydrostatic Pressure ANOVA Between Finishes (Polyester) 25 Washes

60

70

80

90

100cm

C-P C-W

finish

Excluded Rows 3

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.2329960.0412453.81466569.08333

6

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-3.4333.1155.214

-12.0810.95

t RatioDFProb > |t|Prob > tProb < t

-1.102314

0.33220.83390.1661 -10 -5 0 5 10

t Test

finishErrorC. Total

Source145

DF17.68166758.20666775.888333

Sum of Squares17.681714.5517

Mean Square1.2151F Ratio

0.3322Prob > F

Analysis of Variance

C-PC-W

Level33

Number70.800067.3667

Mean2.20242.2024

Std Error64.68561.252

Lower 95%76.91573.482

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cm By finish washes=25

149

Appendix E: Hydrostatic Pressure ANOVA Within Finishes (Polyester) Calendered Conventional (C-W)

60

70

80

90

100cm

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.8459030.7881172.61947871.23333

12

Summary of Fit

washesErrorC. Total

Source38

11

DF301.3333354.89333

356.22667

Sum of Squares100.444

6.862

Mean Square14.6385F Ratio

0.0013*Prob > F

Analysis of Variance

051025

Level3333

Number67.100079.500070.966767.3667

Mean1.51241.51241.51241.5124

Std Error63.61276.01267.47963.879

Lower 95%70.58882.98874.45470.854

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cm By washes finish=C-W

150

Appendix E: Hydrostatic Pressure ANOVA Within Finishes (Polyester) Calendered Plasma (C-P)

60

70

80

90

100cm

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.9500790.9313592.60144280.48333

12

Summary of Fit

washesErrorC. Total

Source38

11

DF1030.3767

54.14001084.5167

Sum of Squares343.459

6.768

Mean Square50.7512F Ratio

<.0001*Prob > F

Analysis of Variance

051025

Level3333

Number95.566779.733375.833370.8000

Mean1.50191.50191.50191.5019

Std Error92.10376.27072.37067.337

Lower 95%99.03083.19779.29774.263

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cm By washes finish=C-P

151

Appendix E: Hydrostatic Pressure ANOVA Within Finishes (Polyester) Non-Calendered Plasma (NC-P)

30

40

50

60cm

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.123869-0.204681.59085941.89167

12

Summary of Fit

washesErrorC. Total

Source38

11

DF2.862500

20.24666723.109167

Sum of Squares0.954172.53083

Mean Square0.3770F Ratio

0.7722Prob > F

Analysis of Variance

051025

Level3333

Number41.666741.400041.800042.7000

Mean0.918480.918480.918480.91848

Std Error39.54939.28239.68240.582

Lower 95%43.78543.51843.91844.818

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cm By washes finish=NC-P

152

Appendix E: Air Permeability ANOVA Between Finishes (Polyester) As Received

0.2

0.4

0.6

0.8

1

1.2cf

m

C-P C-W

finish

Excluded Rows 3

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.9854670.981834

0.030540.535667

6

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

0.4106670.0249350.4798990.341435

0.95

t RatioDFProb > |t|Prob > tProb < t

16.469184

<.0001*<.0001*1.0000 -0.5 -0.3 -0.1 .0 .1 .2 .3 .4 .5

t Test

finishErrorC. Total

Source145

DF0.252970670.003730670.25670133

Sum of Squares0.2529710.000933

Mean Square271.2337

F Ratio<.0001*

Prob > F

Analysis of Variance

C-PC-W

Level33

Number0.3303330.741000

Mean0.017630.01763

Std Error0.281380.69205

Lower 95%0.379290.78995

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cfm By finish washes=0

153

Appendix E: Air Permeability ANOVA Between Finishes (Polyester) 5 Washes

0.2

0.4

0.6

0.8

1

1.2cf

m

C-P C-W

finish

Excluded Rows 3

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.9908570.9885710.0187260.579167

6

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

0.3183330.0152900.3607850.275882

0.95

t RatioDFProb > |t|Prob > tProb < t

20.819994

<.0001*<.0001*1.0000 -0.4 -0.3 -0.2 -0.1 .0 .1 .2 .3 .4

t Test

finishErrorC. Total

Source145

DF0.152004170.001402670.15340683

Sum of Squares0.1520040.000351

Mean Square433.4720

F Ratio<.0001*

Prob > F

Analysis of Variance

C-PC-W

Level33

Number0.4200000.738333

Mean0.010810.01081

Std Error0.389980.70832

Lower 95%0.450020.76835

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cfm By finish washes=5

154

Appendix E: Air Permeability ANOVA Between Finishes (Polyester) 10 Washes

0.2

0.4

0.6

0.8

1

1.2cf

m

C-P C-W

finish

Excluded Rows 3

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.9665580.9581970.0094160.815667

