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Physico-chemical Aspectsof Textile Coloration

Current and Future Titles in the Society of Dyers and Colorists ndash John Wiley Series

PublishedPhysico-chemical Aspects of Textile ColorationStephen M Burkinshaw

Standard Colorimetry Definitions Algorithms and SoftwareClaudio Oleari

The Coloration of Wool and Other Keratin FibresDavid M Lewis and John A Rippon (Eds)

ForthcomingNatural Dyeing for Textiles A Guide Book for ProfessionalsDebanjali Banerjee

Colour for Textiles A Userrsquos Handbook Second EditionRoger H Wardman and Matthew Clark

Gilesrsquos Laboratory Course in Dyeing Fifth EditionUzma Syed


Stephen M BurkinshawSchool of Design University of Leeds UK

Published in association with the Society of Dyers and ColoristsSeries Editor Andrew Filarowski

This edition first published 2016 by John Wiley amp Sons in association with the Society of Dyers and Colorists

copy 2016 SDC (Society of Dyers and Colorists)Perkin House 82 Grattan Road Bradford West Yorkshire BD1 2LU United Kingdomhttpwwwsdcorguk

Registered OfficeJohn Wiley amp Sons Ltd The Atrium Southern Gate Chichester West Sussex PO19 8SQ United Kingdom

For details of our global editorial offices for customer services and for information about how to apply for permission to reuse thecopyright material in this book please see our website at wwwwileycom

The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright Designs andPatents Act 1988

All rights reserved No part of this publication may be reproduced stored in a retrieval system or transmitted in any form or by anymeans electronic mechanical photocopying recording or otherwise except as permitted by the UK Copyright Designs and PatentsAct 1988 without the prior permission of the publisher

Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available inelectronic books

Designations used by companies to distinguish their products are often claimed as trademarks All brand names and product namesused in this book are trade names service marks trademarks or registered trademarks of their respective owners The publisher is notassociated with any product or vendor mentioned in this book

Limit of LiabilityDisclaimer of Warranty While the publisher and author have used their best efforts in preparing this book theymake no representations or warranties with respect to the accuracy or completeness of the contents of this book and specificallydisclaim any implied warranties of merchantability or fitness for a particular purpose It is sold on the understanding that thepublisher is not engaged in rendering professional services and neither the publisher nor the author shall be liable for damages arisingherefrom If professional advice or other expert assistance is required the services of a competent professional should be sought

The advice and strategies contained herein may not be suitable for every situation In view of ongoing research equipmentmodifications changes in governmental regulations and the constant flow of information relating to the use of experimentalreagents equipment and devices the reader is urged to review and evaluate the information provided in the package insert orinstructions for each chemical piece of equipment reagent or device for among other things any changes in the instructions orindication of usage and for added warnings and precautions The fact that an organization or Website is referred to in this work as acitation andor a potential source of further information does not mean that the author or the publisher endorses the information theorganization or Website may provide or recommendations it may make Further readers should be aware that Internet Websiteslisted in this work may have changed or disappeared between when this work was written and when it is read No warranty may becreated or extended by any promotional statements for this work Neither the publisher nor the author shall be liable for any damagesarising herefrom

Library of Congress Cataloging-in-Publication Data

Burkinshaw Stephen MPhysico-chemical aspects of textile coloration Stephen M Burkinshaw

pages cmIncludes bibliographical references and indexISBN 978-1-118-72569-6 (cloth)

1 Dyes and dyeingndashTextile fibers 2 Color in the textile industries I TitleTP897B87 2016667 2ndashdc23

2015018225

A catalogue record for this book is available from the British Library

Set in 10125pt Times by SPi Global Pondicherry India

1 2016

Contents

Society of Dyers and Colourists xi

Preface xiii

1 Fundamental Aspects of Textile Fibres 111 Textiles 1

111 Yarn 2112 Fabric 4113 Textile Markets 6

12 Textile Fibres 6121 Textile Fibre Classification 7122 Textile Usage 9123 The History and Development of Textile Fibres 9124 Textile Polymers 12125 Textile Fibre Morphology and Fine Structure 16

13 General Physical and Mechanical Characteristics of Textile Fibres 27131 Length 27132 Fineness 27133 Twist 32134 Fibre Specific Surface Area Sm or Sv 33135 Cross-Sectional Shape 33

14 Properties of Textile Fibres 35141 Mechanical Properties 35142 Thermal Properties 37143 Optical Properties 48

References 51

2 Dyes 65Introduction 6521 Dyes 65

211 Historical Aspects 66212 Classification of Colorants 71213 Colour and Constitution 75214 Commercial Dye Forms 75215 Commercial Dye Names 76216 Global Dye Consumption 76

References 76

3 The Role of Water in Aqueous Dyeing 81Introduction 8131 Water Structure 8232 Water Availability and Global Consumption 84

321 Water Footprint 8533 Water Use in Dyeing 86

331 Water Used in Cotton Production 86332 Water Used in Fibre Processing 87333 Water Used in Dyeing 87

34 Water and Textile Fibres 91341 Hydrophilicity and Hydrophobicity 93

342 Moisture Sorption 94343 The Porous Nature of Fibres 103344 Wetting and Wicking 105345 Swelling 109346 Water Plasticisation 110

35 Water and Dyes 116351 Solvation 117352 Dye Solubility 120353 Dye Aggregation in Solution 123354 Dye Aggregation in the Fibre 129355 Aqueous Dye Dispersions 129

36 pH and pK 134361 Water Ionisation (Ionic Product of Water) 134362 The pH Scale 135363 pKa and pKb 136364 Buffer Systems and the HendersonndashHasselbalch Equation 136

References 137

4 Fundamentals of Dyeing 153Introduction 15341 DyendashFibre Systems 15442 Fundamental Principles of Dyeing 156

421 DyendashFibre Substantivity 156422 Driving Force for Dyeing 157423 Dye Exhaustion 157424 Rate of Dyeing 158425 Depth of Shade 159426 Liquor Ratio 159427 Dye Fixation 160428 Wash-Off 161429 Fastness 1624210 Dyeing Auxiliaries 163

References 164

5 DyendashFibre Interactions 167Introduction 16751 Intermolecular Interactions (or Forces) between Atoms and Molecules 167

511 Covalent Bonds 169512 IonndashIon Interactions (aka ChargendashCharge Coulomb Electrostatic Interactions) 169513 IonndashDipole Interactions (aka ChargendashDipole MonopolendashDipole) 169514 Van der Waals Interactions (aka van der Waals Forces) 170515 Hydrogen Bonds 172516 Hydrophobic Effect and Hydrophobic Interactions 172517 Total (Attractive and Repulsive) Intermolecular Potentials 173518 Aromatic Interactions (aka π-Interactions π-Effects) 173

52 Intermolecular Interactions (or Forces) between Macromolecules and Surfaces 176521 Dispersion Interactions 176522 Electrostatic Forces 178

53 Intermolecular Forces in the Context of Textile Fibres and Dyes 190531 Intermolecular Forces in Textile Polymers 190532 Intermolecular Forces between Dyes and Fibres 191

54 Solubility Parameter 192541 Hildebrand Solubility Parameter 193542 Hansen Solubility Parameters 193543 Solubility Parameters and DyendashFibre Substantivity 194544 Carriers 194

vi Contents

55 Fibre Modification to Enhance DyendashFibre Substantivity 195551 Mercerisation 195552 Plasma 197553 Pre-treatment with Cationic Compounds 199554 Nucleophilic Dyes on Modified Substrates 200

References 200

6 Dyeing Theory 209Introduction 20961 Background 21062 Dyeing Systems at Equilibrium (the Thermodynamics of Dyeing) 211

621 Adsorption 213622 Standard Affinity Standard Heat and Standard Entropy of Dyeing 216

63 Kinetics of Dyeing 221631 Diffusion 222632 Steady-State and Non-Steady-State Diffusion 223633 Fickrsquos Laws of Diffusion 223634 Experimental Methods for Determining Diffusion Coefficient 224635 Approximate Solutions to Diffusion Equations 228636 Characterisation of the Rate of Dyeing 228637 Apparent Diffusion Coefficient 229638 Boundary Layers in Diffusion 231639 Effect of Temperature on Dye Diffusion 2336310 Influence of Fibre Structure on Diffusion 2356311 Influence of Dye Structure on Diffusion 237

References 241

7 Cellulosic Fibres 249Introduction 24971 Cotton 24972 Viscose Fibres 250

721 SkinndashCore Structure 25173 Lyocell Fibres 25274 CA and CTA Fibres 25475 Cellulose Chemistry and Molecular Structure 256

