Textile Science

Textile fiber chemical and physical properties

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Textile Science

Textile fiber chemical and physical properties

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Rayas Hassan

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Introduction to fibre polymers and fibre properties
The cellulosic fibres
The ester-cellulose fibres
The protein fibres
The synthetic fibres

Textile science E.P.G, Gohl L.D. Vilensky Longman Cheshire iffLongman Cheshire Pty Limited Longman House Kings Gardens 95 Coventry Street Melbourne 3205 Australia Offices in Sydney, Brisbane, Adelaide, and Perth Associated companies, branches, and representatives throughout the world © 1980 Longman Cheshire © This edition 1983 Longman Cheshire First published 1980 Reprinted 1981 Second edition 1983 Reprinted 1985, 1986 All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the copyright owner. Printed in Malaysia by Percetakan Jiwabaru Sdn. Bhd., Kuala Lumpur Designed by Joanne Waite National Library of Australia Cataloguing-in-Pubiication data Gohl, E, P. G, (Erhard Paul Gottlieb). ‘Textile science. 2nd ed. Previous ed.: Melbourne : Longman Cheshire, 1980. For senior secondary school students. includes index. ISBN 0 582 68595 8. 1. Textile fabrics. _ I. Vilensky, L. D. (Leo David). I. Titl. 677Contents Preface to the first edition Preface to the second edition Acknowledgements 1 Noan om 8 Introduction to fibre polymers and fibre properties The cellulosic fibres ‘The ester-cellulose fibres The protein fibres ‘The synthetic fibres Dyeing and printing The chemical finishing of textiles Colour Glossary Appendix — Physical properties of fibres Index vi vil 41 60 68 89 120 165 177 204 210 2141 Introduction to fibre polymers and fibre properties 1 have often thought, that probably there might be a way found out, to make an artificial glutinous composition, much resembling, if not fully as good, nay better, than that excrement, or what ever substance it be out of which, the silkworm wire-draws his clew... This hint ... may give some ingenious inguisitive person an occasion of making some trials, which if successful ... 1 suppose he will have no occasion to be displeased. This speculation on making a filament was written in 1664 by the English physicist Dr Robert Hooke in his book Micrograpkica. His speculation became a reality from 1900 onward. It became a reality because of the continuing scientific investigations being carried out on natural and man-made fibres and similar materials. These investigations have yielded a steadily increasing understanding of fibre composition, structure, properties and behaviour, and have enabled the large-scale manufacture of fibres not found in nature, i.e. man-made fibres. The knowledge and understanding gained from manufacturing fibres, as distinct from growing them, has assisted in increasing the understanding of the very complex molecular or polymer composition of the natural fibres. Even though very much more is now known about fibres, there are still many un- answered questions about their properties and behaviour. Some of the answers will, no doubt, be provided in the years to come. In the meantime, in order to understand some of the reasons why a fibre possesses certain properties and behaves in a particular manner when in use, it is necessary to acquire a knowledge of the following properties. Polymerisation Textile fibres, like most substances, are made up of molecules. Fibre molecules are called polymers (derived from the Latin poly = many and mer = unit). The ‘unit’ of a polymer is the monomer, also derived from the Latin (mono = one). At the molecular level the polymer is extremely long and linear, whereas the monomer is very small. Monomers are usually chemically reactive, whereas polymers tend to be unreactive. This is illustrated by the chemical reaction called polymerisation, which causes the monomers to join end-to-end to form a polymer.Textile science Although the polymer tends, in general, to be chemically unreactive, this does not prevent its being subsequently attacked by chemicals and other degrading agents. ‘The length of the polymer is most important. All fibres, both man-made and natural, have long to extremely long polymers. Measuring the length of a polymer is a complicated, if not impossible, task. Estimates of the length of a polymer can be obtained by determining its degree of polymerisation. This is often abbreviated to DP and defined by the following mathematical expression: average molecular weight of polymer degree of polymerisation, = molecular weight of the repeating unit in the polymer Nove: Some fibre polymers may have been polymerised from two or more different monomers; thus, the repeating unit is the combination or segment formed by these two or more different monomers which repeat regularly along the length of the polymer. In determining the degree of polymerisation of cotton, for instance, a figure of 5000 is obtained. This means that, on average, each cotton polymer consists of about 5000 repeating units. With cotton the repeating unit is cellobiose, which may also be taken as its monomer. Cotton provides an example to illustrate the size relationship between polymer and monomer. Imagine the cotton polymer to be as thick as an ordinary 8 mm pencil; the polymer would then be about 50 m long. As it consists on average of about 5000 repeating units or monomers, then each one of these would be about 10 mm long — a ratio of 5000:1. A polymer is often described as having a backbone, consisting of the atoms which are bonded to each other in a linear configuration and which are responsible for the length of the polymer. This is illustrated in Table 1.2. Although it is not yet known how cellulose and keratin are polymerised in nature, the polymerisation of man-made, synthetic monomers to polymers is quite well understood. The manufacture of the synthetic, polymeric material which will be extruded to form the synthetic, man-made filament is categorised into two types of polymerisation: addition and condensation polymerisation. Addition polymerisation With this type of polymerisation the monomers add or join end-to-end without liberat- ing any by-product on polymerisation. Some fibres consisting of addition polymers are acrylic, modacrylic, polyethylene or polyethene, polypropylene or polypropene, polyvinyl alcohol and the chlorofibres, namely polyvinyl chloride and polyvinylidene chloride. Condensation polymerisation With this type of polymerisation the monomers join end-to-end and liberate a by- product. This by-product is usually a simple compound — generally water — but it may alternatively be hydrogen chloride or ammonia, depending upon the specific monomers involved. Some fibres consisting of condensation polymers are elastomeric, nylon and polyester.Introduction to fibre polymers and fibre properties Note: The polymers of acetate, cotton, flax, silk, triacetate, viscose and other regenerated cellulose fibres, and wool, do not fit readily into the above classification, because not enough is known as yet about the way their polymers are synthesised in nature. A knowledge of addition and condensation polymerisation is of importance in the synthesis and large-scale manufacture of the textile polymeric substances and their extrusion as textile filaments. Such knowledge belongs more to chemical engineering technology than to textile technology. Similarly, a knowledge of the propagation, growth, nurturing and harvesting of natural fibres belongs more to the specialised agricultural sciences of animal husbandry and crop cultivation. The textile technologist recognises such knowledge as being peripheral and to be used for rounding off explanations and understanding of fibre properties and behaviour. Synthetic fibre polymers and their respective fibres are at times referred to by the appropriate name found in the categorisation below. It will be noted that the natural, regenerated and ester-cellulose fibres are not included. The reason is that insufficient is known about the growth, formation and/or synthesis of their polymers. Types of polymer Homopolymer Such a polymer is polymerised from the same (= homos in Greek) or only one kind of monomer. Some homopolymer fibres are: nylon 6, nylon 11, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile as distinct from acrylic and modacrylic. See also Tables 1.1 and 1.2. Copolymer Such a polymer is polymerised from two or more different monomers. There are four sub-categories of copolymers, as follows. Alternating copolymer Usually two monomers polymerise in an alternating sequence, as shown in Table 1.2. Some alternating copolymer fibres are: nylon 6.6 and polyester; see also Table 1.1. Block copolymer Two or more different monomers polymerise in blocks or segments before linking up to form the polymer; see Table 1.2. Block copolymers are still largely experimental. Graft copolymer ‘The polymer is polymerised in such a manner that a segment, polymerised from the two or more different monomers used, attaches itself as a side-chain or forms a branch of the polymer; see Table 1.2, Sometimes the side-chain may be polymerised only from ‘one of the three monomers. Then the other two monomers form the backbone of the polymer, usually as an altering or random copolymer. In general, graft copolymer 3‘Table 1.1 Chemical composition and structure of the most commonly used textile fibres. Fibre Basic unit or monomer Polymer Acetate The hydroxyl groups on the CH,00CCH, H Hsccoo cellulose polymer are L mee acetylated to the degree that A \R A AH the acetate or secondary H \/ \fOH HAY cellulose acetate polymer has ‘oH HA RY AL less than 92 per cent but at jo ¢ HH ¢—___¢ least 74 per cent ofits hydroxy! HO] 4h Hyccod Gx,0000H, groups acetylated; that is, 2.3 ° to 2.4 of the OH-groups per The acetate or secondary cellulose acetate po- glucose unit are acetylated. lymer, which has a degree of polymerisation of ‘This is usually shown as 4 about 130 units (i.e. = 130). acetate groups per cellobie cuso000t ¥racco9 The triacetate or primary ¢ © ¢ @ cellulose acetate polymer has | /1 \ALboccn, \e at least 92 per cent of its Prooccr, 4 & Arr ok hydroxyl groups acetylated. In Vee ZN /$4 general, this isshownas6 yo'| —§ § io acetate groups per cellubiose HH H,CC0O CH,OOCCH, unit, The triacetate or primary cellulose acetate poly- ‘mer, which has a degree of polymerisation