6

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-0.082670.00769

-0.06132-0.10401

0.95

t RatioDFProb > |t|Prob > tProb < t

-10.75224

0.0004*0.99980.0002* -0.10 -0.05 .00 .05 .10

t Test

finishErrorC. Total

Source145

DF0.010250670.000354670.01060533

Sum of Squares0.0102510.000089

Mean Square115.6090

F Ratio0.0004*

Prob > F

Analysis of Variance

C-PC-W

Level33

Number0.8570000.774333

Mean0.005440.00544

Std Error0.841910.75924

Lower 95%0.872090.78943

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cfm By finish washes=10

155

Appendix E: Air Permeability ANOVA Between Finishes (Polyester) 25 Washes

0.2

0.4

0.6

0.8

1

1.2cf

m

C-P C-W

finish

Excluded Rows 3

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.9887880.9859850.0154540.898167

6

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-0.237000.01262

-0.20197-0.27203

0.95

t RatioDFProb > |t|Prob > tProb < t

-18.78224

<.0001*1.0000<.0001* -0.2 -0.1 .0 .1 .2

t Test

finishErrorC. Total

Source145

DF0.084253500.000955330.08520883

Sum of Squares0.0842540.000239

Mean Square352.7711

F Ratio<.0001*Prob > F

Analysis of Variance

C-PC-W

Level33

Number1.016670.77967

Mean0.008920.00892

Std Error0.991890.75489

Lower 95%1.04140.8044

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cfm By finish washes=25

156

Appendix E: Air Permeability ANOVA Within Finishes (Polyester) Calendered Conventional (C-W)

0.25

0.5

0.75

1

1.25cf

m

0 5 10 25

washes

Excluded Rows 30

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.8902590.8491070.0080780.758333

12

Summary of Fit

washesErrorC. Total

Source38

11

DF0.004234670.000522000.00475667

Sum of Squares0.0014120.000065

Mean Square21.6330F Ratio

0.0003*Prob > F

Analysis of Variance

051025

Level3333

Number0.7410000.7383330.7743330.779667

Mean0.004660.004660.004660.00466

Std Error0.730250.727580.763580.76891

Lower 95%0.751750.749090.785090.79042

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cfm By washes

157

Appendix E: Air Permeability ANOVA Within Finishes (Polyester) Calendered Plasma (C-P)

0.25

0.5

0.75

1

1.25cf

m

0 5 10 25

washes

Excluded Rows 30

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.9940940.99188

0.0272060.656

12

Summary of Fit

washesErrorC. Total

Source38

11

DF0.99670870.00592131.0026300

Sum of Squares0.3322360.000740

Mean Square448.8668

F Ratio<.0001*Prob > F

Analysis of Variance

051025

Level3333

Number0.330330.420000.857001.01667

Mean0.015710.015710.015710.01571

Std Error0.294110.383780.820780.98045

Lower 95%0.36660.45620.89321.0529

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cfm By washes

158

Appendix E: Air Permeability ANOVA Within Finishes (Polyester) Non-Calendered Plasma (NC-P)

7.5

8

8.5

9

9.5

10

10.5cf

m

0 5 10 25

washes

Excluded Rows 30

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.9678720.9558240.2065199.475833

12

Summary of Fit

washesErrorC. Total

Source38

11

DF10.2788920.341200

10.620092

Sum of Squares3.426300.04265

Mean Square80.3352F Ratio

<.0001*Prob > F

Analysis of Variance

051025

Level3333

Number7.8933

10.22009.80339.9867

Mean0.119230.119230.119230.11923

Std Error7.61849.94509.52849.7117

Lower 95%8.168

10.49510.07810.262

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of cfm By washes

159

Appendix E: Warp Tensile ANOVA Between Finishes (Polyester) As Received

160

165

170

175

180W

arp

C-P C-W

Finish

Excluded Rows 15

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.7067980.6701472.80838172.88

10

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

7.80001.7762

11.89593.7041

0.95

t RatioDFProb > |t|Prob > tProb < t

4.3914588

0.0023*0.0012*0.9988 -10 -5 0 5 10

t Test

FinishErrorC. Total

Source189

DF152.1000063.09600

215.19600

Sum of Squares152.100

7.887

Mean Square19.2849F Ratio

0.0023*Prob > F

Analysis of Variance

C-PC-W

Level55

Number168.980176.780

Mean1.25591.2559

Std Error166.08173.88

Lower 95%171.88179.68

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Warp By Finish Washes=0

160

Appendix E: Warp Tensile ANOVA Between Finishes (Polyester) 5 Washes

160

165

170

175

180W

arp

C-P C-W

Finish

Excluded Rows 5

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.077292-0.038054.28789173.71