751 Crystal Forms 25776 Cellulosic Fibre Fine Structure 26077 Hydroxyl Groups in Cellulosic Fibres 261

771 Accessibility 26178 WaterCellulose Interactions 263

781 Moisture Sorption 263782 Free and Bound Water 265783 Pore Structure 266784 Swelling 267785 Bleaching of Cotton and Other Cellulosic Fibres 270786 Plasticisation 270

79 Dye Classes Used on Cellulosic Fibres 272710 The Role of Electrolyte in Cellulosic Fibre Dyeing 273

7101 Nature of the Charged Cellulosic Fibre 2747102 Zeta Potential of Cellulosic Fibres 2747103 The Amount of Electrolyte Required to lsquoNeutralisersquo the Negative Surface Charge 2797104 Effect of Electrolyte on Dye Aggregation and Dye Solubility 280

711 Direct Dyes 2817111 Classification of Direct Dyes 2827112 Thermodynamics of Dyeing 2837113 Kinetics of Dyeing 2977114 Aftertreatment 301

viiContents vii

712 Sulphur Dyes 3027121 Fundamentals of the Chemistry and Application of Sulphur Dyes for Cellulosic Fibres 3037122 Dye Application 304

713 Vat Dyes 3057131 Fundamentals of the Chemistry and Application of Vat Dyes for Cellulosic Fibres 3067132 Reduction 3087133 Adsorption of the Leuco Derivative (Dyeing) 3127134 Kinetics of Leuco Vat Application 3177135 Oxidation of the Adsorbed Dye 3187136 Soaping 319

714 Reactive Dyes 3197141 Fundamentals of the Chemistry and Application of Reactive Dyes for Cellulosic Fibres 3207142 Mechanism of Dyeing 3257143 Wash-Off 3347144 Aftertreatment 337

715 Azoic Colorants 3377151 Naphtholation 3387152 Development 3387153 Wash-Off 339

716 Disperse Dyes 340References 340

8 Polyester Fibres 359Introduction 35981 PES Fibres 359

811 Fibre Production and Properties 360812 Physical Structure 361813 Oligomers 363814 SheathCore Structure 365815 Transitions (Relaxations) 365816 PESWater Interactions 366817 Dyeing of PES Fibres 367

82 PLA Fibres 403821 Polymer Synthesis 404822 PLA Biodegradability 405823 Fibres 405

References 413

9 Polyamide Fibres 427Introduction 42791 Aliphatic Polyamide Fibres 427

911 Nomenclature and Types of Polyamides 427912 PA 6 and PA 66 429913 Physical Structure 430

92 Dyeing of Aliphatic Polyamides 445921 Effect of Physical Processing on Dyeing 446922 Barreacute Effects 446923 Levelling Agents 447

93 Acid Dyes 447931 Non-metallised Acid Dyes 448932 Pre-metallised Acid Dyes (Aka Metal Complex Dyes) 464933 Aftertreatment 465

94 Disperse Dyes 46795 Mordant Dyes 46796 Direct Dyes 46897 Reactive Dyes 468

viii Contents

971 Anionic Reactive Dyes 469972 Disperse Reactive Dyes 470

98 Sulphur Dyes 47099 Vat Dyes 471910 Azoic Colorants 471911 Microfibres 471912 Semi-Aromatic Polyamides 473913 Aromatic Polyamides 474

9131 Fine Structure 4759132 WaterAramid Interactions 4769133 Dyeing of Aromatic Polyamide Fibres 478

References 479

10 Wool Fibres 491Introduction 491101 Wool Chemistry and Molecular Structure 491

1011 Proteins and Amino Acids 4911012 Fibre Morphology 4941013 Fine Structure 4961014 WaterWool Interactions 4971015 Swelling and Heat of Sorption 4981016 Sorption of Acids and Alkalis 4991017 Water Plasticisation 4991018 Effect of Physical and Chemical Properties on Dyeing 500

102 Dyes for Wool 500103 Non-metallised Acid Dyes 501

1031 Thermodynamics of Dyeing 5011032 Effect of Electrolyte on Dye Adsorption 5091033 Affinities of Acids and Dye Anions 5111034 Kinetics of Dyeing 513

104 Pre-metallised Acid Dyes (Aka Metal Complex Dyes) 5161041 1 1 Metal Complex Dyes 5171042 1 2 Metal Complex Dyes 518

105 Mordant Dyes 5191051 Mechanism of Chroming 520

106 Reactive Dyes 5211061 Historical Aspects 5211062 Chemistry and Application of Reactive Dyes 5211063 Levelling Agents 522

References 524

11 Acrylic (polyacrylonitrile) Fibres 531Introduction 531111 Fibre Production and Properties 531112 Physical Structure 532

1121 Crystallinity or Pseudocrystallinity 5331122 Transitions (Relaxations) 5331123 Theories of Fine Structure 533

113 PANWater Interactions 5351131 Water Plasticisation 535

114 Dyes for PAN Fibres 536115 Basic Dyes 536

1151 Historical Aspects 5361152 General Characteristics of Basic Dyes 5371153 Thermodynamics of Dyeing 5381154 Kinetics of Dyeing 543

ixContents ix

1155 Effect of Electrolytes on Dyeing 5451156 Effect of pH on Dyeing 5471157 Effect of Temperature on Dyeing 5481158 Retarding Agents 5501159 Dyes in Admixture 55011510 Carriers 551

116 Disperse Dyes 5511161 Thermodynamics of Dyeing 5521162 Kinetics of Dyeing 552

References 553

12 Silk Fibres 559121 Fibre Morphology 559122 Silk Chemistry and Molecular Structure 559123 Fine Structure 560124 SilkWater Interactions 564

1241 Water Plasticisation 564125 Dyes for Silk 565

1251 Acid Dyes 5661252 Reactive Dyes 567

References 568

13 Non-aqueous Dyeing 571Introduction 571131 Dyeing from Air (Vapour-Phase Dyeing Thermofixation) 571

1311 General Introduction 5711312 Thermodynamics of Dyeing 5711313 Kinetics of Dyeing 573

132 Dyeing from Supercritical Carbon Dioxide 5751321 General Introduction 5751322 Properties of Supercritical CO2 Fluids 5751323 Solubility of Dyes in Supercritical CO2 5771324 Effect of Supercritical CO2 on Fibres 5791325 Dyeing from Supercritical CO2 582

133 Dyeing from Liquid (Non-aqueous) Solvents 5921331 PER Dyeing 5921332 Solvent-Assisted Dyeing 594

References 594

Colorants Index 601

Subject Index 605

x Contents

Society of Dyers and Colourists

Society of Dyers and Colourists (SDC) is the worldrsquos leading independent educational charity dedicated to advancingthe science and technology of colour Our mission is to educate the changing world in the science of colour

SDC was established in 1884 and became a registered educational charity in 1962 SDC was granted a Royal Charterin 1963 and is the only organisation in the world that can award the Chartered Colourist status which remains thepinnacle of achievement for coloration professionals

We are a global organisation With our Head Office and trading company based in Bradford UK we have membersworldwide and regions in the UK China Hong Kong India and Pakistan

Membership To become a member of the leading educational charity dedicated to colour Please emailmemberssdcorguk for details

Coloration Qualifications SDCrsquos accredited qualifications are recognised worldwide Please email edusdcorgukfor further information

Colour Index The unique and definitive classification system for dyes and pigments used globally by manufac-turers researchers and users of dyes and pigments (wwwcolour-indexcom)

Publications SDC is a global provider of content helping people to become more effective in the workplace andin their careers by educating them about colour This includes text books covering a range of dyeing and finishingtopics with an ongoing programme of new titles In addition we publish Coloration Technology the worldrsquos leadingpeer-reviewed journal dealing with the application of colour providing access to the latest coloration research globally

For further information please email infosdcorguk or visit wwwsdcorguk

Preface

The dyeing of textile fibres is a major global industry that has developed over several thousand years from small-scalepractices undertaken by a relatively small number of skilled artisans to contemporary large-scale complex proceduresthat are carried out by large numbers of expert technicians and which on an annual basis result in the coloration ofmillions of tonnes of fibre using hundreds of thousands of tonnes of dye

The more recent developments in textile dyeing as gauged in terms of the thousands of years over which dyeing hasevolved benefited from advances that were made in understanding the nature of the interactions that occur betweendyes and fibres Such developments in dyeing theory which reflected advances in general scientific enquiry that aroseduring the latter part of the eighteenth century helped fuel both invention and innovation in terms of the developmentof synthetic dyes and processes for their application to natural man-made and synthetic textile fibres