of about 225 units (i.e. n = 225). Acrylic Acrylic At least 85 per cent of the mass HOH HOW of the acrylic fibre must be i 4 1 ot composed of acrylonitr Ho-|—¢— S—) = |e —¢—)-|-H ‘monomers; that is, ea sie How m P. ‘and no more than 15 per cent is complosed of the ‘copolymer; that is, HOH too c=c HO x where X is usually an anionic radical, e.g. —Cl, —OOCCHs, —CONH,, ete. Modacrylic At least 35 per cent but no more than 85 per cent of the mass of the modacrylic fibre polymer must be composed of acrylonitrile monomers, and the remainder is composed of the copolymer. ‘The acrylic polymer. The values of m and p de- pend upon the mass of copolymer present; hence, whether it will be an acrylic or a modacrylic poly- ‘mer fibre. The degree of polymerisation is about 2000 units (ive. = 2000).Table 1.1 (continued) Basic unit or monomer Polymer HOH de tA NA Aa AS Avo ahs, NI /\,, oH.0H Cellobiose, the basic unit of cellulose, CH-OH HOH tA NP AAS ARS NE /\ HO 4 oOW GH.0H Cellulose, the polymer of cotton, with a degree of polymerisation of about 5000 celloboise tnit = 5000). em Cuprammonium or cupro, polynosic or modal, and viscose Cellobiose is the basic unit of the cuprammonium, polynosic anid viscose polymer. See cotton for chemical formula details. Note: The name rayon is no longer preferred for these three fibres; see page 54. Cellulose, in regenerated form, is the polymer of these three regenerated cellulose fibres; their degree of polymerisation is about: 250 cellobiose units (Le. n = 250) for cuprammonium; 300 cellobiose units (i.e. n = 300) for polynosic; 175 cellobiose units (i.e. m = 175) for viscose. Elastomeric The complexity and length of the elastomeric monomers and the repeating units of their polymers makes it impossible to reproduce them satisfactorily within the con- fines of this table. Refer, therefore, to the section on elastomeric fibres in Chapter 5, “The Synthetic Fibres’ for the two types of elastomeric monomers and polymers; that is, the polyester and polyether types. Flax Cellobiose — see cotton for chemical formula details. Cellulose is also the polymer of flax, with a degree of polymerisation of 18 000 cellobiose units; that is, n = 18000. See cotton for chemical formula details. Nylon For nylon 6,6 the monomers and hexamethylene diamine: HN(CH,)NE2 for nylon 6 the monomer is caprolactam: we cH, CHe le a I PS CHe co Nc, [-OC(CH)),CONH(CH2).NH |, Polyhexamethylene diamino adipate, the repeating unit of the nylon 6,6 polymer, with a degree of polymerisation of 50 to 80 units (i.e. n = 50 to 80) [-(CH,)sCONH-}, Polycaprolactam, the repeating unit of the nylon 6 polymer, with 2 degree of polymerisation of 200 units (i.e, = 200).Textile science ‘Table 1.1 (continued) Fibre Basic unit or monomer Polymer Polyester ‘The monomers of the most. [-OOC. <0oy- COO-(CH;)-], common polyester are ethylene py ; z thas lyethylene terephthalate, the repeating unit of ore Lee ee the polyester polymer, with a degree of poly- and terephthalic a merisation of 115 to 140 units (ie. n = 115 to HOOC-O)~ COOH 140). Rayon Note: the name rayon is no longer preferred (see page 54) and wool The silk fibroin polymer is R v Re composed of 16 different | _y44-CH-CO-NH-CH-CO-NH-GH~CO~],- OH simino side, whist the wool keratin polymer is composed The general formula for the polypetide polymer. of 20 different amino acids. Depending upon the type of radicals R, R’, R's Amino acids have etc, the polypeptide polymer would be identified general formula: either as being a silk fibroin polymer or a wool R keratin polymer. H.N-C-COOH, ‘The degrees of polymerisation for silk and wool are not known, H where R = a radical, which is different for each of the 20 known amino acids. fibres tend to have softening points which are too low for apparel and household textile use. However, Zefran, an acrylic graft copolymer fibre, has become successful. Its manufacturer describes Zefran as ‘a graft copolymer of dye-receptive groups on a backbone of heat-resistant polyacrylonitrile’. Random copolymer ‘The monomers are polymerised in no particular order or in a random fashion as shown in Table 1.2. Random copolymers tend to be polymerised mainly from only two different monomers. Some random copolymer fibres are acrylic and modacrylic; see also Table 1.1. ‘The term comonomer is also used. It refers to the monomer which is added to the polymerisation reaction to impart the special properties desired in the copolymer, e.g. greater affinity for dyes as in the case of acrylic and modacrylic fibres. For instance, the comonomer of acrylic and modacrylic polymers, which incidentally gave rise to the term copolymer, is the ‘monomer other than acrylonitrile’ as defined and described on pages 91 to 94, Table 1.1 summarises the chemical composition and gives an indication of the structure for the polymers of the more commonly used textile fibres. Explanations of the chemical terms used can be found in the text and in the Glossary. Should further information be required, reference should be made to The Penguin Dictionary of Science by E.B. Uvarov et al., Penguin Books.ct ea (szomouow wuazayp oasyp iuosoudas 01 sjoquids ap 2q © pur OV 197) sraussjod a1qy Jo sous0B91e 7° aIQeLTextile science Intrapolymer bonding Intrapolymer bonding means the bonds holding the atoms together to make up the fibre polymer. The fibre polymer is equivalent to a molecule — the smallest portion of a substance capable of existing independently and retaining the properties of the original substance. Textile fibre polymers are organic compounds; the exceptions being the molecules comprising the man-made inorganic fibres and the natural mineral fibres. Describing HoH H eee H H ' I I | 1 1 1 1 1 I -c-c-c-c-c-c-c-Cc- ie. -c-c- I | I I I 1 ' \ 1 ! H HH H H H H H H H n oxtended structural formula of basic structural formula of the polyethylene polymer the polyethylene polymer, where m= 5400 approx. H H H H H H H H A H I 1 ' I 1 I I I | 1 -c-c-c-c-c-c-c-c~ le. -c-c- iaees gear eee geen ee io H H-@-H H H-¢-H H H-¢-H H H-G-H HH ¢ H H H H H H n extonded structural formula of basic structural formula of the polypropylene polymer the polypropylene polymer, were 7 = 1800 approx. FOF F F F F F FOF 1 I I 1 1 1 1 ! ! -c-c-c-c-c-c-Cc~ ie -|-c-c-|-H Prot trot 1 4 re F F FOF F F F sn extonded structural forma of the poiytetraluoroethyiene basio structural formula of polymer or fluorocarbon polymer, the polyttratiuoroathyiene polymer, 9, Tetlon where n= not avaiable H HoH H H oH H HOH 1 1 1 I 1 I 1 I 1 -¢-c-c-c-c-C-C7 le. -c-c-]|-H I I | I I 1 ' | 1 H cloH cl oH CoH H Cl L aA extended structural formula of the basic structural formula of the polyvinyl chloride polymer, the polyiny chiorde polymer, e.g. Ahov! where n = 1250-1450 approx Figure 1.1 Four examples of fibre polymers to illustrate the fact that they are organic compounds predominantly composed of carbon and hydrogen atoms; other examples of fibre polymers are given in Tables 1.1 and 1.2. 8Introduction to fibre polymers and fibre properties fibre polymers as organic compounds signifies that they are predominantly composed of carbon and hydrogen atoms, with some oxygen, nitrogen, chlorine and/or fluorine atoms. This may be seen from the polymer formulae given in Tables 1.1 and 1.2 and Fig. 1.1. The bonds between atoms in polymers In general, single covalent bonds join the atoms forming the polymer. The single covalent bond is represented by a single short line drawn between the letters or symbols used to represent the atoms of each polymer; see Tables 1.1 and 1.2. Single covalent bonds, defined and explained on page 2], are chemically very stable and unreactive. In fact this type of bond is practically indestructible when it occurs between carbon and carbon atoms, carbon and hydrogen, carbon and oxygen, carbon and chlorine, and carbon and fluorine atoms: a ee i ee i i It will be noticed (Tables 1.1 and 1.2) that much of the backbone of any fibre polymer Lokobo gogo FFF ‘The reason for this is the ready formation of such segments which, owing to their single covalent bonding, contribute significantly to the chemical stability of the polymer and hence of the fibre. ‘The stability and unreactive nature of the single covalent bond joining the atoms of fibre polymers may also be expressed objectively. It has been estimated that the bond energy or bond strength is between 330 and 420 kilojoules for these single covalent bonds. This indicates a magnitude of bond strengths in excess of any other intra- or inter-polymer forces of attraction. It is for this reason also that it usually requires severe and prolonged exposure to chemicals and/or heat before fibre polymer breakdown occurs. ‘There are, of course, segments of the polymer backbone that are composed of other atoms, which influence the properties of the polymer as follows. consists of carbon segments of varying length, i The amide or peptide group ‘This group is given in Fig. 1.2. When present in nylon polymers it is called the amide group; it is also present in silk, wool, mohair and all other animal or protein fibres, and is then called the peptide group. Figure 1.2 also shows the acid and alkaline hydrolysis of the amide or peptide group. This hydrolysis represents the most common chemical destructive attack upon the amide or peptide group during the life of the polymer, and hence of the fibre. Such hydrolysis (see Fig. 1.2) breaks the amide or peptide bonds, i.e. the single covalent bond between the carbon and nitrogen atoms. It is also important to note that the carbonyl oxygen of the amide or peptide group is strongly electronegative. This means it will develop a slight negative charge and give rise to hydrogen bonds. These hydrogen bonds will occur between the carbonyl oxygen and hydrogen atoms on closely aligned and adjacent polymers. An explanation of hydrogen bonds is given on page 16.Textile science carbonyl oxgen carbonyl radical carbon 1 c- | N ' imino 4 radical —— hydrogen amide or peptide bond oF lnk Figure 1.28 The amide or peptide group 9 carbonyl | radical |_g — y— | ' H radical ‘amide or peptide group; during the acid hydrolysis the carbonyl radical becomes a carboxyl group, whilst the imino radical becomes ‘a positively charged amino group ° q + HCl+H,0—» -C-OH + the carbon rysrogon chide [Link] inwalr be ; farce group Freer aaa Sm gTOUD Bremen carboxyl group which is acidic, water-soluble and reactive leading to further degradation of the polymer, hence, fibre