10

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

2.22002.71198.4737

-4.03370.95

t RatioDFProb > |t|Prob > tProb < t

0.8186148

0.43670.21840.7816 -10 -5 0 5 10

t Test

FinishErrorC. Total

Source189

DF12.32100

147.08800159.40900

Sum of Squares12.321018.3860

Mean Square0.6701F Ratio

0.4367Prob > F

Analysis of Variance

C-PC-W

Level55

Number172.600174.820

Mean1.91761.9176

Std Error168.18170.40

Lower 95%177.02179.24

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Warp By Finish Washes=5

161

Appendix E: Warp Tensile ANOVA Between Finishes (Polyester) 10 Washes

160

165

170

175

180W

arp

C-P C-W

Finish

Excluded Rows 5

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.003235-0.121363.140223

174.9610

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-0.32001.98614.2598

-4.89980.95

t RatioDFProb > |t|Prob > tProb < t

-0.161128

0.87600.56200.4380 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6

t Test

FinishErrorC. Total

Source189

DF0.256000

78.88800079.144000

Sum of Squares0.256009.86100

Mean Square0.0260F Ratio

0.8760Prob > F

Analysis of Variance

C-PC-W

Level55

Number175.120174.800

Mean1.40441.4044

Std Error171.88171.56

Lower 95%178.36178.04

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Warp By Finish Washes=10

162

Appendix E: Warp Tensile ANOVA Between Finishes (Polyester) 25 Washes

160

165

170

175

180W

arp

C-P C-W

Finish

Excluded Rows 5

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.165620.0613224.24099171.51

10

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-3.38002.68222.8053

-9.56530.95

t RatioDFProb > |t|Prob > tProb < t

-1.260148

0.24310.87840.1216 -10 -5 0 5 10

t Test

FinishErrorC. Total

Source189

DF28.56100

143.88800172.44900

Sum of Squares28.561017.9860

Mean Square1.5880F Ratio

0.2431Prob > F

Analysis of Variance

C-PC-W

Level55

Number173.200169.820

Mean1.89661.8966

Std Error168.83165.45

Lower 95%177.57174.19

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Warp By Finish Washes=25

163

Appendix E: Warp Tensile ANOVA Within Finishes (Polyester) Calendered Conventional (C-W)

160

165

170

175

180

185

190W

arp

0 5 10 25

Washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.355710.2349063.873016174.055

20

Summary of Fit

WashesErrorC. Total

Source3

1619

DF132.50550240.00400372.50950

Sum of Squares44.168515.0002

Mean Square2.9445F Ratio

0.0646Prob > F

Analysis of Variance

051025

Level5555

Number176.780174.820174.800169.820

Mean1.73211.73211.73211.7321

Std Error173.11171.15171.13166.15

Lower 95%180.45178.49178.47173.49

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Warp By Washes Finish=C-W

164

Appendix E: Warp Tensile ANOVA Within Finishes (Polyester) Calendered Plasma (C-P)

160

165

170

175

180

185

190W

arp

0 5 10 25

Washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.3385520.21453

3.472715172.475

20

Summary of Fit

WashesErrorC. Total

Source3

1619

DF98.76150

192.95600291.71750

Sum of Squares32.920512.0598

Mean Square2.7298F Ratio

0.0783Prob > F

Analysis of Variance

051025

Level5555

Number168.980172.600175.120173.200

Mean1.55301.55301.55301.5530

Std Error165.69169.31171.83169.91

Lower 95%172.27175.89178.41176.49

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Warp By Washes Finish=C-P

165

Appendix E: Warp Tensile ANOVA Within Finishes (Polyester) Non-Calendered Plasma (NC-P)

160

165

170

175

180

185

190W

arp

0 5 10 25

Washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.1721390.0169156.338257173.355