This book concerns the theory of dyeing textile fibres which for the most part relates to the nature of the interactionsthat occur between dyes and fibres under aqueous conditions By way of short explanation dyeing can be considered as theapplication of a dye most commonly in the guise of molecular or ionic solution to a substrate with the intention of obtain-ing a uniform distribution of dye throughout that substrate Although water by some margin is the medium most com-monly employed for dyeing air is utilised in the vapour-phase dyeing of hydrophobic fibres using disperse dyes anddyeing from both liquid non-aqueous (organic) solvents and non-aqueous supercritical fluids has received attention buthave not yet achieved widespread commercial usage In its simplest form aqueous textile dyeing involves three compo-nents namely dye textile fibre and water These three crucially important elements are introduced and discussed in Chap-ters 1 2 and 3 respectively in terms of the fundamental aspects of textile fibres in particular current views on the finestructure of such materials the nature and properties of dyes as well as the multifaceted role of water in aqueous dyeingespecially the plasticising effect that this unique solvent has upon textile fibres A brief introductory account of dyeing as anarea of study as well as the terminology that is employed in the science and technology of dyeing textile materials is cov-ered in Chapter 4 As the majority of the research into the theory of dyeing textiles has focussed principally on the nature ofthe interactions that can occur between dyes and fibres at a molecular level Chapter 5 considers contemporary views ofintermolecular forces This theme is expanded in Chapter 6 in which the theoretical aspects of dyeing as represented bythe thermodynamics and kinetics of dye adsorption are presented Chapters 7ndash12 respectively provide detailed accounts ofthe various mechanisms of dyeing that apply to each of the major types of textile fibre namely cellulosic fibres polyesterpolyamide wool polyacrylonitrile and silk In terms of the discussion of the thermodynamics and kinetics of dye adsorp-tion recounted in Chapters 7ndash12 aspects of the approach adopted build upon those previously reported in the two editionsof the SDC textbook The Theory of Coloration of Textiles [1 2] Non-aqueous dyeing which relates to the use of airorganic solvents and supercritical CO2 fluid as alternatives to water as application medium is considered in Chapter 13

Each chapter includes an introduction that explains the purpose of the chapter and its relevance to dyeing theoryThroughout the book extensive use is made of references to published work In this context as it is neither practical nornecessary to cite all references that relate to a given topic an attempt has been made to provide the reader with refer-ences that are both relevant and illustrative of a particular area of study In an effort to aid understanding supportinginformation is provided in the form of footnotes

The material presented does not profess to constitute a definitive categorical account of the theory of dyeing textilefibres as this does not exist owing to ambiguity that attends textile fibre fine structure the complex nature of aqueousdye solutions and the complicating effects of dyebath components in particular electrolytes as well as the highly com-plex multifaceted nature of the interactions that can occur between dyes and fibres Rather the material provides acontemporary but in most cases nonetheless incompletely resolved interpretation of the theoretical aspects of thecoloration of textile fibres

Units and Symbols

The Systegraveme International drsquoUniteacutes SI (aka International System of Units) has been the preferred system of measure-ment for science and technology since its adoption in 1960 [3 4] However since dyeing theory and textile sciencedeveloped over a long period of time the published literature contains various units of measurement including bothCGS (centimetre gram second) and MKS (metre kilogram second) units many publications also contain formerImperial units (inch lb hour etc) Factors to convert between the different systems of measure are widely available

Terms and Definitions

In an attempt to aid the uninitiated readerrsquos understanding of the theoretical aspects of textile dyeing various terms anddefinitions that relate to textiles textile fibres polymers and dyeing are included in the text However an attempt hasbeen made to direct the reader to comprehensive treatments of terms and definitions of relevance to textiles and textilefibres polymers and dyeing In this context reference is made to terms and definitions published by The InternationalUnion of Pure and Applied Chemistry (IUPAC) which can be located via the interactive version of the IUPACCompendium of Chemical Terminology commonly known as the Gold Book

Commercial Names

Whilst in this book the use of commercial names of polymers textile fibres dyes auxiliaries etc and details of com-mercial application procedures may be used this does not imply superiority of a particular commercial product butrather is intended to serve only as a guide

I would like to thank the permissions production and copy-editing team at John Wiley amp Sons for their dedicatedsupport throughout the preparation of this book

Finally none of this would have been possible without the unwavering support tolerance and patience of my wife towhom I express my sincere appreciation

STEPHEN M BURKINSHAW

Leeds 2015

References[1] Bird CL Boston WS editors The Theory of Coloration of Textiles Bradford Society of Dyers and Colourists 1975[2] Johnson A editor The Theory of Coloration of Textiles 2nd edition Bradford Society of Dyers and Colourists 1989[3] NIST The International System of Units (SI) Washington DC National Institute of Standards and Technology US Department

of Commerce 2008[4] Mesures BIdPe The International System of Units (SI) 8th edition Sevres Bureau International des Poids et Mesures 2008

httpwwwbipmorgenpublicationssi-brochure (accessed 21 September 2015)

xiv Preface

1Fundamental Aspects of Textile Fibres

11 Textiles

The modern definition of the word textile namely (n) a type of cloth or woven fabric [1] reflects the early seventeenthcentury origins of the word as relating to a woven fabric and the process of weaving Nowadays the word has moreextensive meanings and associations such as textile-filament -fibre -yarn and -fabric and relates to the preparation ofknitted tufted and non-woven fabrics as well as woven fabrics In a similar vein the modern definition of the wordfibre as a thread or filament from which a vegetable tissue mineral substance or textile is formed [1] also is the resultof considerable linguistic evolution since its origins in the early fifteenth century [2] to describe lobes of the liver andentrails [1]

Essentially textile materials can be considered as principally cohesive fibrous assemblies in which individualfibres are assembled via friction A wide range of textiles is commercially available the different types of such productsvarying markedly in terms of both the geometric arrangement of the fibrous materials (eg woven fabric yarn andnon-woven) and the derivation structure physical characteristics and chemical properties of the component textilefibres Since in its broadest sense the theory of the dyeing of textiles concerns the nature of the interactions that operatebetween such fibrous assemblies and dyes these interactions can be considered in terms of three aspects

(1) the gross structural arrangement of the fibrous assembly (eg yarn woven fabric and garment)(2) the constituents of the fibrous assembly (ie fibre filament etc)(3) the composite macromolecules

Of the large amount of research that has been carried out on dyeing theory the vast majority has tended to focus lesson the physical form of a textile material (ie fabric garment yarn etc) and more on the constituents of the fibrousassembly (fibres filaments etc) with especial attention being placed on interactions that occur at a macromolecularlevel Whilst it seems appropriate to consider these three particular aspects of textile physics and chemistry withemphasis on the constituents of the fibrous assemblies (ie textile fibres) from a macromolecular perspective anythingother than an outline of this large and inordinately complex area is neither possible nor required here

In the context of the gross structural arrangement of fibrous assemblies textile materials are available in a variety ofdifferent physical forms including for example1

bull yarnstaple spun (comprise staple fibres) eg ring spun air-jet spun rotor spunfilament (comprise one or more mono- or multi-filament(s) withwithout twist) eg untextured (aka flat) textured

interlaced tape stretch bulkycomposite (comprise staple and filament components in at least two strands one core and a wrap strand) eg fil-

ament core staple corefancy (comprise deliberate irregularities to achieve effects) eg chenille boucle fleck etcspecialist (hybrid triaxial woven compound)

bull cordagebull flockbull woven fabric

plain-weave twill fabrics satin fabrics complex (eg leno jacquard etc)bull knitted fabric

weft-knitted single knits (eg jersey purl etc) double knits (eg interlock)warp-knitted tricot raschel net lace

1 ISO 81591987 lsquoTextiles Morphology of Fibres and Yarns ndash Vocabularyrsquo discusses the principal terms that are used to describe various tex-tile forms

Physico-chemical Aspects of Textile Coloration First Edition Stephen M Burkinshawcopy 2016 SDC (Society of Dyers and Colorists) Published 2016 by John Wiley amp Sons Ltd

bull non-wovendry-laid air-laid wet-laid polymer-laid (and associated bonding processes eg hydroentanglement needlepunching thermal chemical stitching)

Textiles can be dyed at various stages of their manufacture (Table 11) depending on the particular manufacturingprocess used cost end use requirements fastness etc Of these various physical forms yarn and fabric are the two mostcommonly encountered forms in dyeing