acid conditions H 1 or HN H the imino group of the amide group has become a positively charged amino group which has attracted the anion of the acid, in this case Cr; the radical - NH* “Clis acidic, water-soluble and reactive leading to further degradation of the polymer and, hence, fibre Figure 1.26 Acid hydrolysis of the amide or peptide group; the hydrolysis occurs at the single covalent bond which exists between the carbon and nitrogen atoms, 9 I -C-N- + 1 H ‘amide or peptide group, the carbonyl radical will form an ester with the sodium of the alkali, whilst the imino radical will become an amino radical Figure 1.2 Alkaline hydrolysis or spaonit sodium hydroxide representing alkaline conditions 9° 7 ——+ -C-ONa + NaOH sodium ester of the ‘amide group; this is Often referred to as a crude soap as itis water soluble, chemically somewhat resembles soap and is capable of further reaction leading to polymer degradation land, hence, the fibre ‘covalent bond which exists between the carbon and nitrogen atoms. The benzene ring amino group; this is reactive and, hence, will lead to further degradation of polymer and fibre ation of the amide or peptide group; the hydrolysis occurs atthe single Benzene rings occur at regular intervals along the backbone of the common textile polyester polymer polyethylene terephthalate, e.g. Dacron, Terylene, Tetoron, Tre- 10Introduction to fibre polymers and fibre properties CoHs or H— or ag a -c (© c-# No Tf H H benzene benzone radical O benzene benzene radical Figure 1.3. Benzene, its molecular and structural formula and symbolic representation. See text below for explanation vira, ete, Invariably the benzene ring is a constituent of dye molecules (see Chapter 6, Figs 6.1 and 6.15 for example). The benzene ring is sometimes referred to as the aromatic radical. This term came about from the pleasant and/or distinctive odours of many naturally occurring substances, such as balsams, resins and by-products from coal tar, which once were the main source of benzene. The benzene molecule is a hexagon, often referred to as a ring structure, composed of carbon and hydrogen atoms as shown in Fig. 1.3. The accepted symbol for benzene in chemical formulae is a hexagon containing a circle; the circle indicates the resonance or orbiting electrons of the benzene molecular structure. It is the unique manner in which the carbon atoms of the benzene molecule adhere to their electrons which makes the benzene molecular structure relatively unreactive. Thus the presence of benzene in fibre polymers and dye molecules may be taken as an indication of chemical stability and resistance to degradation. Of course, this may not have been the primary intention when the fibre polymer or dye molecule was synthesised. Rather, it may have been more the ability of the benzene-containing compound to react in a certain way (i.e. to provide a particular hue, etc.) which prompted its initial use. Its contribution to greater stability of the resultant fibre polymer or dye molecule is of distinct advantage. Ether linkage The ether linkage may be found in such polymers as cellulose, elastomeric, ester- cellulose and polyesters. It exists between carbon and oxygen atoms thus: ¢—0—¢- 79 The linkage obtains its name from the family of organic compounds in which it is found, namely the ethers — diethyl ether being the well known anaesthetic ether.Textile science reuarew o19xor ‘Su pue ogy ou) Jo Guiuayeam e se paonou 9q jm forqy auf ‘2ouay ‘pue 204 0} pea sna jim PUB a1QnIOs- ‘aney Yat Sdno46-H1O 10 AxoApKY omy uy aloU ‘BEY ‘pIso0n)6 aut 18 JaWAjod ay) pound ashioupAy, ‘ney Suopudd prxe ay “i8UiKjod esojnyieo pesftoupAy oul ‘suoqypuco ‘aipioe 01 pasodxe stsouikiod asoinys9 aun Bulueawt uo} ‘uinwouphy 30 sauukjod asoinyjeo out Jo sisKioupAy ploy "t asnBi4, Jeowueyo 01 6eyuy apisoon6 wore ua6heo ayia ue Ospe S1 yolym Wore UaBAxo episooni6 wore aBAx0 seme un 40 Guu epysconi6 04) Jo Wed Buluu0} woye UaBAXo JoY}0 By) WEY yoRTE ndeosns a.0w st wore uaBAxo seule ue Burg Ybnowre "wore UABAKO ep/sconi6 aut :9!0N “soUsKIod esoIn|jag \ yun 0 Buu aprsoon|6 2Introduction to fibre polymers and fibre properties Ethers are chemically quite unreactive. One reason for this is the great chemical stability of the carbon—oxygen linkage found in every ether molecule, In general, an ether linkage in a fibre polymer tends to be the most durable and least affected by degrading agents. There is, however, one exception to the above. This is the ether linkage in cellulose known as the glucoside link, It links the glucose units (see Fig. 2.4). Under acidic conditions the glucoside link will undergo hydrolysis as shown in Fig. 1.4. This is the reason for the destructive effect with acids have upon cellulosic fibres. Ester group Esters may be regarded as organic salts: they correspond to the inorganic salts. They are formed by replacing the hydrogen of an acid with an organic radical. In fibre polymers this is usually the reaction between: a _acarboxyl group, i.e. -COOH, the characteristic group of the commonly occurring organic acids called carboxylic acids; e.g. acetic acid, formic acid, citric acid, etc. and b a hydroxyl group, i.e. -OH, the characteristic group of alcohols, such as the monohydric alcohols (e.g. ethanol) as found in alcoholic drinks, which only have one ~OH group per molecule; and the polyhydric alcohols such as cellulose (see Table 1.2 and Fig. 1.5) which have more than one -OH group per molecule. Figure 1.5 shows the formula of the ester group. The group is not resistant to alkalis — iit is subject to saponification or alkaline hydrolysis, as shown in Fig. [Link]. The saponification of the ester group produces water-soluble and reactive end-groups, leading to further degradation of the polymer and hence of the fibre. Ho H Ho H io 1 14 1 -cC-c-OH + Ho-c- —* -C-C-o0-c- + HO ay | 1 ot Som OF-group ster gioup”—_oraeonol 4 Ho group group i 4 fig "4 i i 4 -c-coo-c- oo —ccooe- ~cococ — 1 1 1 eae H H HOH HoH Figure 1.5a Formation of an ester group, generally as shown, from a carboxyl group and a hydroxyl group, ~OH (group, of alcohol group. The ester group is often also shown as depicted below. Hydroxyl group or -OH group By definition, the hydroxyl group is the univalent -OH group, pronounced O-H- group. It is attached by a single covalent bond as a side-group to fibre polymers (e.g. cellulose polymers; see Figs 1.4 and 2.4). ishes it from the free hydroxyl 1BTextile science H H H 4 ! 1 1 I -c-coo-Cc— + NaOH -——* —C-—COONa + HO-C — I ! I 1 H H sodium hydroxide, H H which is present as ester group in Sodium ion, Na‘, socium carboxyiato hydroxy! end-group, a fibre polymer and hydroxy radicals, end-group, this ~OH end -group, OF, inal common water-solube, alkaline, alcohol group, this akaline iquors, also referredio as is water-soluble Such as laundry water a crude soap and and usually subject atter the laundry ‘subject to further to further cogradation delorgenthas been degradation ‘added Figure 1.5b Alkaline hydrolysis or saponification of an ester group in a fibre polymer. Note: saponification means ‘soap-making and the sodium carboxylate group is the typical water-soluble end-group ofall soaps made from natural olls or fats with sodium hydroxide. group which is the cation, ion or negative radical OH. The presence of -OH groups on fibre polymers is of two-fold significance: a The -OH groups are polar and will therefore attract water molecules, which are also polar. Thus -OH groups are mainly responsible for the moisture absorbency of a fibre, and hence its comfort when worn. b> The polarity of -OH groups will give rise to the formation of hydrogen bonds (see page 16 for explanation). The formation of such hydrogen bonds will contribute significantly towards the coherence of the fibre’s polymer system. The presence of -OH groups on fibre polymers should not be underestimated. Their importance is illustrated by the fact that constant efforts are being made to have -OH groups introduced onto the hydrophobic, synthetic fibre polymers. The presence of OH groups on these polymers would significantly enhance the hygroscopic nature and comfort of these fibres. In general, the -OH group is chemically reactive and may contribute to the degradation of the polymer of which it is a constituent. HoH HOH 1 1 1 1 H-|-C—-C-|—H + NaOH + 2H ——» H— | —C —C — | —H+[Link] I I 1 I GY J, stu nso wi 4 Ja anmonum present as sodium ion, Na*, } hydroxide nitrile radical tnd nyroxy racial, OH Sa all common alkaline liquors, »olyacrylonitrile jou a IaUncey waa the nitrile radical is converted to fore polymer ator the auncry detergent the sodium salt of polyarye acs has been added or sodium polyacrylate; the ssocium carboxylate group, i.e, -COONa, is water-soluble and will lead to further ‘degradation of the polymer and, hence, fibre Figure 1.6 Alkaline hydrolysis or saponification of the polyacrylonitile flbre polymer; the above indicates how polyacrylonitrle segments in acrylic and modacrylic fibres can become degraded by alkalis. 