20

Summary of Fit

WashesErrorC. Total

Source3

1619

DF133.65350642.77600776.42950

Sum of Squares44.551240.1735

Mean Square1.1090F Ratio

0.3745Prob > F

Analysis of Variance

051025

Level5555

Number176.780171.340174.880170.420

Mean2.83462.83462.83462.8346

Std Error170.77165.33168.87164.41

Lower 95%182.79177.35180.89176.43

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Warp By Washes Finish=NC-P

166

Appendix E: Fill Tensile ANOVA Between Finishes (Polyester) As Received

85

90

95

100

105

110

115Fi

ll

C-P C-W

Finish

Excluded Rows 15

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.491710.4281744.205889

103.5210

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-7.4002.660

-1.266-13.534

0.95

t RatioDFProb > |t|Prob > tProb < t

-2.781928

0.0239*0.98810.0119* -10 -5 0 5 10

t Test

FinishErrorC. Total

Source189

DF136.90000141.51600278.41600

Sum of Squares136.90017.689

Mean Square7.7391F Ratio

0.0239*Prob > F

Analysis of Variance

C-PC-W

Level55

Number107.22099.820

Mean1.88091.8809

Std Error102.8895.48

Lower 95%111.56104.16

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Fill By Finish Washes=0

167

Appendix E: Fill Tensile ANOVA Between Finishes (Polyester) 5 Washes

85

90

95

100

105

110

115Fi

ll

C-P C-W

Finish

Excluded Rows 5

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.8962610.8832932.403955

96.2210

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-12.6401.520

-9.134-16.146

0.95

t RatioDFProb > |t|Prob > tProb < t

-8.313638

<.0001*1.0000<.0001* -15 -10 -5 0 5 10 15

t Test

FinishErrorC. Total

Source189

DF399.4240046.23200

445.65600

Sum of Squares399.424

5.779

Mean Square69.1165F Ratio

<.0001*Prob > F

Analysis of Variance

C-PC-W

Level55

Number102.54089.900

Mean1.07511.0751

Std Error100.0687.42

Lower 95%105.0292.38

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Fill By Finish Washes=5

168

Appendix E: Fill Tensile ANOVA Between Finishes (Polyester) 10 Washes

85

90

95

100

105

110

115Fi

ll

C-P C-W

Finish

Excluded Rows 5

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.4984850.4357953.824069

103.1110

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

-6.8202.419

-1.243-12.397

0.95

t RatioDFProb > |t|Prob > tProb < t

-2.819878

0.0225*0.98880.0112* -8 -6 -4 -2 0 2 4 6 8

t Test

FinishErrorC. Total

Source189

DF116.28100116.98800233.26900

Sum of Squares116.28114.623

Mean Square7.9517F Ratio

0.0225*Prob > F

Analysis of Variance

C-PC-W

Level55

Number106.52099.700

Mean1.71021.7102

Std Error102.5895.76

Lower 95%110.46103.64

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Fill By Finish Washes=10

169

Appendix E: Fill Tensile ANOVA Between Finishes (Polyester) 25 Washes

85

90

95

100

105

110

115Fi

ll

C-P C-W

Finish

Excluded Rows 5

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.3208240.2359273.318509

101.5210

Summary of Fit

C-W-C-PAssuming equal variancesDifferenceStd Err DifUpper CL DifLower CL DifConfidence

4.08002.09888.9199

-0.75990.95

t RatioDFProb > |t|Prob > tProb < t

1.9439598

0.08780.0439*0.9561 -8 -6 -4 -2 0 2 4 6 8

t Test

FinishErrorC. Total

Source189

DF41.6160088.10000

129.71600

Sum of Squares41.616011.0125

Mean Square3.7790F Ratio

0.0878Prob > F

Analysis of Variance

C-PC-W

Level55

Number99.480

103.560

Mean1.48411.4841

Std Error96.06

100.14

Lower 95%102.90106.98

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Fill By Finish Washes=25

170

Appendix E: Fill Tensile ANOVA Within Finishes (Polyester) Calendered Conventional (C-W)

85

90

95

100

105

110

115Fi

ll

0 5 10 25

Washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.7046320.6492513.664014

98.24520

Summary of Fit

WashesErrorC. Total

Source3

1619

DF512.42950214.80000727.22950

Sum of Squares170.81013.425

Mean Square12.7233F Ratio

0.0002*Prob > F

Analysis of Variance

051025

Level5555

Number99.82089.90099.700

103.560

Mean1.63861.63861.63861.6386

Std Error96.3586.4396.23

100.09

Lower 95%103.2993.37

103.17107.03

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Fill By Washes Finish=C-W

171

Appendix E: Fill Tensile ANOVA Within Finishes (Polyester) Calendered Plasma (C-P)

85

90

95

100

105

110

115Fi

ll

0 5 10 25

Washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.5244360.4352683.335753

103.9420

Summary of Fit

WashesErrorC. Total

Source3

1619

DF196.33200178.03600374.36800

Sum of Squares65.444011.1272

Mean Square5.8814F Ratio

0.0066*Prob > F

Analysis of Variance

051025

Level5555

Number107.220102.540106.52099.480

Mean1.49181.49181.49181.4918

Std Error104.0699.38

103.3696.32

Lower 95%110.38105.70109.68102.64

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Fill By Washes Finish=C-P

172

Appendix E: Fill Tensile ANOVA Within Finishes (Polyester) Non-Calendered Plasma (NC-P)

85

90

95

100

105

110

115Fi

ll

0 5 10 25

Washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.3464250.2238792.029224108.815

20

Summary of Fit

WashesErrorC. Total

Source3

1619

DF34.9215065.88400

100.80550

Sum of Squares11.64054.1177

Mean Square2.8269F Ratio

0.0718Prob > F

Analysis of Variance

051025

Level5555

Number107.560109.540110.620107.540

Mean0.907500.907500.907500.90750

Std Error105.64107.62108.70105.62

Lower 95%109.48111.46112.54109.46

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of Fill By Washes Finish=NC-P