111 YarnYarn [4ndash10] is defined as [11] a product of substantial length and relatively small cross-section of fibres andor fila-ments with or without twist and fabric as a manufactured assembly of fibres andor yarns that has substantial area inrelation to its thickness and sufficient cohesion to give the assembly useful mechanical strength2 Yarn is essentially atransitional product insofar as it is mostly converted into more significant textile products such as woven fabric (byinterweaving) knitted fabric (by interlooping) or rope and braid (by intertwisting) Some 90 of fibres are first spuninto yarn [5] which is employed in the form of long fine fibres that consist of either a twisted assembly of staple fibres(fibre of finite usually short length) or parallel continuous filaments (fibres of infinite length) As such two types ofyarn are produced namely spun yarn and filament yarn

It seems appropriate at this point to consider briefly what is meant by the use of the term spinning from a textileperspective Confusingly spinning relates not only to the processes employed in the formation of yarn by the insertionof twist in the case of staple natural or man-made fibres but also relates to the extrusion3 of filaments from both natural(eg silk) and man-made (ie polymers) sources4

Filament yarn is typically represented by man-made fibres although silk is extruded as a natural continuousfilament Monofilament yarn consists of a single filament as opposed to multifilament yarn that comprises several indi-vidual filaments Man-made continuous filaments often are converted into bulked yarn via texturing prior to beinginterwoven or interlooped to form woven or knitted fabrics respectively (Figure 11) In contrast spun yarns are man-ufactured from staple fibre of natural man-made or synthetic origin in which several processes are required to preparethe fibre for spinning (eg blending carding combing etc) this being especially so in the case of natural fibres such aswool and cotton (Figure 11)

Yarns can be classified in several ways according to either their structural complexity (single yarns plied yarns etc)method of fibre preparation (carded worsted woollen) or spinning method used (ring spun rotor spun etc) Productionmethods for yarn were initially developed for spinning natural fibres such as cotton wool and silk different processesbeing devised to accommodate the different physical characteristics of the fibres (eg [13ndash17]) With the advent of man-made fibres other spinning systems were developed for continuous filament and staple fibres (eg [4 5 7 8 10 18ndash20])

Table 11 Stages of textile processing at which dyeing can be undertaken

fibre mass colorationa gel dyeingb loose stockc yarn piece garment

Cotton minus minus + + + +CACTAd + minus minus + + +CVd + minus + + + +PAd + minus + + + +PANd + + + + + +PESd + minus + + + +Wool minus minus + + + +

a a method of colouring man-made fibres by incorporation of colourants in spinning composition before extrusion into filaments [3]b a continuous tow-dyeing method in which soluble dyes are applied to wet-spun fibres (eg acylic or modacrylic fibres) in the gel

state (ie after fibre extrusion and coagulation but before drawing and drying) [3]c fibres in the randomised stated please refer to Figure 17 for definitions of the various textile fibre generic names

2 fabrics are most commonly woven or knitted but the term includes assemblies produced by felting lace-making net making nonwoven processesand tufting [11]3 solidifying extruded fibres (sometimes also hardened fibres) are drawn so as to impart strength and other properties4 the four common types of spinning process employed for man-made fibres are melt spinning (eg PA and PES) dry spinning (eg PAN and CA)wet spinning (eg CV and CLY) and gel spinning (eg AR) ndash for fibre names see Figure 17

2 Physico-chemical Aspects of Textile Coloration

A large number of different types of yarn can be produced depending on fibre type (eg natural and man-made) andphysical nature (filament core spun flat yarn plied yarn etc) (Figure 12)

Whilst not all aspects of the highly complex process by which polymers are converted into natural fibres duringgrowth have been entirely resolved in the case of man-made fibres the polymers are transformed into fibres commonlyvia either the molten state (melt-spinning (eg [18 21ndash23])) or solution state (wet-spinning or dry spinning (eg [1824])) though other spinning routes (eg electrospinning and gel spinning [18 25ndash30]) can be used as appropriate to theparticular polymer involved (Figure 13) The majority of man-made fibres are produced using melt spinning (eg PAPES fibres) which generally offers a lower cost less complicated route than either of the two solution-based extrusionprocesses However as not all polymers possess a stable melt phase recourse is therefore made to spinning fromsolution of which there are two types of process that can be used

(1) dry spinning in which the polymer is dissolved in a highly volatile solvent and the fibre is formed by evaporationof the solvent during extrusion (eg CA and CTA fibres)

(2) wet spinning in which the polymer can be dissolved only in a solvent of low volatility the fibre being formed byextrusion into a coagulating medium which removes the solvent (eg CV fibres)

polymer

spinneret

bulked yarn stretch yarn

texturised yarns

continuous monofilament yarn

continuous multifilament yarn

(a)

natural staple fibresman-made staple fibresnaturalman-made fibres

- opening- drawing- consolidation- twisting amp winding

spun yarn

(b)

Figure 11 (a) Continuous filament yarns and (b) spun yarns Reproduced from [12] with permission from Elsevier

monofilament multifilament core spun yarn flat yarn bulked yarn single yarn two-ply yarn

Figure 12 Different types of yarn (See insert for colour representation of the figure)

3Fundamental Aspects of Textile Fibres 3

Spinning has a marked effect on the structure and properties of the extruded filament For example whereas wetspun fibres tend to be round or kidney bean shaped dry-spun fibres are generally dumbell-shaped because duringevaporation of the highly volatile solvent from the polymer solution the outer regions of the extruded fibre solidifybefore the inner regions which causes the outer regions to collapse inwards In this context many man-made fibresirrespective of their mode of extrusion possess a skincore structure in which the skin and core display differencesin physical structure which often are reflected in differences in their dyeability as exemplified by CV fibres (seeChapter 7)

112 Fabric (eg [31ndash39])Three types of fabric can be differentiated

(1) woven fabric in which warp yarns (lengthwise) pass under and over weft yarns (widthways)(2) knitted fabric in which yarns are interlooped with adjoining rows either along the length (warp knitting) or across

the length (weft knitting)(3) non-woven fabric (which is usually shortened to non-woven) is produced directly without intermediary yarn

formation

Three main methods can be used to mechanically transform yarn into woven and knitted fabrics namely interweav-ing (more commonly referred to as weaving) intertwining and interlooping the latter process being most commonlyemployed in knitting (Figure 14) (eg [33 34 38 39 41])

Non-woven fabric comprises individual fibres or filaments that are bound together in the form of a web by means offriction andor cohesion andor adhesion (eg [42ndash52]) (Figure 15) As non-wovens typically are not based on inter-meshed or interlaced yarns these fabrics differ fundamentally from conventionally manufactured woven or knittedfabrics furthermore yarn spinning and subsequent processing steps such as knitting and weaving are not requiredin non-woven manufacture Woven and knitted fabrics are most commonly encountered in aqueous dyeing the col-oration of non-wovens being mostly undertaken using mass coloration or dispersed pigments (eg [53 54])

meltedpolymer

(a) melt spinning (b) dry spinning (c) wet spinning

cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret

Figure 13 (a) Melt (b) dry and (c) wet spinning Reproduced from [24] with permission from Elsevier


1121 Knitted Fabrics (eg [32ndash35])There are two different types of knitted structure namely weft-knitted fabrics and warp-knitted fabrics (Figure 16) ofwhich there are many variants (eg jersey purl interlock double tricot raschel) In warp knitting each warp yarn ismore or less in line with the direction in which the fabric is produced whereas in weft-knitting the weft yarn lies more

interweaving intertwining interlooping

Figure 14 Methods used to produce fabrics Reproduced from [40] with permission from Elsevier

Figure 15 Non-woven fabric

(a) (b)

Figure 16 (a) Weft- and (b) warp-knitted structures Reproduced from [32] with permission from Elsevier


or less perpendicular to the direction in which the fabric is produced [11] Knitted fabrics are available as flat tubularand shaped structures whilst a weft knitted fabric can be unravelled a warp knitted fabric cannot [32]

1122 Woven Fabrics (eg [39 41 55 56])In a woven fabric the warp and weft yarns are interlaced (ie change direction recurrently from the surface (aka face) tothe underside (ie back) of the fabric) perpendicularly to each other Each warp yarn is referred to as an end and eachweft yarn is termed a pick The pattern of the interlacing of the warp and weft yarns (ie the weave pattern) influencesseveral characteristics of the fabric including drape handle etc Fabric attributes are also influenced by yarn charac-teristics such as colour fibre constitution countlinear density as well as the number of picks and ends per given areaSeveral basic types of woven structure are produced (plain woven twill satin) and more complex structures aregenerated using two or more sets of yarn (eg pique crepe etc)