4Introduction to fibre polymers and fibre properties Nitrile group This is the characteristic polymer side-group of acrylic and modacrylic fibres, i.e. -CN (see also Tables 1.1 and 1.2). In general, the nitrile group does not react with acids or break down in acidic conditions. It is, however, subject to alkaline hydrolysis or saponification, as would occur during normal laundering. Under normal circumstances this is not very noticeable, because the crytallinity or good orientation of the polymer system of the acrylic fibre allows such hydrolysis to occur only on the surface of the fibre. Inter-polymer forces of attraction It is stated on pages 1, 8 that textile fibres are composed of polymers; polymers being the equivalent of molecules of other substances. This statement of fact requires the development of some sort of abstract or real picture of a coherent mass of polymers forming the fibre, which may be called the polymer system of the fibre. The coherence of the polymer system of a fibre is due to the four inter-polymer forces of attraction: van der Waals’ forces, hydrogen bonds, salt linkages, and cross- links (see Table 1.3 for a detailed summary of these forces). ‘A more detailed description of the four inter-polymer forces follows. Van der Waals’ forces These are very weak inter-polymer forces of attraction, named after the Dutch physicist Johannes Diederik van der Waals who first postulated their existence. Van der Waals’ forces may be defined as very weak electrostatic forces which attract neutral molecules to each other in gases, liquefied and solidified gases, organic liquids, and, most importantly in this context, organic solids such as textile fibres. They become an inter-polymer force of attraction as a result of electrons of very closely adjacent atoms moving in sympathy with one another. A more detailed explanation of the formation of van der Waals’ forces requires the use of quantum mechanics, which is beyond the scope of this book. Provided any two or more atoms and/or molecules are close enough together, then van der Waals’ forces will come into existence between them. Fibre polymers need to be about 0.2 nm apart for van der Waals’ forces to occur along their length. Such very close alignment of polymers occurs in the crystalline regions of the polymer system of any fibre. Thus, it may be assumed that van der Waals’ forces exist between the polymers of the crystalline regions of any fibre’e polymer system. It is important to remember that the diameter or size of the atoms which give rise to van der Waals’ forces influerices the relative strangth of this very weak inter-polymer force of attraction. This means that larger atoms give rise to stronger van der Waals’ forces than smaller atoms. For instance, the hydrogen atom is the smallest, being about 0.06 nm in diameter. By comparison, the chlorine atom is about 0.2 nm, i.e. more than three times as large in diameter. Consider now the polymer system of polyethylene and polyvinylidene chloride fibres. The polymer systems of both fibres are held together by only van der Waals’ forces. However, because of the presence of 15Textile science H-ol tot H- |-c—c-|-H H- tot van der Waals" Hcl | forces formed between the oH bracketed atoms H- |-c-c-—]|-H H- 1 oi aw J, a b Figure 1.7 a. Two adjacent or very closely aligned polyvinylidene chloride polymers; owing to the presence of the chlorine atoms, stronger van der Waals’ forces will be formed. 'b Two adjacent or very closely aligned polyethylene polymers; owing to the presence of only hydrogen atoms, ‘weaker van der Waals’ forces will be formed. chlorine atoms on the polyvinylidene chloride polymers, the van der Waals’ forces formed in the polymer system of this fibre will be stronger than those formed in polyethylene (see also Fig. 1.7). Van der Waals’ forces become of utmost importance when none of the other forces of inter-polymer forces of attraction is present to a significant degree. This is the case with such fibres as acrylic, polyester, polyethylene, polypropylene, and the chlorofibres. Their polymer systems need to be made highly crystalline. Only then will sufficient van der Waals’ forces occur along the lengths of their polymers to make them useful fibres. ‘The influence of the difference in strength of the van der Waals’ forces in the above two fibres is illustrated by their melting points. In general, the stronger the inter- polymer forces of attraction, the higher the melting point of the polymer system and, hence, of the fibre: Fibre Melting point range polyethylene 110- 140°C polyvinyl chloride 170-200°C Van der Waals’ forces are also formed between fibre polymers and dye molecules, when these come close enough together. In this way, van der Waals’ forces contribute towards the colour-fastness of dyed or printed textile fibres. Hydrogen bonds ‘These may be written as H-bonds, Hydrogen bonds are weak electrostatic bonds which occur between covalently bonded hydrogen atoms and the strongly electronegative atoms: oxygen, nitrogen, fluorine and chlorine. ‘The formation of a hydrogen bond requires that: a the hydrogen atom assumes a very slight positive charge or polarity, shown as 6* in Fig. 1.8, and pronounced delta positive; b_ the oxygen, nitrogen, fluorine or chlorine atoms, i.e. the strongly electronegative 16Introduction 0 fibre polymers and fibre properties atoms, assume a very slight negative charge or polarity, shown as 3" in Fig. 1.8 and pronounced delta negatives and ¢ the distance is less than about 0.5 nm between the two very slightly polar, but oppositely charged atoms of a and b above. ‘The most common hydrogen bond in the polymer system of textile fibres is that formed between hydrogen and oxygen atoms. This means that the hydrogen bond may be formed between: the -OH groups on closely adjacent cellulose polymers; the amide groups of nylon polymers; and the peptide groups of the polymers of the protein fibres (see also Fig. 1.8). It is now considered doubtful that significant hydrogen bonding occurs between the nitrile nitrogen of acrylic polymers and hydrogen atoms on adjacent polymers (sec also Table 1.2). It is necessary to point out that hydrogen bonds formed between hydrogen and nitrogen atoms are weaker than those formed between hydrogen and oxygen atoms, because nitrogen becomes less electronegative than oxygen. Before a hydrogen bond can form, the two participating atoms, say hydrogen and oxygen, must develop or assume very slight, but opposite, charges or polarity. The development of this polarity may be explained by considering the hydrogen bond which can come into existence between the imino hydrogen of an amide or peptide group on one polymer, and the carbonyl oxygen on an amide or peptide group on a 1 1 -~c- c- imino {oe # | hydrogen c=o0 H-N NU! 1 H-N c=0 1 7) Nearbonyl -co- c- oxygen I 1 b H soe lot HOH o -c-c— Pot tg. torod -c-c-o0 HOH Io HH Hebonds Figure 1.8 a The existence of a hydrogen bond between the carbonyl oxygen and imino hydrogen of two very closely adjacent amide or peptide groups. Note how the very slight polarity or partial charge, as itis sometimes called, is shown against the relevant atoms. The existence of a hydrogen bond between two hydroxy! groups on very closely adjacent cellulose polymers. Note that two hydrogen bonds are formed between any two ~OH groups. 7Textile science very closely adjacent polymer (see also Fig. 1.8). The nitrogen atom, to which the imino hydrogen atom is bonded, is a strongly electronegative atom. This means that the nitrogen atom will disproportionately concentrate its own electrons and the one electron of the hydrogen atom about itself. This tends to give the nitrogen atom an excess of electrons and thus cause it to assume a very slight negative polarity. This is shown as 5- in Fig. 1.8. The lopsided concentration of electrons towards the nitrogen atoms leaves the hydrogen atom with a deficiency of electrons. This will cause it to assume a very slight positive polarity, shown as 5* in Fig. 1.8. In the carbonyl group of the amide or peptide group a similar electron displacement occurs. The oxygen, which is linked by a double covalent bond to the carbonyl carbon atom, is also a very strongly electronegative atom. It will therefore tend to concentrate its own electrons and those of the carbon atom about itself. This gives a disproportionate concentration of electrons about the oxygen atom, causing it to assume a very slightly negative polarity. The carbonyl carbon atom will, of course, assume a very slightly positive polarity. ‘These polarities are shown as 6 and * respectively in Fig. 1.8. Thus, as the carbonyl oxygen and the imino hydrogen assume opposite polarities, a force of attraction known as the hydrogen bond will form between them. With regard to the hydrogen bond formed between two ~OH groups on adjacent cellulose polymers, the oxygen atom will assume a very slight negative polarity as explained above. This causes the hydrogen atom of the -OH group to assume a very slight positive polarity, resulting in the formation of a hydrogen bond as shown in Fig. 1.8. It is also possible for hydrogen bonds to form within the one polymer as depicted in Chapter 4, Fig. 4.7b. ‘The presence of a predominant number of hydrogen bonds in any polymer system will advantageously influence the tenacity, elastic-plastic nature, durability, and heat- setting properties of the fibre. The presence of hydrogen bonds also indicates, of course, the existence of polar sites along the polymer lengths. These polar sites will attract water molecules, which are also polar (sce page 22). Thus, if the polymers attract water molecules, the polymer system will tend to be moisture absorbent or hydrophilic, which will tend to make the fibre more comfortable to wear. Salt linkages These are also called salt links or salt bridges, and are electrovalent or ionic bonds. Salt linkages occur between negatively and positively charged radicals on very closely adjacent fibre polymers, as shown in Table 1.3. The formation of a negatively charged radical occurs when it gains one or more electrons over its normal electron complement. Electrons are negative and, being in excess, cause the radical to become negatively charged. This negative charge is shown on the radical with a small negative sign. The number of negative signs shown against a radical indicates the number of electrons the radical has gained over its normal complement of electrons. In the formation of a positively charged radical, electrons are lost by the radical. Losing electrons causes the 18Introduction to fibre polymers and fibre properties Table 1.3 Inter-polymer force of Bond energy or Relative Occurs between. Relative importance attraction and its bond strength in strength _the polymers of formation kilojoules* van der Waals’ forces 84 very weak all fibres they are the only inter- formed between atoms polymer force of attraction along the length of adjacent existing in the polymer sys- polymers when these are tem of polyethylene, polyp- less than 0.3 nm apart but ropylene, polyvinylehloride, no closer than about 0.2 nm polyvinylidene chloride, primary cellulose acetate and 100 per cent polyacrylonitrile fibres; they are considered to be the predominant —inter-polymer force of attraction in the polymer system of acrylic, modacrylic and polyester fibres hydrogen bonds 20.9 weak natural, they are mainly reponsible formed between hydrogen regenerated for the tenacity and the elas- and oxygen atoms, and, cellulose, nylon, _tic-plastic nature of the natu- hydrogen and nitrogen polyvinyl alcohol, ral, regenerated cellulose, atoms on adjacent polymers polyester, protein nylon, polyvinyl alcohol and when these are less than and secondary protein fibres; they contri 0.5 nm apart; note, the cellulose acetate bute significantly towards the hydrogen—oxygen bond is fibres heat setting