173

Appendix F: Nylon Additional Tables and Figures

Photograph of Nylon Fabric Used in This Research

174

Appendix F: XPS Binding Energy Scan of Nylon

Fl 1

s

Fl A

uger

Pea

ks

O 1

s

C 1

s

Fl 1

s

Fl A

uger

Pea

ks

O 1

s

C 1

s

175

Appendix F: Individual Repellency Tests for Nylon

Washes Finish Rating Washes Finish Water Absorbed (g) Finish Element Composition0 CTRL 0 0 PA 0 CTRL N 2%0 CTRL 0 0 PA 0 CTRL O 2%0 CTRL 0 0 PA 0.1 CTRL C 96%0 PA 100 0 PB 0 W C 34%0 PA 100 0 PB 0 W Fl 62%0 PA 100 0 PB 0 W O 4%0 PB 100 0 W 0.3 PA C 32%0 PB 100 0 W 0.4 PA Fl 63%0 PB 100 0 W 0.4 PA O 5%0 W 100 5 PA 0.1 PB C 33%0 W 100 5 PA 0.1 PB Fl 62%0 W 100 5 PA 0.1 PB O 5%5 PA 100 5 PB 05 PA 100 5 PB 05 PA 100 5 PB 05 PB 100 5 W 0.15 PB 100 5 W 0.25 PB 100 5 W 0.25 W 100 10 PA 05 W 100 10 PA 0.15 W 100 10 PA 010 PA 100 10 PB 010 PA 100 10 PB 010 PA 100 10 PB 010 PB 100 10 W 0.110 PB 100 10 W 0.110 PB 100 10 W 0.210 W 95 25 PA 010 W 100 25 PA 0.110 W 100 25 PA 0.125 PA 100 25 PB 025 PA 100 25 PB 025 PA 100 25 PB 025 PB 100 25 W 0.125 PB 100 25 W 0.125 PB 100 25 W 0.125 W 10025 W 10025 W 95

Spray Test Impact Test XPS Test

176

Appendix F: Individual Repellency Tests for Nylon (cont.)

Contact Angle Washes Finish Contact Angle Washes Finish Contact Angle

0 PA 150 10 PA 156 0 PA 143 10 PA 145 0 PA 151 10 PA 151 0 PA 145 10 PA 151 0 PA 145 10 PA 146 0 PB 138 10 PB 151 0 PB 143 10 PB 147 0 PB 148 10 PB 154 0 PB 147 10 PB 158 0 PB 142 10 PB 145 0 W 149 10 W 147 0 W 143 10 W 142 0 W 153 10 W 141 0 W 154 10 W 143 0 W 158 10 W 150 5 PA 144 25 PA 145 5 PA 150 25 PA 152 5 PA 146 25 PA 134 5 PA 149 25 PA 138 5 PA 146 25 PA 142 5 PB 149 25 PB 145 5 PB 153 25 PB 148 5 PB 153 25 PB 143 5 PB 148 25 PB 143 5 PB 152 25 PB 142 5 W 140 25 W 132 5 W 142 25 W 140 5 W 144 25 W 149 5 W 151 25 W 155 5 W 144 25 W 145

177

Appendix F: Contact Angle ANOVA between Finishes (Nylon) As Received

130

135

140

145

150

155

160co

ntac

t ang

le

PA PB W

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.3873030.2851864.501851147.2667

15

Summary of Fit

finishErrorC. Total

Source2

1214

DF153.73333243.20000396.93333

Sum of Squares76.866720.2667

Mean Square3.7928F Ratio

0.0529Prob > F

Analysis of Variance

PAPBW

Level555

Number146.800143.600151.400

Mean2.01332.01332.0133

Std Error142.41139.21147.01

Lower 95%151.19147.99155.79

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=0

178

Appendix F: Contact Angle ANOVA between Finishes (Nylon) 5 Washes

130

135

140

145

150

155

160co

ntac

t ang

le

PA PB W

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.5043180.4217043.093003

147.415

Summary of Fit

finishErrorC. Total

Source2

1214

DF116.80000114.80000231.60000

Sum of Squares58.40009.5667

Mean Square6.1045F Ratio

0.0148*Prob > F

Analysis of Variance

PAPBW

Level555

Number147.000151.000144.200

Mean1.38321.38321.3832

Std Error143.99147.99141.19

Lower 95%150.01154.01147.21

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=5

179

Appendix F: Contact Angle ANOVA between Finishes (Nylon) 10 Washes

130

135

140

145

150

155

160co

ntac

t ang

le

PA PB W

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.3199410.2065984.527693148.4667

15

Summary of Fit

finishErrorC. Total

Source2

1214

DF115.73333246.00000361.73333

Sum of Squares57.866720.5000

Mean Square2.8228F Ratio

0.0989Prob > F

Analysis of Variance

PAPBW

Level555

Number149.800151.000144.600

Mean2.02482.02482.0248

Std Error145.39146.59140.19

Lower 95%154.21155.41149.01

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=10

180

Appendix F: Contact Angle ANOVA between Finishes (Nylon) 25 Washes

130

135

140

145

150

155

160co

ntac

t ang

le

PA PB W

finish

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.025075-0.137416.572671143.5333