113 Textile MarketsTextiles enjoy manifold applications (eg [57ndash69]) and are traded in four main markets

(1) apparel many and varied clothing items such as shirting hosiery and lingerie(2) interior furnishings for example carpets curtains and upholstery in both domestic and contract markets(3) household textiles for example bed linen towels and blankets in both domestic and contract markets(4) industrialtechnical textiles medical-textiles geo-textiles agro-textiles high performance fibres etc

For convenience the four markets are often grouped into two main manufacturing sectors namely textiles(eg yarns household textiles industrialtechnical fabrics) and clothing (eg apparel clothing accessories) The globaltextile and clothing sectors are large and diverse industries that comprise both commodity products that are produced inhigh volume and at relatively low cost as well as high-value added products for which both research and developmentare vitally important and fibre technology is a key competitive issue The textile and clothing industries are very largecomplex global manufacturing businesses dominated by small and medium-sized enterprises (SMEs) and encompassseveral sub-sectors that range from the production of the raw materials via semi-processed goods (eg yarns andwoven fabrics) to final products (household textiles clothing etc) In 2011 global clothing and textiles trade reachedUS$ 706 billion the leading importers being the EU-27 and the United States [70] Textiles and clothing are majorglobal employers for instance in 2009 the textiles and clothing sectors within the EU which account for 29 ofworld textiles and clothing exports (not including trade between EU member states) and rank second only to Chinaand which generate 40 of global exports [71] employed 23 times 106 workers across 150 000 SMEs [72] Howeverfrom a worldwide market perspective despite the considerable scale of the global clothing and textiles sectors in2011 clothing (US$ 412 billion) and textiles (US$ 294 billion) accounted for only 16 and 23 respectively of worldmerchandise trade and contrasted markedly with that in chemicals ($US 1997 112) and fuels (US$ 3171 billion178) [70]

12 Textile Fibres

As mentioned dyeing theory has tended to focus less on the physical form of a textile material (ie fabric garmentyarn etc) and more at the fibre and especially at molecular levels This section concerns the first of these latter twoaspects of textile physics and chemistry namely textile fibres

A fibre can be considered [11] as a textile raw material generally characterised by flexibility fineness and highratio of length to thickness However within this definition several different types of fibre can be differen-tiated [11]

bull natural fibre a fibre occurring in naturebull regenerated fibre a fibre formed from a solution of natural polymer or of a chemical derivative of a natural

polymer and having the same chemical constitution as the natural polymer from which the solution or derivativewas made

bull chemical fibre a literal translation of various non-English terms having the same meaning as manufactured fibreor man-made fibre

bull manufactured fibre (aka man-made fibre) a fibre that does not occur in nature although the material of which it iscomposed may occur naturally


bull synthetic fibre a fibre manufactured from a polymer built up from chemical elements or compounds in contrast tofibres made from naturally occurring fibre-forming polymers

These various types of fibre are briefly discussed below

121 Textile Fibre ClassificationTextile fibres can be classified in several ways That shown in Figure 17 follows conventional practice differen-tiating six groups spread across two main derivation classes namely natural fibres and man-made fibres Figure 17shows both the generic names (eg viscose polyester) and the appropriate abbreviations (eg CV PES etc)that are used for man-made fibres (see Section 1211) In this book the abbreviated fibre names are usedpreferentially

Natural fibres These are of vegetable (cellulosic) animal (protein) or mineral origin and are staple fibres (ie offinite usually short length) with the exception of silk which is formed in continuous filaments In terms ofusage this category is dominated by the cellulosic fibres cotton and flax as well as the protein fibres wool andsilk with other textile substrates of organic origin including cellulosic fibres of seed (eg coir) bast (eg juteand ramie) and leaf (eg sisal) derivation as well as protein fibres derived from hair (eg cashmere) providingeffectively niche goods The inorganic fibre asbestos is of course no longer available because of its toxicity Suchis the global popularity of natural fibres that a considerable proportion of global agriculture is concerned with theirproduction

Man-made fibres (aka manufactured fibres) These include natural polymer fibres obtained from naturallyoccurring polymers (mostly cellulose) via chemical transformation (eg CV) or derivation (eg CA) synthetic pol-ymer fibres derived from synthetic materials (eg PES) as well as the so-called inorganic fibres such as glassceramic and carbon Whilst man-made fibres are produced as continuous filament often these are cut to producestaple fibres for use in knitwear or carpets and for blending with natural fibres (eg PEScotton)

Figure 17 Classification of textile fibres


As Figure 17 shows the majority of fibres derived from organic sources (which constitute by far the majorityof textile fibres) belong to a relatively small number of chemical classes

bull natural cellulosic and proteinbull man-made polyamide polyester polyolefin polyurethane and polyvinyl

Furthermore such fibres which enjoy traditional widespread textile usage for the most part are composed of par-tially crystalline partially oriented linear polymers Interestingly fibres that fall outside these somewhat simplisticparameters such as glass ceramic fibres and fluoropolymers which for instance are highly oriented or of pronouncedcrystallinity do not enjoy extensive conventional textile usage

1211 Fibre NamesWhilst the names of natural fibres have evolved over several millennia those of man-made fibres have developed ina far more systematic way in more recent times Natural fibres are given a common name (eg cotton silk andflax) whereas man-made fibres are ascribed a generic name many textile fibres are also given trade names5 In thecontext of man-made fibre generic names in 1971 the European Commission (EC) issued a Directive which soughtto harmonise the names of textile products as well as their use on labels and in marketing documents [73] The Directivehas been subsequently amended several times and from 8 May 2012 Regulation (EU) No 10072011 [74] whichconcerns textile fibre names and related labelling and marking of the fibre composition of textile products (whichrepealed and replaced former directives 2008121EC 9673EC and 7344EEC [73 75]) governs the use of fibrenames in the EU [73] In the United States textile generic names are allocated by the Federal Trade Commission [76]Unfortunately for some fibres different generic names are applied in the United States and the EU as exemplified byviscose (EU)rayon (US) and elastane (EU)spandex (US) In this book the generic names of man-made fibres arethose allocated by la Bureau International pour la Standardisation des Fibres Artificielles (BISFA) [77] these beingshown in Figure 17 together with the relevant BISFA abbreviation (eg CA and CV)

From the viewpoint of dyeing textile fibres can be classified as hydrophilic or hydrophobic in terms of theirwater sorption properties (Table 12) as water sorption is a fibre property of fundamental importance to aqueousdyeing and which varies markedly for different fibre types Whilst the concepts of hydrophilicity and hydropho-bicity are discussed in Chapter 3 in essence a surface which when contacted with water is termed hydrophilicwhen it displays good wettability with water (and generates a contact angle6 θ le 90 ) and is hydrophobic whenit displays low wettability with water (and θ gt 90 ) [78] For instance hydrophilic fibres such as natural cellulosicfibres characteristically absorb large amounts of water and undergo sizeable radial swelling whereas hydrophobicsynthetic fibres such as PES absorb almost no water and do not swell As subsequently discussed the watersorptive properties of a fibre determine the type of dyes that are employed for its coloration For examplehydrophilic cotton and wool fibres are readily dyed using water-soluble direct dyes and acid dyes respect-ively whereas the hydrophobic synthetic fibre PES is dyeable only using sparingly water-soluble disperse dyes(Table 12) The relative hydrophilicityhydrophobicity of textile fibres in relation to dyeing are discussed later

Table 12 Classification of fibres based on water sorption characteristics

fibre dye class

Wool hydrophilic Acid mordant reactiveSilk Acid mordant basic vatCLY Direct vat sulphur reactiveCV Direct vat sulphur reactive

Cotton Direct vat sulphur reactiveCA hydrophobic DisperseCTA DispersePA 6PA 66 Acid mordant direct disperse reactivePAN Basic dispersePES Disperse

5 neither the common name nor the generic name is trademark protected6 see Chapter 3 for a discussion of contact angle


122 Textile UsageWorld textile fibre demand in 2012 was 789 times 106 T [79] resulting in per capita consumption of 113 kg assuming aworld population of ~70 times 109 [80 81] Of this global textile fibre usage PES fibres accounted for ~55 (433 times 106 T)and cotton fibres ~30 (234 times 106 T) with wool silk and other natural fibres making up only a very small proportion(~15 12 times 106 T) and other man-made and synthetic fibres comprising ~135 (~11 times 106 T)