property of nylon stronger than the and protein fibres; hydrogen-nitrogen bond hhydrogen bonds occurring in the polymer system of polyester fibres are very weak and not consider to be importants insignificant hydrogen bonds are formed in the polymer system of secondary cellulose fibres; there is doubt about hydrogen bond formation in the polymer system of acrylic and modacrylic fibres salt linkages 54.4 strong protein and they contribute towards the formed between the nylon fibres tenacity of the fibre; attract carboxyl radical on one water molecules, hence, en- polymer and the positively hance the hygroscopit nature charged or protonated of the fibre; attract the anion amino group on an adjacent of acid dyes, i.e, they are polymer, i.e. very good dye sites; may i" make the fibre’s polymer sys- -C-O0 "HN tem liable to chemical degradation. tess than Ont nm 19Textile science Table 1.3 (continued) Inter-polymer force of Bond energy or Relative Occurs between Relative importance attraction and its bond strength in strength _the polymers of, formation Kilojoules* cross-links 245.3 very strong all protein fibres, they contribute significantly formed as a single covalent except silk, and to the elastic nature of elas- bond between adjacent elastomeric fibres tomerics; contribute towards polymers of wool due to the the tenacity of wool; are disulphide bond or . broken and re-formed under 1 -N -¢ i Ic) T ink, ic. controlled conditions for heat and chemical setting of wool and other protein fibres, but 1 fy WH oe not silk. “G88 ogee F- Woes HA A oan also formed in elastomeric, but details not known, * from ‘Dyeing and Chemical Technology of Textile Fibres’ by E.R. Trotman, Sth Edition, Griffin, United Kingdom. radical to become positively charged. The number of small positive signs shown on the radical indicates not only its positive charge but also the number of electrons it has lost. ‘Atoms may also gain or lose electrons. Such a gain or loss alters the normal complement of electrons of the atom, It is then called an ion, i.e. it is either a positively or negatively charged atom. This is the reason why salt linkages are also called ionic bonds, or electrovalent bonds (electro- = electric, from the strongly positive and negative charges which must always be present; and valent from valence). Valence is the combining power of an atom, which means the number of hydrogen atoms with which the atom can combine or which it can displace. It is thus also the number of electrovalent or ionic bonds the atom or radical can form. If the radicals of the fibre polymers carry only one charge, i.e. one negative and one positive sign as shown in Table 1.3, then they will form only one electrovalent bond or salt linkage. These inter-polymer forces of attraction are described as salt linkages (or salt links, or salt bridges) because ionic or electrovalent bonds are formed between the ions and/ or radicals of the chemical compounds called salts. Table or common salt, which is sodium chloride, is the best known example of a salt. Salt linkages occur between the polymers of protein fibres and at the ends or termin- als of nylon polymers (see Table 1.3). They are a strong inter-polymer force of attraction and, therefore, contribute to the cohesion of the appropriate fibre’s polymer system. In this way, salt linkages enhance the tenacity, elastic-plastic nature, and durability of the fibre and its textile materials. The strong polarity of salt linkages makes them the prime site to which the anion of (acid) dyes attaches itself (see also pages 132 and 133). Furthermore, their polarity will attract water molecules. This contributes to the 20Introduction to fibre polymers and fibre properties hydrophilic nature of the fibre’s polymer system, making the fibre more absorbent and, hence, more comfortable to wear. In general, it will also be found that fibres, whose polymer systems contain salt linkages, will be more reactive than those without these intet-polymer forces of attraction. Cross-links These occur between the polymers of elastomeric and protein fibres, except silk. Cross- links are covalent or valence bonds and, more specifically, single covalent bonds. Sing- le covalent bonds are formed when two atoms share one pair of electrons. The sharing of a pair of electrons by two atoms (i.e. the single covalent bond) is represented in the structural formulae of organic compounds such as fibre polymers by a single, short line drawn between the letters representing the atoms. The carbons atoms, occasionally joined by oxygen and/or nitrogen atoms, in the backbone of fibre polymers are linked by single covalent bonds thus: I I 1 | I I l —¢—¢—cG—N—G—C—c—0— rretor ft ti Single covalent bonds occur not only within fibre polymers, but also at selected points berween the polymers in such fibres as elastomeric, wool, mohair, but not in silk. ‘When single covalent bonds link adjacent polymers, they are called cross-links (see also Table 1.3, page 20). The number of cross-links or the amount of cross-linking between polymers in a polymer system is spoken of as the degree of cross-linking. Thus the degree of cross- linking in the polymer system of a fibre significantly influences that fibre’s elastic~ plastic nature and tenacity. In general, the greater the degree of cross-linking or the more cross-links between polymers, the stiffer, less flexible, more rigid will be the fibre. Fibres such as wool, which have relatively few cross-links or a low degree of cross-linking, will have good to very good elastic properties. When the degree of cross- linking is even lower, such as in clastomerics, then the elastic property will be very good to excellent. Synthetic resins applied to textile materials to make them easy-care have very highly cross-linked polymers. Such a very high degree of cross-linking makes these resins, when set, very rigid and thereby imparts the necessary stiffness to the textile to achieve the easy-care property. The considerable stiffness and rigidity of these resins is considered to be due to the three-dimensional cross-linking of their polymers; this means that these polymers are able to form cross-links in three directions — length, breadth and depth — within their polymer system (see also page 167). The water molecule and textile fibres The comfort of textile materials depends very much upon the moisture absorbency, hygroscopic or hydrophilic nature of such material. The comfort derived from textile 2Textile science a H.0 b c hydrogen = ‘oxygen atom Figure 1.9 a The conventional molecular formula of the water molecule The structural formula of the water molecule. The angle between the two hydrogen atoms is about 105°. Note the dipolarity of the structure: two poles, one negative and one positive, € Simplified representation of the structural formula for water, retaining the angle between the hydrogen atoms as well as the proportion in size between the hydrogen and oxygen atoms, fibres is critically dependent upon the ability of the fibre to absorb moisture or the ability of its polymer system to take up or attract water molecules. Water plays a very important role in textiles and clothing, hence it is important to become familiar with the water molecule and its polarity. Each water molecule consists of two atoms of hydrogen and one atom of oxygen. This gives the familiar chemical formula for water: HO, which is convenient to write, but does not give the important structural formula of the water molecule. The structure is shown in Fig. 1.9. As may be seen, the two hydrogen atoms are more to one side of the molecule, while the oxygen atom is on the opposite side. This arrangement of atoms in the water molecule permits the ready development of its dipolar nature. Dipole means two poles, which implies a positive and a negative pole. The dipolar nature of the water molecule is due to the very electronegative oxygen atom (see also hydrogen bonding, page 16). The oxygen atom, because of its strong electronegativity, will disproportionately concentrate its own electrons, and the one electron from each of the hydrogen atoms, about itself. This tends to give the oxygen atom an excess of electrons, causing it to assume a very slight negative charge or polarity. On the other H. H H. H 3. \/ V7 A i oO. H H. H ' \ / H H 1 1 c- c= on H H hydroosn ? bones HOH He H ° H Figure 1.10 An indication of how water molecules, because of their dipolarity, are attracted to each other and to polar sites on the fibre polymer; in this example the polar sites on the fibre polymer are due to an amide group. 22Introduction to fibre polymers and fibre properties side of the water molecule, the two hydrogen atoms tend to be disproportionately deficient in electrons and therefore to assume a very slight positive charge or polarity. Itis for this reason that water molecules are always dipolar (ie. very slightly positively charged at their hydrogen end and very slightly negatively charged at their oxygen end). This is indicated by delta-negative and delta-positive in Fig. 1.10. The polarity of water molecules causes them to be attracted to one another and partly linked together by hydrogen bonding. For the same reason, they will also be attracted to any polar sites on fibre polymers, as shown in Fig. 1.10. Requirements of fibre-forming polymers Fibre-forming polymers of apparel fibres should be: hydrophilic chemically resistant linear long capable of being oriented, and able to form high-melting-point polymer systems. aAnewne This does not necessarily mean that the various polymers, which constitute the polymer systems of the different fibres, meet ail these requirements. However, the polymer systems of such commonly used apparel fibres as the acetates, acrylics, cotton, flax, nylon, polyester, silk, viscose and wool consist of polymers which do, to a very large extent, meet the above requirements. On the other hand, man-made fibres such as the chloro-fibres, polyethylene and polypropylene fibres are restricted in their apparel use because they do not satisfactorily meet the first, fifth and sixth requirements listed above. On the other hand, polyvinyl alcohol is not so commonly used, although it has similar properties to nylon. It is probably this similarity to nylon which makes it very difficult for polyvinyl alcohol to compete against the longer established, successful nylon. Natural cellulose fibres such as abaca, coir, hemp, jute, kenaf, ramie and sisal have very restricted apparel use because they are very stiff. These fibres are examples of the fifth requirement, which has, so to speak, been ‘overdone’. Their polymers are far too well oriented, and this imparts stiffness to the fibres. The polymers of the natural fibres angora, cashmere and mohair largely meet the above requirements, but because the fibres are relatively scarce, they are expensive and therefore infrequently used. Leaving economic considerations aside, the usefulness of a fibre for apparel purposes is generally dependent upon the extent to which its polymers meet the requirements of fibre-forming polymers listed above. An explanation of these requirements is now given. 