15

Summary of Fit

finishErrorC. Total

Source2

1214

DF13.33333

518.40000531.73333

Sum of Squares6.6667

43.2000

Mean Square0.1543F Ratio

0.8587Prob > F

Analysis of Variance

PAPBW

Level555

Number142.200144.200144.200

Mean2.93942.93942.9394

Std Error135.80137.80137.80

Lower 95%148.60150.60150.60

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By finish washes=25

181

Appendix F: Contact Angle ANOVA Within Finishes (Nylon) Conventional (W) Finish

130

135

140

145

150

155

160

cont

act a

ngle

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.2504670.1099295.926635

146.120

Summary of Fit

washesErrorC. Total

Source3

1619

DF187.80000562.00000749.80000

Sum of Squares62.600035.1250

Mean Square1.7822F Ratio

0.1911Prob > F

Analysis of Variance

051025

Level5555

Number151.400144.200144.600144.200

Mean2.65052.65052.65052.6505

Std Error145.78138.58138.98138.58

Lower 95%157.02149.82150.22149.82

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By washes finish=W

182

Appendix F: Contact Angle ANOVA Within Finishes (Nylon) First Plasma (PA) Finish

130

135

140

145

150

155

160co

ntac

t ang

le

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.3038140.1732794.612483

146.4520

Summary of Fit

washesErrorC. Total

Source3

1619

DF148.55000340.40000488.95000

Sum of Squares49.516721.2750

Mean Square2.3275F Ratio

0.1133Prob > F

Analysis of Variance

051025

Level5555

Number146.800147.000149.800142.200

Mean2.06282.06282.06282.0628

Std Error142.43142.63145.43137.83

Lower 95%151.17151.37154.17146.57

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By washes finish=PA

183

Appendix F: Contact Angle ANOVA Within Finishes (Nylon) Second Plasma (PB) Finish

130

135

140

145

150

155

160co

ntac

t ang

le

0 5 10 25

washes

RsquareAdj RsquareRoot Mean Square ErrorMean of ResponseObservations (or Sum Wgts)

0.5348350.4476163.708099

147.4520

Summary of Fit

washesErrorC. Total

Source3

1619

DF252.95000220.00000472.95000

Sum of Squares84.316713.7500

Mean Square6.1321F Ratio

0.0056*Prob > F

Analysis of Variance

051025

Level5555

Number143.600151.000151.000144.200

Mean1.65831.65831.65831.6583

Std Error140.08147.48147.48140.68

Lower 95%147.12154.52154.52147.72

Upper 95%

Std Error uses a pooled estimate of error variance

Means for Oneway Anova

Oneway Anova

Oneway Analysis of contact angle By washes finish=PB

184

Appendix G: Conventional Finish Cost Analysis Calculations

The cotton fabric was finished by Cotton Incorporated in Cary, NC. The first set of

calculations estimates the cost associated with the chemicals used. Table 7.1 gives the name

and cost of each of the chemicals given in Table 3.2.

Table 7.1. Conventional Chemical Cost per Pound

g/L Chemical Cost per pound 70 Clarient Nuva HPU $7.00 50 Huntsman Phobotex JVA $0.85 15 Huntsman Ultratex REP $1.25 20 Apollo Fluftone NPE $0.65

The chemical bath given above was padded on at 75 percent wet-pick-up (wpu), dried

at 250 °F, and cured at 350 °F for one minute. Assumptions used in the following

calculations are as follows:

- Fabric Weight = 6.7 oz/yd2

- 10 g/L = 1% on weight of bath (owb)

In order to determine the cost of chemicals, the amount of solution picked up into the

fabric to be dried and cured is calculated as shown below.

2 2

dry wt. wpu 6.7 28.35 75wt. of bath picked up = = = 142.5100 100

oz g gyd oz yd

⋅⋅ ⋅

Equation 7.1. Weight of Conventional Bath Picked Up

185

Although the weight of the bath picked up was 142.5 grams per square yard, much of

it was water. In order to determine the amount of chemicals in the bath, it was assumed that

10 g/L of chemical is 1% owb. There was a total of 155 g/L of chemicals added to the bath;

therefore, 15.5% of the 142.5 g/yd2 of bath picked up were the chemicals in Table 7.1. The

amount of chemicals picked up by the bath after padding to be dried and cured is given

below.

2 2chemicals picked up = 142.5 15.5% = 22.1g gyd y

⋅d

Equation 7.2. Conventional Chemicals Picked Up

Since the amount of chemicals picked up was determined, they were broken down

into the individual chemicals given in Table 7.1 in order to determine the costs for each

chemical. This is calculated on the following page in Equation 7.3.