As Figure 18 shows between 1900 and 2000 world fibre production grew ~10 fold which contrasts with a 38-foldincrease in world population and a 27-fold increase in per capita economic prosperity over the same period [83] How-ever between 2000 and 2010 world fibre production grew by ~45 compared to an increase in world population ofonly 13 [84] Such a contemporary high rate of increase in textile demand seems likely to continue for the foreseeablefuture not simply because world population is predicted to grow to gt9 billion by 2050 and exceed 10 billion by 2100[85] but also since global economic growth appears set to continue to increase despite the recent global fiscal austerityhigh public debt burden and financial fragility [86] indeed it has been estimated that world fibre production will reach140 times 106 T by 2050 [83] Figure 18 also shows the marked increase in global textile production of synthetic fibres thathas occurred over the past 30 or so years a trend that seems unlikely to change

123 The History and Development of Textile FibresAs the history and development of textiles and textile fibres has been the subject of many publications the followingserves only as a brief outline of the origins of this significant facet of human progress

1231 Natural FibresFor an overview see Refs [5 25 87ndash93] From an historical perspective precise knowledge of the origins of the use ofthese substrates and their development as textile materials which also includes their dyeing is not possible As earlytextiles were of organic origin and therefore susceptible to degradation only very few samples of textiles have sur-vived from prehistory written records did not appear until around 3100 BCE Recourse is therefore made to archaeo-logical evidence provided by the few textile remnants related tools art etc

Whilst the earliest known woven textiles from the southern Anatolian (present day Turkey) Neolithic settlementCcedilatal Hϋyϋk date from 6000 BCE these are pre-dated by some 100ndash500 years [90 94] by nets mats and other similarlyless complex structures However it is generally accepted that long before weaving had been developed prehistoric manwas able to join animal hides and skins use gut vines and sinew as threads and string and also had discovered the impor-tance of twisting fibres to enhance the strength of such threads and strands Indeed needles which could be used for thejoining of animal skins as well as seeds shells etc were first employed in Europe around 26 000ndash20 000 BCE Beads thatwere likely strung with vines gut etc dating from 38 000 BCE as well as three-ply cordage that dates from 18 000 to 15000 BCE have been found in France [90] As such whilst the precise origins of spinning and weaving are unknown it islikely that spinning as practiced in theproductionof cordage string etc precededweaving It is commonlyaccepted thattheweavingof textiles on loomsbegan in theNeolithic period 6000ndash5000 BCETheEgyptians are generally considered tobe the worldrsquos first skilled weavers linen weaving having become a staple industry in Egypt by ~5500 BCE [95]

80

60 synthetic

regenerated cellulosic

raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010

Figure 18 World textile fibre production 1900ndash2010 Data from [82]


Although five main types of natural fibre were exploited by primitive man namely hemp flax wool cotton and silkother fibre types were also used such as those derived from for example goat tree bark rabbit and papyrus Fibreblends were also utilised in prehistoric times as exemplified by samples of cotton and raw silk dating from 1500 to1000 BCE [90] The two bast fibres hemp (which provides linen) and flax were the foremost fibres of prehistory prob-ably due to their abilities to adapt to a range of habitats and climates and to afford uses other than fibres (eg linseed oiland animal feed [90 96]) Indeed fragments of woven flax dating from 3000 BCE have been discovered [97] and linensamples dating from 10 000 BCE have been found in Switzerland Seeds of cultivated flax from 8000 BCE were discov-ered in Syria [94] and hemp seeds dating from 5500 to 4500 BCE in northern Europe [90]

Although sheep were domesticated by or before 7000 BCE [97] it is unclear as to whether wool was first used inde-pendently of the hide for textiles at this time or the woolly fleece did not develop until the early Bronze Age Cottonwas probably cultivated in Pakistan before 4000 BCE and records of cotton date from around 4300 BCE in Mexico and~3300 BCE in Peru [98] The ruins of Mohenjo-daro provide evidence that cotton spinning was practiced in the IndusValley around 2500ndash3000 BCE (eg [99 100]) and cotton seeds have been found dating from the second half of thesecond millennium BCE [100] It is generally agreed that the Chinese were the first to cultivate the silkworm and man-ufacture silk from around 4000 BCE with the earliest surviving silk samples dating back to 2850ndash2650 BCE howeverwild silk fibre was woven in India as early as 2500 BCE [101] Details of the fibrersquos manufacture remained a closelyguarded secret for much of this time despite the famous trade explorations commonly represented by the Silk Roadwhich began around 206ndash220 CE indeed sericulture was introduced to Japan around 195 CE reaching Constantinoplein the seventeenth century and then gradually spreading to the Western world [102]

1232 Man-Made FibresSee Refs [25 103ndash108] for a summary The prospects of producing an artificial version of the then most prized oftextile fibres silk fascinated scientists of the seventeenth and eighteenth centuries Hooke is generally credited withinspiring this pursuit of lsquoartificial silkrsquo fibres by theorising in 1665 that an lsquoartificial glutinous compositionrsquo similar tothat secreted by silkworms might be made which could be lsquodrawn outrsquo into lsquosmall wiresrsquo or filaments [109] Reacuteaumur(1734) produced coarse fibres using varnish passed through holes in a can thereby demonstrating the first dry-spinningprocess and Schwabe (1840) invented the precursor of the spinneret extruding molten glass filaments Between around1850 and 1900 considerable research was undertaken and commercial success achieved in the search to produce lsquoarti-ficial silkrsquo fibres All of the ensuing commercially significant fibres were derived from the natural polymer celluloseby means of its chemical transformation entailing cellulose derivatisation spinning of filaments and subsequentregeneration of the cellulose polymer As such the term regenerated cellulosic is often applied to such man-madefibres of cellulosic origin although regenerated protein fibres were also produced as exemplified by casein

The first commercial man-made fibre Chardonnet silk obtained from cellulose nitrate was introduced in 1889This major landmark in textile fibre development stemmed from Schoumlnbeinrsquos discovery (1846) of nitratedcellulose7 as well as Audemarsrsquo (1855) observation that fibres could be drawn from an alcoholic ether solution ofcellulose nitrate together with the first demonstration of the lsquospinningrsquo of lsquoartificial silkrsquo fibres by Swan (1883)The introduction of Chardonnet silk was closely followed by that of cuprammonium silk (Cupro CUP 1899) whicharose from both Schweizerrsquos earlier discovery (1857) that cellulose dissolved in ammoniacal copper oxide could beregenerated in a coagulation bath as well as from spinning process developments by Despeissis and other researchers(eg [110 111]) The most commercially important of all regenerated cellulosic fibres viscose (CV) resulted from thediscovery by Cross Bevan and Beadle (1891) that cellulose could be dissolved in NaOH and CS2 and the ensuingviscous solution (later called lsquoviscosersquo) could be coagulated in NH2SO4 to produce fibres The viscose process becameindustrially viable in 1905 with staple CV fibre being introduced in the 1920s and in the late 1930s high-strength CVtyre yarns were launched In the 1960s High Wet Modulus (HWM) CV fibres were introduced that display propertiesmore similar to their cotton counterparts (eg lower shrinkage and more pleasant wet texture) and which are termedmodal (CMD) fibres (eg [89 112ndash116]) Although CV has dominated the regenerated fibre market since the fibrersquosinception in more recent times owing to environmental concerns and price competition from synthetic fibres simplerless-polluting manufacturing routes to the production of man-made cellulosic fibres were sought Of various non-aqueous solvents capable of dissolving cellulose directly and which could be readily recovered N-methyl morpholineoxide (NMMO) was commercially utilised to produce lyocell (CLY) fibres8 (1992) (eg [116ndash119]) Whilst Schuumltzen-berger first isolated cellulose triacetate (CTA) in 1865 commercial applications of the new material were hindered bythe high price of the raw materials and the polymerrsquos insolubility in low-cost solvents Miles (1904) synthesised theacetone-soluble cellulose acetate (CA) by the partial hydrolysis of CTA and large-scale textile fibre production

7 and the explosive material Schiesswolle or gun-cotton8 strictly CLY fibres are reconstituted cellulosic fibres since their production does not involve cellulose derivatisation prior to regeneration ofcellulose


occurred in 1921 Very strong (high orientation high crystallinity) CV fibres (Fortisan) were introduced in the 1940sand CTA fibres were commercially introduced in 19549 (eg [112 120ndash122]) Although regenerated protein fibresobtained from milk (casein) and gelatin were investigated as potential lsquoartificial silkrsquo fibres at the end of the nineteenthcentury the commercial possibilities of this type of regenerated fibre were revived in the 1930s and over the ensuingtwo or so decades commercial products appeared derived from sources including milk as well as ground nut proteincorn and soya bean (eg [108 111 123]) From the mid 1970s commercial interest also developed in producing fibresfrom spider silk (eg [124ndash129]) However with the exception of alginate fibres which are utilised in the form ofadvanced wound-care non-wovens regenerated protein fibres have not experienced the widespread commercial useenjoyed by their regenerated cellulosic counterparts