1 Hydrophilic properties Fibre polymers should be hydrophilic. This means that the polymers should be polar, enabling them to attract water molecules. A fibre is comfortable to wear if its polymer 23Textile science system consists of hydrophilic polymers, and the system itself permits the entry of water molecules. The latter is explained under 5 below. There are, of course, fibres whose polymers are not hydrophilic (i.e. their polymers ate hydrophobic) and yet these fibres are used for the manufacture of apparel. In order to make the textile materials of these fibres more absorbent and, hence, more or less comfortable, hydrophilic-polymer fibres need to be blended with the hydrophobic- polymer fibres. Nylon and polyester, for example, are hydrophobic-polymer fibres and are often blended with cotton, viscose or wool (e.g. two-thirds polyester/one-third cotton blend). Such blending improves the absorbency and comfort of their textile materials. Acrylics are also hydrophobiec-polymer fibres. Knitted outerwear made of acrylics is very popular; but it will be found that it is usual to wear this non-absorbent knitwear over an absorbent or hydrophilic-polymer fibre garment to counter or reduce the potential discomfort which might otherwise be experienced. A fibre consisting of hydrophilic polymers attracts water molecules which prevent, or enable, the discharge of any static electricity accumulating on the fibre. The static electricity is discharged by the water molecules, because of their polarity, to the sur- rounding atmosphere. A build-up of static electricity on a fibre is undesirable because it will cause the fibre to attract dirt particles more readily and thus to soil more quickly. Garments that become charged with static electricity may cling together to such an extent as to create discomfort during wear. 2 Chemical resistance Fibre polymers should be chemically resistant for a reasonable length of time against the common degrading agents such as sunlight and weather, common types of soiling, body exudations, laundry liquors and dry cleaning solvents. Chemically resistant polymers should also not be toxic or hazardous to wear against human skin; this is a most important requirement which is usually taken for granted. Although fibre polymers should be chemically resistant, they should not be inert (ie. totally unreactive). Chemical inertness of fibre polymers tends to have a de- trimental effect on other fibre-forming requirements. For instance, the polymers of chlorofibres, fluorocarbon, polyethylene and polypropylene may be regarded as chemically inert from a practical point of view. For this reason the polymers are non-polar and hence hydrophobic, making the textiles of these fibres non-absorbent, with a greasy, slippery, aesthetically displeasing handle. The degree of chemical resistance desirable from the common fibre polymers may be deduced from the section on intra-polymer bonding (pages 8-15) 3 Linearity Fibre polymers should be linear (i.e. the polymers should not be branched; see also Fig. 1.11). As explained in 5 below, only linear polymers allow adequate polymer alignment to bring into effect sufficient inter-polymer forces of attraction to give a cohesive polymer system and, hence, useful textile fibre. It is, however, a normal occurrence for many fibre polymers, which need to be linear, to have side groups, as distinct from branches. Side groups may be thought of 4Introduction to fibre polymers and fibre properties as causing ‘bulges’ along the polymer backbone, rather than the distinct projection of a branch. Thus the nitrile group of acrylics, the hydroxyl and methylol groups of the cellulose fibres, and the hydroxyl and acetyl groups of ester-cellulose fibres are some examples of side groups. By examining Tables 1.1 and 1.2 other fibre polymers with side groups will be found. Note that the Zefran polymer given in Table 1.2 is a branched polymer: seemingly the only one which gives a useful fibre. The importance of considering side groups on polymers is the fact that they give rise to three types of linear polymer configurations, better referred to as three types of stereo-polymers. Stereo, from the Greek, is used here in the sense of spatial or three- | dimensional arrangements of the side groups on the polymer backbone, In man-made fibre manufacture it is important to have the right stereo-polymer for the extrusion of useful filaments. The three types of stereo-polymers are described below. \ The atactic polymer This is a stereo-irregular polymer. It has its side groups arranged at random (i.e. in no particular order) above and below the plain of the polymer backbone. Two- dimensionally this may be represented thus: aoe eee 8 — polymer backbone side group Atactic polymers are usually not found in the polymer systems of fibres. This is because they do not allow close enough alignment or orientation of polymers for the formation of effective inter-polymer forces of attraction. If atactic polymers were used they would give an insufficiently cohesive polymer system, as indicated by the wax-like substance formed. The syndyotactic polymer This is a stereo-regular polymer. It has its side groups arranged in a regular alternating fashion above and below the plane of the polymer backbone. Two-dimensionally this may be represented thus: ~-B--g--0--8- 8 Boe B ae Such a regular polymer structure permits close enough alignment or orientation of polymers to form effective inter-polymer forces of attraction, giving a cohesive enough polymer system to form a useful fibre. The polymers of cellulose and some chlorofibres are thought to be syndyotactic polymers. | The isotactic polymer This is also a stereo-regular polymer. It has, however, all its side groups arranged on the same side or plane of the polymer backbone. Two dimensionally this may be shown thus: 25Textile science =-9--0--p--0- 2-0-0 -0--B--0--Q--0-~ ae BB Bee Isotactic polymers orient themselves readily and very closely. This permits effective formation of inter-polymer forces of attraction to give a cohesive polymer system and, thus, a useful fibre. Polypropylene and pure acrylonitrile fibres are known to have their polymer system constituted of isotactic polymers. 4 Length Fibre polymers should be long. It has been found that the length of the polymers constituting the commonly used apparel fibres is in excess of one hundred nanometres. Polymers of such length can readily be oriented. This is explained under 5 below. Having the polymers oriented can give rise to sufficiently effective inter-polymer forces of attraction to form a cohesive polymer system and, hence, a useful fibre. In general, the longer the polymers the more cohesive will be the polymer system and the stronger will be the fibre. For this to occur the polymers have to be closely aligned or well oriented so that the maximum formation of inter-polymer forces of attraction can take place. (See also Figs 1.11 and 1.12.) STS ES OO Figure 1.11a Linear polymers: they can assume various configurations as shown; however, they can be oriented Cr aligned to form a cohesive polymer system suitable for useful fibre formation. Figure 1.11b Branched polymers: they can assume various configurations as shown; however, they cannot be sufficiently oriented to form a polymer of adequate cohesion; therefore, they are unsuitable for fibre formation, 26Introduction to fibre polymers and fibre properties Figure 1.12a A strong fibre because It has long polymers which are well aligned or oriented, giving it a long ‘path of break’ path of break Figure 1.12b A weak fibre because it has short polymers; although they are well oriented, the shortness ofits path of break tends to make it weak 8 Orientation Fibre polymers should be capable of being oriented, as foreshadowed under 4 above. This means that the polymers are or can be arranged or aligned (i.e. oriented) into more or less parallel order in the direction of the longitudinal axis of the fibre or filament. It is not known how the orientation of polymers occurs during the growth of natural fibres. With man-made fibres, the operation called drawing, which stretches the extruded and coagulated filament, causes the polymers to orient themselves longitudinal- ly into a more or less parallel order. The extent of this drawing markedly influences the properties of the filament and those of the staple fibre which may be cut from it. Perfect orientation of polymers is usually not obtained, nor is it desirable, as explained in Table 1.4. The orientation of polymers in the polymer system of any fibre consists of two distinct, yet integrated forms. The two forms of polymer orientation are called the amorphous and the crystalline regions. (See Table 1.4 for definition, explanation, comparison and influence upon fibre properties of the amorphous and crystalline regions.) 