186

2

2

2

70 $7 $0.15Clarient Nuva HPU: 22.1454155

50 $0.85 $0.013Huntsman Phobotex JVA: 22.1454155

15 $1.25 $0.0059Huntsman Ultratex RFP: 22.1454155

Apollo Flu

gg lbL

g L lb g ydL

gg lbL

g L lb g ydL

gg lbL

g L lb g ydL

⋅ ⋅ ⋅ =

⋅ ⋅ ⋅ =

⋅ ⋅ ⋅ =

2

20 $0.65 $0.0041fftone NPE: 22.1454155

gg lbL

g L lb g ydL

⋅ ⋅ ⋅ =

2

$0.18(chemical cost) = yd∑

Equation 7.3. Conventional Chemical Cost

To determine the energy cost associated with the drying and curing process,

American Monforts was contacted. American Monforts is a large company specializing in

supplying tenter machines to the textile industry and they agreed to determine the energy

consumption that would be required to dry and cure the cotton fabric with the chemical bath

as described above. Table 7.2 on the following page shows the variables that were used by

American Monforts in order to determine the energy consumption.

187

Table 7.2. Information Used by American Monforts

Fabric Type 100% Cotton Fabric Weight 6.7 oz/sq yd Fabric Width 65 inches

Desired Speed 25 yards/minute Dry at 350 deg. F

Cure at 350 deg. F for 1 min

The results returned from American Monforts are given below in Table 7.3. The

energy consumption results are in a ± 10 percent tolerance.

Table 7.3. Information Returned by American Monforts

Machine Montex-TwinAir Stenter, 10 zones Actual Speed 24 yards/min

Heat Energy without Heat Recovery 1405861 BTU/hr Heat Requirement per kg Evaporated H20 3056 BTU/kg H20

Total Electrical Power 224 KW

With the total amount of energy consumed by a tenter known, the energy costs can be

calculated. It will be assumed that the energy required to cure the chemicals is negligible

compared to the energy required to evaporate water. In addition, the following assumptions

will be made to determine energy cost.

- Electricity costs = $0.1265/KWh

- Natural Gas costs = $7.85/MMBTU

Equation 7.4 was used to determine the cost of electricity to power the tenter.

2

Electricity Cost $0.1265Power 224 $0.01160 60=Width Speed 65 24

36

hr KWKW hr min

yd yds ydinin min

⋅ ⋅ ⋅⋅ =

⋅ ⋅ ⋅

188

Equation 7.4. Tenter Electricity Cost

To determine the cost to dry and cure the fabric, the energy required to heat the tenter

and the energy to dry and cure the fabric will be calculated separately. Equation 7.5 below

was used to calculate how much it costs to use natural gas to keep a tenter at a set 350 °F.

6 2

1, 405,861$7.85 $0.004260

1065 2436

BTU hrhr min

yd yds BTU ydinin min

⋅⋅ =

⋅ ⋅

Equation 7.5. Natural Gas Cost to Maintain Tenter at 350 °F

Equation 7.6 was used to determine the cost associated with drying and curing the

amount of bath that was picked up as calculated in Equation 7.1.

2 6

142.5 3,056 $7.85 $0.00341000 10

g kg BTUyd g kg BTU yd

⋅ ⋅ ⋅ = 2

Equation 7.6. Natural Gas Cost to Dry and Cure

Equation 7.5 and Equation 7.6 result in the total cost of natural gas per square yard of

fabric to be $0.0077. These results suggest that it costs $0.20 per square yard to treat a fabric

with the conventional pad-dry-cure finish.

189

Appendix H: APPLD Cost Analysis Calculations

The following calculations were used to determine the approximate costs associated

with the APPLD process. There are three main costs linked with the APPLD treatment:

process gas, chemical precursors used, and electricity. The chemical cost will obviously be

the most expensive because the precursor chemicals used in this research were specialty

monomers. For this reason, multiple chemical vendors were contacted to determine a bulk

rate.

Out of five requests sent to different chemical manufacturers for each chemical, there

was only one response. A Chinese company called Feiyang provided a quote for the

HDFDA at 99.95 USD per kilogram for a 500 pound minimum order not including any

shipping charges. Because there was no response from any of the chemical vendors

contacted regarding a bulk price for the HDFD, the HDFD price was estimated by using the

same ratio as the HDFDA’s research to bulk price.

Table 7.4. Price of Chemical Precursors

Chemical CAS # Density (g/mL) Research Price Bulk Price HDFD 21652-58-4 1.67 $24.8 for 5 grams *$23.33 per lb

HDFDA 27905-45-9 1.64 $48.3 for 5 grams $45.43 per lb * estimated from HDFDA

The following calculations will determine the total cost associated with the APPLD

process used in this research. The APPLD settings from Table 4.2 will be used for the

following calculations along with the assumptions below.

190

- Electricity costs = $0.1265/KWh

- Helium costs = $0.0198/L

The calculations below determine the cost of electricity and helium in the APPLD

process.