1233 Synthetic FibresRefs [25 111 130ndash133] provide an overview of this topic The development of synthetic fibres has been the subject ofa great many articles The origin of synthetic textile fibres stems from the discovery by Klatte (1913) of a process forwet-spinning polyvinyl chloride (PVC) fibres although commercial realisation was delayed until the 1930s owing tothe polymerrsquos insolubility in commercial-scale solvents by 1934 PVC was widely used in Germany [134 135] How-ever this discovery and the technical successes achieved by the producers of regenerated cellulosic fibres during theearly part of the twentieth century were accomplished despite a marked lack of understanding of textile chemistry andpolymer science This particular situation changed gradually owing to the ground-breaking studies made in the 1920sand 1930s by both Staudinger10 [137] who showed that compounds such as natural rubber were of very high molarmass and were composed of a large number of small molecules that were connected by a covalent linkage via a reactionthat he called lsquopolymerisationrsquo and by Carothers11 on the condensation polymerisation of esters and amides [139]

PVC was first melt-spun in 1932 and the discovery that copolymerisation improved solubility resulted in the intro-duction of the chlorinated polvinyl chloride fibre Pe-Ce and the vinyl chloridevinyl acetate fibre Vinyon in the mid1930s [140ndash142] What many authors consider to be a landmark in the production of synthetic fibres occurred in 1939when PA 66 (aka nylon 66) fibre was commercially produced fibres having been first prepared in 1935 [143] This wasquickly followed by the appearance of many other synthetic fibres such as PA 6 (aka nylon 6) prepared by Schlack in193812 [144] and polyethylene (PE) in 1939 as well as acrylic (aka polyacrylonitrile PAN) and modacrylic (MAC) inthe 1940s and polyester (PES) polypropylene (PP) and elastane (EL) in the 1950s (eg [111 145ndash153]) The pop-ularity of synthetic fibres is reflected in the world fibre production data shown in Figure 18 Clearly whilst cotton fibreproduction has increased steadily over the past 100 or so years and that of its regenerated counterparts has remainedreasonably stable over the past 70 years or so synthetic fibres have enjoyed sustained increasing growth since theirintroduction in the 1950s wool fibre production has declined in recent decades

Developments over the past 40 or so years have resulted in what some authors refer to as a lsquosecond generationrsquo ofman-made fibres which possess significant superiority in one (or more) property compared to conventional textilefibres such as high strength and stiffness marked chemical or thermal resistance Such fibres are referred to as specialistfibres or more commonly nowadays high performance fibres the latter term mostly relating to fibres that possess high-modulus coupled with high-tenacity (HM-HT)13 Whilst such fibre types are not widely used in conventional textilemarkets (ie apparel interior furnishings household) they nevertheless enjoy widespread industrial engineeringand biomedical applications In the 1960s interest in producing specialist fibres resulted in the semi-aromatic polyam-ide PA 6T and the high-temperature-resistant m-aramid fibre poly(m-phenylene isophthalamide) (MPIA aka Nomex)Subsequently various types of high-performance fibre have been developed including the aromatic rigid rod lyotropicliquid crystalline poly(p-phenylene terephthalamide) (PPTA aka Kevlar) fibres in the 1970s thermotropic liquidcrystalline polymers (TLCP) such as the aromatic polyester fibre Vectran the temperature-resistant and chemical-resistant poly(phenylene sulphide) (PPS) fibres (FCT generic name sulfar) in the 1980s as well as heterocyclic rigidrod polymers exemplified by both the high-temperature-resistant polybenzimidazole (PBI) and poly(p-phenylenebenzobisoxazole) (PBO aka Zylon) gel-spun PE fibres (aka high-performance polyethylene (HPPE) or high-moduluspolyethylene (HMPE)) as exemplified by Dyneema fibres as well as high thermal resistant thermosets such as mela-minendashformaldehyde fibres (eg Basofil) in the 1980 and 1990s In addition to organic high-performance fibres such asthose mentioned above several inorganic high-performance fibres are produced namely carbon fibres ceramic fibresand glass fibres The reader is directed elsewhere for fuller accounts of this large area (eg [18 154ndash161])

9 in the manufacture of CA fibres as CAT is produced prior to the diacetate variant in many publications CTA is often referred to as primarycellulose acetate and diacetate referred to as secondary cellulose acetate10 Staudinger first proposed the term lsquomacromoleculersquo in 1922 [136]11 see for example [138]12 marketed in the late 1940s under the trade name Perlon [135]13 whilst the maximum strength and modulus of conventional synthetic fibres is about 1 and 15 GPa respectively that of high performance fibres isgt2 and gt55 GPa


124 Textile PolymersBoth natural and synthetic polymers are an essential part of everyday life major examples of their use including plastics[162 163] such as low density (aka branched) and high density (aka linear) PE elastomers [164 165] which includenatural rubber and the synthetic variant styrene-butadiene rubber and of course textile fibres Since generally alltextile fibres that enjoy widespread usage are organic polymers this section considers some of the fundamental prin-ciples and properties of such polymers of relevance to textile fibres

1241 PolymersBerzelius first used the term polymer in 1832 [166 167] although this researcherrsquos early definition differs markedlyto that in contemporary usage The origins of polymer technology lay in the early nineteenth century as representedby the spreading of masticated natural rubber on cloth in 1820 [168] and the first patents on vulcanised rubberin the 1840s whilst those of polymer science stem from the pioneering work of Staudinger in the 1920s who firstintroduced the term makromolekuumll (macromolecule) to designate long-chain molecules with colloidal nature[166] This account provides only a brief introduction to the extremely large diverse and complex areas of polymerchemistry and polymer technology Comprehensive and informative accounts of the fundamentals of both polymerchemistry and polymer technology are available in several well-cited textbooks (eg [163 168ndash174]) Useful defini-tions in polymer science are available [175] and various polymer terms and definitions are available from IUPAC[176 177]

In the latter context according to IUPAC [175] the term polymer refers to a substance composed ofmacromolecules where the term macromolecule (aka polymeric molecule) refers to a single molecule for the purposesof this book the terms macromolecule and polymer will be used interchangeably In simple terms a polymer is a largemolecule that is made up of smallermonomers that are linked together covalently A monomer comprisesmonomermole-culeswhich can undergopolymerisation a process by which themonomer is converted into a polymer Monomersvary inthe number of covalent bonds that they can form with other reactants this being expressed by their functionality f Thepolymerisation of a bifunctional monomer (f = 2) such as acrylonitrile (I) results in a linear polymer in this casepoly(acrylonitrile) PAN (II) whereas that of polyfunctional monomers (f gt 2) yields branched polymers14 whenbranches interconnect three-dimensionally crosslinked polymers (aka network polymers) arise (eg phenol-formaldehyde resins III)

CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2

A homopolymer is formed when only one type of monomer is used as exemplified by cotton in which the cellulosicmacromolecular chains comprise D-glucopyranose monomers joined by β 1 4 linkages (ie the C-1 and C-4 groupsof adjacent monomeric molecules link successively through a β-configuration) The repeat unit of cellulosic materialsoften is depicted as two glucose monomeric units IV (referred to as the disaccharide cellobiose) since the β positionof the OH groups at C-1 dictates a 180 rotation of the following glucose unit around the 14 axis of the pyranosering In the case of undegraded cotton fibre the degree of polymerisation DP (see Section 1244) may be gt20 000D-glucopyranosyl monomer units [25]

OO

OHOH

O

OH

O

OH

HO

HO

nIV

14 which can take several forms such as ladder comb and star-shaped


ndashAAAAAAAAAAAAAAAndash

BBB

BBB

BBB

V

If two or more types of monomer are employed the ensuing material is a copolymer as exemplified by the poly-merisation of hexamethylene diamine (NH2(CH2)6NH2) and adipic acid (HOOC(CH2)4COOH) which results in thecopolymer PA 66 (NH(CH2)6NHCO(CH2)4CO) Copolymers derived from bifunctional monomers are dividedinto four types based on whether the distribution of the two monomers A and B in the polymer is

(1) random (random copolymers AABAABBBAABABB)(2) alternating (alternating copolymers ABABABAB)(3) sequential (block copolymers AAABBBAAABBB) or(4) blocks of monomer are grafted onto another (graft copolymers (V))