6 Formation of high-melting-point polymer systems A fibre consisting of a high-melting-point polymer system tends to have adequate heat resistance to enable it to withstand the various heat treatments of textile finishing, 27 \i. Textile science attraction and free the polymers from each other. Once this has occurred, the polymers are free to move independently of each other, and gravity tends to cause them to flow to the lowest point of the plane on which they are situated. This flowing or moving of the polymers in a mass is seen and recognised as melting of the fibre. When heat is applied to a fibre it may melt. Continued heating may lead to the fibre’s ignition and burning. Heat is a form of energy; the heat energy possessed by a substance, polymer system or polymer is in the form of kinetic energy which is due to the atomic or molecular translation, rotation or vibration, In other words, at any temperature above absolute zero (-273.15°C = 0°Kelvin), the atoms, molecules or polymers of any substance constantly vibrate or are in a constant state of excitement, This rate of vibration or the state of excitement may be increased by applying heat, that is by increasing the temperature of the polymer system or polymer; or decreased by removing heat, that is by cooling, which decreases the temperature. Exposure to a heat source such as a naked flame can increase the kinetic energy of a polymer system and its polymers to such a degree that most of the interpolymer forces of attraction are broken. This will tend to free the polymers and is seen, as described above, as melting of the fibre. Further exposure to the heat source may provide so much kinetic energy as to raise the state of excitement of the individual polymers to such a level that their intra-polymer bonding is broken. This would free individual atoms of the polymer from each other. As soon as this occurs, the atoms would react immediately and violently with the oxygen of the atmosphere. This is seen and recognised as combustion of the fibre. The heat resistance and heat conductivity of any fibre are directly related. From a textile viewpoint, a fibre resistant to heat, such as cotton or viscose, will also conduct heat. On the other hand, a fibre of poor heat resistance, such as wool or nylon, will be a non-conductor or insulator of heat. It seems that the ability of a fibre to conduct heat, which means passing it along its polymers and through its polymer system, depends upon the degree of polarity of its polymers. Polar sites along the lengths of the polymers may provide the necessary free electrons to convey the heat or kinetic energy along. This is not unlike the conduction of an electric current travelling through a copper wire. The thermoplastic nature of a fibre is largely a question of whether or not most of the inter-polymer forces of attraction can be broken at the one time, under controlled conditions of heating (i.e. increasing the kinetic energy of the polymers and polymer system). In the very brief time when the polymers are more or less free of each other, they can be induced, by manipulation of the fibre, to assume new positions in the polymer system of the fibre. These new positions are retained by the polymers when they cool because the inter-polymer forces of attraction reform. The fibre is then said to be heat-set. It will be realised from the above that, if a fibre can be melted, then it is thermoplastic and can be heat-set, and vice versa. A thermoplastic fibre does not lost its heat-setting property. However, this is not the case with thermo-setting materials, which lose their plasticity once they have been heat-set, and usually become hard, stiff and even brittle. For this reason no thermo-setting fibres are used in textile and apparel manufacture. (See also Thermoplasticity, page 116.) 30Introduction to fibre polymers and fibre properties General definition of a textile fibre anda textile filament A fibre or staple fibre is a unit of matter which is usually at least 100 times longer than it is thick. Usually, fibres are several thousand times longer than they are thick, Most apparel fibres range in length from about 15 mm to 150 mm, with exceptions: for example, flax ranges up to 500 mm and sometimes even longer. The thickness of these fibres tends to range from about 10 pm to 50 um. A filament is a very long fibre. The length of filaments may range from a few hundred metres, as in the case of silk, to several kilometres in the case of man-made fibres. The thickness of filaments tends to be similar to that of fibres. General considerations with regard to fibre properties The general considerations given below provide the background information upon which the explanations of a fibre’s properties are based. An awareness of these considerations will improve one’s understanding of fibre properties. Fibre morphology Morphology is the study of the size, shape, and structure of a material or textile fibre, and the relationship between these properties. The morphology of textile fibres and filaments may be divided into the following. The macro-structure of a textile fibre and filament Fibre length (See also ‘general definition of a textile fibre and textile filament’, above.) Fibres shorter than about 15 mm tend to have insufficient length to permit them to be twisted into a strand of adequate cohesion, regularity and evenness to make it a useful yarn structure. Fibres longer than about 150 mm tend to require specialised spinning machinery which adds to the cost of converting them into yarn. Filaments, of course, are so long that they need, in principle, only to be gathered together to form a suitable yarn structure. Fibre thickness (See also ‘general definition of a textile fibre and textile filament, above.) Fibres or filaments finer than about 10 jum tend to become too delicate or fragile for ready conversion into a yarn structure. Fibres or filaments exceeding about 50 jum in thickness 31Textile science tend to give a yarn structure which is too coarse and too thick for comfort when used as apparel. Fibre length to fibre breadth (thickness) ratio This ratio determines whether or not a fibre is suitable for spinning into yarn, provided it first meets the fibre Jength and thickness requirements given above. The smallest suitable ratio of fibre length to fibre breadth (thickness) is about 350:1. Anything less than this — say about 200:1 — indicates a fibre which probably will not permit twisting into a yarn structure. But a ratio of 1000:1 or more indicates a fibre which should readily spin into a useful yarn. Colour White or colourless fibres and filaments are preferred. Natural fibres and delustred man-made fibres are white to off-white in colour. Bright-lustre man-made fibres and filaments are colourless because they are translucent. White ot colourless fibres and filaments are preferred because they can be dyed or printed with any hue of colour. Translucency ‘A translucent fibre will transmit light but is not transparent. In general silk and man- made fibres, when bright-lustred, are translucent. Cotton, flax and wool, and also delustred man-made fibres, tend to be opaque; but if these fibres are made into light- to very light-weight fabrics, then their fineness tends to make them somewhat translucent. The acceptability of translucent fibres, their translucent textile materials, and apparel items depends upon the prevailing mores of the particular community or peer group(s). With the increasing use of man-made fibres over the years, problems have been encountered in the manufacturing of textiles that are sufficiently opaque to satisfy the requirements of modesty. Lustre ‘This is a subjective measure of the reflection of incident light from a fibre, filament or textile material. The more lustrous a fibre, the more evenly does it reflect the incident light. The less lustrous or duller a fibre or filament, the less evenly does it reflect or the more does-it scatter the incident light. Cotton has a convoluted fibre structure and wool a serrated surface structure; the result is that these fibres scatter the incident light, and are thus dull fibres. The more regular and even surface structure of flax, mercerised cotton and silk gives these fibres a distinct lustre, due to the even reflection of incident light. Table 1.5 shows the reflection of incident light by various man-made fibres. The irregular specks of delustring agent contained within delustred man-made fibres scatter sufficient of the incident light to make these fibres or filaments duller than their bright-lustre equivalents. A preference for non-lustrous or dull textile fibres and fila~ ments exists. This is evident in the predominance of dull-lustred or non-lustrous apparel and household textiles normally purchased and used by consumers. 32Introduction wo fibre polymers and fibre properties ‘Table 1.5 The general effect of fibre cross-sectional upon lustre and other physical fibre properties Generalised shape of fibre General effect of cross-sectional General effect of cross-section shape upon fibre lustre cross-sectional shape upon other physical fibre properties cident att ‘Theoretically this cross-sectional This cross-sectional shape im- 7 shape should impart only a soft parts the greatest bending stiff- < lustre to the fibre or filament ness, is the most rigid, least & because the incident light is flexible and least pliable be- &s reflected so unevenly; in fact it cause it is so regular in dia- tends to impart a rather harsh, __-meter; its smooth regularity of strong lustre; this is because, no surface imparts a waxy, slip- matter how the fibre or filament pry handle and causes the may be twisted in the yarn or fibre or filament to make max- fabric, its circular shape always imum contact with the skins permits it to reflect the same this may be aesthetically dis- amount of incident light despite pleasing circular type the unevenness of its reflection. ‘Theoretically these cross-sectional These cross-sectional shapes, shapes should be the most tend to impart the least bend- lustrous because they can reflecting stiffness, are the most pli- the incident light most evenly; in able, most flexible, most sup- fact though, because the fibre or _ple and even limp because they filament would be twisted upon _are so readily deformed across itself in the yarn and fabric, the the shorter of their two dia- oval type incident light is not reflected as meters; the smooth regularity evenly as expected and asofter of their surfaces may impart a lustre results waxy, slippery handle and causes the fibre or filament to ‘make maximum contact with the skin; this may be aesthetically displeasing. The distinct edges of the more triangular cross-sectional shape _create dog-bone or bean type more friction between fibre or filament and the skin giving it a crisper, less waxy, less slippery handle triangular type 33Textile science Table 1.5 (continued) Generalised shape of fibre cross-section General effect of cross-sectional shape upon fibre lustre General effect of cross-sectional shape upon other physical fibre properti ag trilobal type mult-lobal type ‘These cross-sectional shapes reflect the incident light quite unevenly; theoretically they should therefore impart to the fibre or filament a very dull lustres in fact they impart a distinct and very bright sparkle or glitters the reason for this is that when the fibre or filament is twisted upon itself in the yarn and fabric the already irregular reflection of incident light is further reduced; thus only ‘bursts’ of evenly reflected incident light from the less curved surfaces of the cross-sectional shape are seen along the length of the fibre, filament, yarn and/or fabric; the tri-lobal cross-section plossess the sparkling lustre to the greatest degrees as the number of lobes in the cross-sectional shape are increased (i.e. it becomes multi-lobal), the incident light is scattered to such an extent on reflection that no sparkle and only a very dull lustre can be seen. These cross-sectional shapes are not stiff, easy to bend, pliable, flexible with a soft to firm handle; the handle may also be crisp because the lobes may create increased friction between the fibre or filament and the skin; the regularity and evenness of the lobes may still, however, give a somewhat smooth and slippery handle. gO O The irregular cross-sectional shapes and uneven longitudinal surfaces of such fibres as cotton, flax and wool makes them dull or non-lustrous fibres; however, flax with its polygonal or many sided cross-section and relatively flat, regular longitudinal surfaces tends to display a slight lustre. for the general effect of the cross-sectional shape upon the ‘other physical fibre properties see the individual Chapters on these fibres. —-. 