2

Electricity Cost $0.1265Power 1.8 $0.006260 60#Passes= 35Width Speed 1236

hr KWKW hr min

yd m yds ydinin min 0.91m

⋅ ⋅ ⋅⋅⋅ ⋅

⋅ ⋅ ⋅ ⋅=

Equation 7.7. APPLD Electricity Cost

2

Total He Flow $He 25 / $0.0198 $0.81#Passes = 35Width SpeedL min

yd m ydsL L yd12in36 in min 0.91m

⋅ ⋅ ⋅ ⋅ =⋅ ⋅ ⋅ ⋅

Equation 7.8. APPLD Helium Cost

Next, the total cost of the chemical precursors used in the APPLD process was

calculated. This calculation contained three steps. The first step was to determine the total

mass of the chemical precursors that are injected into the plasma every minute as given in

Equation 7.9. Then the total mass of the precursors that was injected into the plasma region

per minute was converted to the total mass of precursors that polymerized on the surface of

the fabric per square yard, assuming 100 percent efficiency as shown in Equation 7.10.

Lastly, the amount of chemical precursors used was multiplied by the bulk cost of the

chemicals to determine the cost of chemical precursors per square yard of fabric.

191

The mass of the precursors that were injected into the plasma region per minute was

calculated by taking the total flow of each precursor and multiplying it by its density. The

precursors used in this research were a 50:50 blend by volume.

1.5 1.67 50 1.5 1.64 50 1.25 1.23HDFD HDFDA HDFD HDFDAmL g mL g g g% %

min mL min mL min min⎛ ⎞ ⎛ ⎞⋅ ⋅ + ⋅ ⋅ = +⎜ ⎟ ⎜ ⎟⎝ ⎠ ⎝ ⎠

Equation 7.9. Mass of Precursor Injected into Plasma Region

2 2

1.25 1.233 3 2.06 2.02

12 5.47 12 5.4736 36

HDFD HDFDA

HDFD HDFDAg g

g gmin minpasses passesyd yds yd yds yd ydin inin min in min

⋅ + ⋅ = +⋅ ⋅ ⋅ ⋅

Equation 7.10. Mass of Precursor on Fabric

2 2 2

$23.33 $45.43 $0.11 $0.202.06 2.02454 454

HDFD HDFDA HDFD HDFDAg lb g lb

yd g lb yd g lb yd yd⎛ ⎞ ⎛ ⎞ ⎛ ⎞ ⎛

⋅ ⋅ + ⋅ ⋅ = +⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜⎝ ⎠ ⎝ ⎠ ⎝ ⎠ ⎝

2

⎞⎟⎠

Equation 7.11 . Cost of Chemical Precursors

The results from the above calculations show that the chemicals used in this research

costs $0.31 per square yard. This results in the total cost per square yard of fabric tested in

this research at $1.13.

192

Appendix I: Chemical Material Safety Data Sheets

Clarient Nuva HPU MSDS pg 1 of 6

193

Appendix I: Clarient Nuva HPU MSDS pg 2 of 6

194

Appendix I: Clarient Nuva HPU MSDS pg 3 of 6

195

Appendix I: Clarient Nuva HPU MSDS pg 4 of 6

196

Appendix I: Clarient Nuva HPU MSDS pg 5 of 6

197

Appendix I: Clarient Nuva HPU MSDS pg 6 of 6

198

Appendix I: Huntsman Phobotex JVA MSDS pg 1 of 7

199

Appendix I: Huntsman Phobotex JVA MSDS pg 2 of 7

200

Appendix I: Huntsman Phobotex JVA MSDS pg 3 of 7

201

Appendix I: Huntsman Phobotex JVA MSDS pg 4 of 7

202

Appendix I: Huntsman Phobotex JVA MSDS pg 5 of 7

203

Appendix I: Huntsman Phobotex JVA MSDS pg 6 of 7

204

Appendix I: Huntsman Phobotex JVA MSDS pg 7 of 7

205

Appendix I: Huntsman Ultratex REP MSDS pg 1 of 6

206

Appendix I: Huntsman Ultratex REP MSDS pg 2 of 6

207

Appendix I: Huntsman Ultratex REP MSDS pg 3 of 6

208

Appendix I: Huntsman Ultratex REP MSDS pg 4 of 6

209

Appendix I: Huntsman Ultratex REP MSDS pg 5 of 6

210

Appendix I: Huntsman Ultratex REP MSDS pg 6 of 6

211

Appendix I: Apollo Fluftone NPE MSDS pg 1 of 4

212

Appendix I: Apollo Fluftone NPE MSDS pg 2 of 4

213

Appendix I: Apollo Fluftone NPE MSDS pg 3 of 4

214

Appendix I: Apollo Fluftone NPE MSDS pg 4 of 4

215

Appendix I: HDFDA MSDS pg 1 of 6

216

Appendix I: HDFDA MSDS pg 2 of 6

217

Appendix I: HDFDA MSDS pg 3 of 6

218

Appendix I: HDFDA MSDS pg 4 of 6

219

Appendix I: HDFDA MSDS pg 5 of 6

220

Appendix I: HDFDA MSDS pg 6 of 6

221

Appendix I: HDFD MSDS pg 1 of 4

222

Appendix I: HDFD MSDS pg 2 of 4

223

Appendix I: HDFD MSDS pg 3 of 4

224

Appendix I: HDFD MSDS pg 4 of 4