1242 NomenclatureAlthough polymer science and technology have their origins in the 1920s there is still no universally adopted systemfor naming polymers despite the quite remarkable developments that have occurred within these fields over the past~100 or so years As might be expected this can lead to confusion indeed a very wide range of trade names commonnames trivial names abbreviations and chemical names are employed for polymers The development of a systematicapproach to the naming of polymers was initiated by IUPAC in the 1950s which has continued up to the present timeAlthough IUPAC has developed a nomenclature system for polymers it is not universally applied Briefly three sys-tems of polymer nomenclature are in general use The first of these systems namely trade names or brand names (andabbreviations) is widely used by manufacturers processors fabricators and the like to describe and differentiate com-mercial products The two further types of naming system are based on the source of the polymer (ie a system that usesthe name of the monomer) and a more explicit structure-based nomenclature that can be used when the polymer struc-ture is known However traditional polymer names continue to be used

12421 Source-Based Nomenclature System In this system the name of the monomer is prefixed by the wordpoly such as polyethylene in the case of polymers derived from single monomers When the monomer has a very longname or a multi-word name parentheses are placed around its name as exemplified by poly(ε-caprolactam)15 or PA 6

12422 Structure-Based Nomenclature Systems Essentially two such nomenclature systems are in general usenamely a non-IUPAC system and an IUPAC system In the former case polymers derived from two different mono-mers (eg PES) are named by prefixing the name of the structural unit which is enclosed within parentheses by theword poly as in poly(ethylene terephthalate) The IUPAC nomenclature system is based on the use of a preferred con-stitutional repeat unit CRU this being the smallest constitutional unit of the polymer and which is named according tothe IUPAC procedures employed for the naming of small organic compounds (eg [176 178]) In recognition of thefact that some polymers have well-established source-based trivial or traditional names (eg polyethylene and pol-ypropylene) the IUPAC nomenclature system retains such names The intricacies of the formalised procedural IUPACpolymer naming system are outside this introductory discussion and the reader is directed elsewhere [178 179] Impor-tantly the CRU differs to the term that is commonly utilised in relation to polymer structure namely the repeat unitinsofar as for example in the case of PE whilst the CRU is CH2 the repeat unit is CH2CH2 Table 13 shows thesource-based and structure-based names as well as repeat units of some common polymers used in textile fibres

1243 Molar MassThe two properties that distinguish polymers from other molecules are their very large molecular size and long chainstructure The size of a polymer molecule can be defined in terms of either itsmolar mass or its degree of polymerisation

15 which often is also named as the equivalent poly(6-aminocaproic acid)


the latter parameter being a measure of the number of monomeric units in the polymer chain molecule Rather than molarmass the term molecular weight is often (inaccurately) used to describe the size of a polymer molecule this being thedimensionless relative molar mass Mr (aka relative molecular mass molecular weight [177] or RMM) of a uniformpolymer molecule (aka monodisperse polymer16 or polymer composed of molecules of the same mass) which is themass of the molecule relative to that of 12C To convert the dimensionless quantity Mr to molar mass M which isthe mass of 1 mole of the polymer (unit g molminus1) Mr is multiplied by the unified atomic mass unit17 u or dalton18

(symbol Da) the latter parameter often being used as a unit for the molar mass of a polymer However since polymersusually comprise molecules that are non-uniform with respect to their molar mass (ie they are non-uniform polymersor polydisperse polymers) and contain molecular chains of varying lengths their molar mass is related to their degree ofpolymerisation Thus linear and branched polymers (with the exception of some naturally occurring polymers) consist ofmolecules with a molar mass distribution as illustrated by the idealised simple molecular mass distribution inFigure 19

Such a distribution can be described in terms of several averages the two most commonly employed being thenumber average Mn and the mass average (aka weight average) Mw Eqs 11 and 12 where Ni is the numberof molecules of molar mass Mi and denotes summation over i molecules19 As Mw is influenced by the relativelysmaller number of large molecules Mw gtMn

Table 13 Structure- and source-based names of some polymers

common name structure-based name source-based name repeat unit

Polyethylene Poly(methylene) Polyethylene (CH2CH2)n

Polypropylene Poly(1-methylethane-12-diyl) Polypropylene (CHCH2)n

CH3

Acrylic Poly(1-cyanoethane) Polyacrylonitrile (CHCH2)n

CNPolyester Poly(oxyethane-12-

diyloxyterephthaloyl)Poly(ethylene

terephthalate) CO)n(O(CH2)2OOC

Nylon 66 Poly(imino (16-dioxo-16-hexanediyl) imino-16-hexanediyl)

Poly(hexamethyleneadipamide)

(NH(CH2)6NHCO(CH2)4CO)n

Nylon 6 Poly(imino(1-oxohexane)-16-diyl)

Poly(ε-caprolactam) or poly(6-aminocaproic acid)

(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules

Figure 19 Idealised molecular mass distribution

16 IUPAC no longer recommends the use of the terms monodisperse polymer or polydisperse polymer [180]17 atomic mass unit AMU is equal to 112 the mass of one atom of 12C (=16606 times 10minus27 kg)18 1 Da = 1 g molminus1 although strictly it is a unit of molecular mass (ie 1 Da = 1660 538 782(83) times 10minus27 kg19Mv and the z-average Mz are less widely used



























2015018225



1 2016

Contents


Preface xiii






References 51



References 76








References 137



References 164






vi Contents


References 200




References 241









viiContents vii









References 413






viii Contents




References 479








References 524






ixContents ix



References 553




References 568





References 594

Colorants Index 601

Subject Index 605

x Contents










Preface






Units and Symbols




Commercial Names





Leeds 2015




xiv Preface


11 Textiles































polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules




Contents


Preface xiii






References 51



References 76








References 137



References 164






vi Contents


References 200




References 241









viiContents vii









References 413






viii Contents




References 479








References 524






ixContents ix



References 553




References 568





References 594

Colorants Index 601

Subject Index 605

x Contents










Preface






Units and Symbols




Commercial Names





Leeds 2015




xiv Preface


11 Textiles































polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules







References 137



References 164






vi Contents


References 200




References 241









viiContents vii









References 413






viii Contents




References 479








References 524






ixContents ix



References 553




References 568





References 594

Colorants Index 601

Subject Index 605

x Contents










Preface






Units and Symbols




Commercial Names





Leeds 2015




xiv Preface


11 Textiles































polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules





References 200




References 241









viiContents vii









References 413






viii Contents




References 479








References 524






ixContents ix



References 553




References 568





References 594

Colorants Index 601

Subject Index 605

x Contents










Preface






Units and Symbols




Commercial Names





Leeds 2015




xiv Preface


11 Textiles































polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules












References 413






viii Contents




References 479








References 524






ixContents ix



References 553




References 568





References 594

Colorants Index 601

Subject Index 605

x Contents










Preface






Units and Symbols




Commercial Names





Leeds 2015




xiv Preface


11 Textiles































polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules







References 479








References 524






ixContents ix



References 553




References 568





References 594

Colorants Index 601

Subject Index 605

x Contents










Preface






Units and Symbols




Commercial Names





Leeds 2015




xiv Preface


11 Textiles































polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules






References 553




References 568





References 594

Colorants Index 601

Subject Index 605

x Contents










Preface






Units and Symbols




Commercial Names





Leeds 2015




xiv Preface


11 Textiles































polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules













Preface






Units and Symbols




Commercial Names





Leeds 2015




xiv Preface


11 Textiles































polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules






Commercial Names





Leeds 2015




xiv Preface


11 Textiles































polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules





11 Textiles































polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules





















polymer

spinneret


texturised yarns



(a)



spun yarn

(b)









formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules








formation



meltedpolymer


cool air

spinneret

dissolvedpolymer

spinneret

evaporatingcabinet

dissolvedpolymer

solventextraction

spinneret







(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules








(a) (b)








12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules









12 Textile Fibres





















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules

















fibre dye class










80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules









80

60 synthetic


raw woolraw cotton

40

20fibre

pro

duct

ion

x 1

06 T

01900 1910 1920 1930 1940 1950 1960 1980 1990 2000 2010


















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules



















CH2=CH

ICN

II

(CH3CH2)

CNn

III

CH2ndashRndashCH2

CH2


OO

OHOH

O

OH

O

OH

HO

HO

nIV




BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules





BBB

BBB

BBB

V
















CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules











CH3










(NH(CH2)5CO)n

molecular mass

Mn

Mz

Mw

num

ber

of m

olec

ules




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