34Introduction to fibre polymers and fibre properties Table 1.5 (continued) Generalised shape of fibre General effect of cross-sectional General effect of cross-section shape upon fibre lustre cross-sectional shape upon other physical fibre properties Titanium dioxide Titanium dioxide is a white substance. It is ground to a very fine powder so as to have a particle size of less than one micromette. It is, added to the spinning solution of man-made fibres as a delustring ec > g agent. The many different shapes of the titanium dioxide particles (Gce left) reflect the light at random or in no particular order. Thus A 2 when they are within the extruded filament, it will display a reduced lustre. Filaments or staple fibres containing no titanium dioxide have o o a bright lustre. To manufacture filaments with a semi-lustre about A half a per cent of titanium dioxide has to be added to the spinning solution. For the manufacture of delustred or dull lustre filaments and staple fibre up to two per cent of titanium dioxide may have to be added to the spinning solution, The micro-structure of a textile fibre and filament Microscopic longitudinal and cross-sectional structure and appearance ‘The microscopic structure is of importance for two main reasons: 1 conclusive identification 2 influence on skin contact comfort. With, for example, cotton, flax, viscose or wool it is possible to make a conclusive identification by examination under the microscope of the longitudinal and cross- sectional structure of the fibre or filament. The individual characteristics of the textile micro-structure have a decisive influence on its skin contact comfort. For instance, the minute surface irregularities of the otherwise regular and even fibre structure of cotton and silk make them comfortable and pleasant to wear against the skin. In contrast, the extremely smooth, even, regular surface structure of such fibres as nylon and polyester tends to feel aesthetically un- pleasant and uncomfortable against the skin. (See also ‘hygroscopic nature’, page 39.) Figure 1.14 shows that manufacturers can determine the longitudinal and cross sectional structure and appearance of man-made fibres. However, most of these modifications have not been very successful (see also Fig. 1.15). The conventional structure of the man-made fibres used for apparel is the result of their extrusion through circular orifices in the spinnerets. The only intentionally modified man-made fibres are the tri-lobal nylon and polyester, which are extruded through T-shaped orifices to give the three-lobed cross-section (see Figs 1.15 and 5.10). The only natural fibres on which significant surface modifications are carried out are cotton and wool. The modifications are usually made during the conversion of the fibres into fabric. Cotton may be mercerised; this is a process by which the fibres are swollen (see also page 47). Wool may be made shrink-resistant, by altering the friction- al properties of the wool fibre surface; the process is described on page 176. 35Textile science Profiled fibres shape of spinneret orifice ‘cross-section of extruded filament shape of spinneret Y orifice filament extruded ction of TH XZ w A x © ve @ Figure 1.14 Modifying the morphology of man-made fibres. These diagrams show how solid and hollow profiled filaments can be produced. From them, profiled staple fibres may be made Profiling filaments reduces the contact they make with the skin, thus making them aesthetically more pleasing to handle, Profiing also increases the friction that develops between filament surface and skin, giving a more pleasant handle than the non-profled equivalent, Hollow filaments are lighter in weight, more insulating and possible more absorbent than their solid core equivalents. ‘The disadvantage of proflng is that it adversely affects extensibility, tenacity, permanent flexing and resistance to abrasion. This adverse effect becomes worse, the more pronounced the profiling. However, profiled solid and hollow filaments and their staple fibres have the following advantages: better cover factor, greater bulk, better handle, greater crimp effect, greatly increased permeability to air, better absorption of perspiration, higher water absorbency, considerably less tendency to pill, reduced slippage, Detter dimensional stability of knitted fabrics. Nevertheless, the only profiled filaments which have been successfully utilised are the nylon and polyester trllobal flaments as shown in Fig. 1.15. Sub-microscopic fibre features ‘These are the morphological features of the fibre which are more readily seen under the electron microscope than under the optical microscope. Most of the natural fibres tend 36Introduction to fibre polymers and fibre properties Figure 1.15 Cross-section of profiled trilobal nylon filaments, magnified 200 times. Trilobal polyester is also ‘manufactured. These two are so far the only profiled man-made fibres which have become established. They tend to be used mainly as fashion fibres for specialised knitted outerwear for women, and in the pile of certain carpets. to have distinct sub-microscopic features: for example, the fibre walls of cotton; or the variety of cells found in wool fibres. At this level, silk appears more like a man-made fibre, and tends to lack readily identifiable sub-microscopic features. ‘Man-made fibres, though mainly lacking distinguishable sub-microscopic features, are considered to have a distinct surface skin. This skin is considered to be more crystalline in its polymer orientation than the core of the fibre. Its existence appears to \ be of no particular relevance. Natural fibres, more than man-made fibres, tend to consist of fibrils (exceedingly small fibres). These may be considered as strands of polymers, which vary considerably in diameter and length. The fibrils found in natural fibres vary in thickness from about 4 to 10 nm; no estimate of their length has been reported. While some fibrillar features of certain fibres might be seen using an optical microscope, only the electron microscope will reveal any details of a fibre’s polymer system. ‘The polymer system is the coherent mass of polymers which determines to a very large extent the physical properties, and to a somewhat lesser extent the chemical properties, of the fibre. The polymer system consists of randomly arranged amorphous and crystalline polymer regions. Table 1.4 shows how these randomly arranged polymer re~ i gions may influence fibre properties. ‘Amorphous and crystalline regions consist of polymers which tend to influence fibre properties according to: 1 how well or otherwise they fulfil the requirements of fibre-forming polymers given from page 23 onwards; 2 the number and types of inter-polymer forces of attraction formed between the polymers (see also page 15 onwards); 3. their intra-polymer bonding (see also page 8 onwards). 37Textile science Table 1.6 Dimensional relationships between some fibre features Fibre feature Approximate range of its dimensions Visual filament length from several hundred metres to several kilometres fibre length from shorter than 15 mm to longer than 150 mm length of crimp waves in man-made and natural from just less than | mm to more than 25 mm fibres Microscopic spacings of convolutions of cotton fibres 0.1 mm or 100 pm fineness or diameter of filaments and fibres fyom finer than 10 jum to thicker than 75 jam. cortical cells of wool length 100 yum to 200 jum ‘maximum thickness 2umto5 um ‘Sub-microscopic fibrils of natural fibres Iength not known thickness 2nmtoS am fibre polymers length from not much less than 75 nm to 5000 nm and longer thickness 1 nm to 10 nm Fibre tenacity ‘The tenacity or strength of a fibre is in general directly related to the length of its polymers, degree of polymer orientation, and strength and types of inter-polymer forces of attraction formed between polymers. Thus, the longer the polymers, the more crystalline can be their orientation, and the stronger may be the inter-polymer forces of attraction formed, the stronger and more inflexible may then be the fibre (see also Table 1.4). Elastic-plastic nature of fibres It has already been stated that a fibre with a rather crystalline polymer system tends to be stiff and inflexible, owing to restricted polymer movement. Excessive bending or stretching of such a fibre tends to cause polymer rupture, resulting in irreparable dam- age to the polymer system, which will now be weak where polymer rupture has occurred. This will cause undesirable fibre wrinkling and creasing due to these weakened regions of the polymer system. ‘A more amorphous polymer system has sufficiently large interpolymer spaces into which polymers can be displaced when the fibre is bent or stretched, giving fibres with this characteristic a softer handle. Should the fibre’s polymer system be held together only by weak interpolymer forces of attraction, fibre polymer displacement will occur readily from bending or stretching, because these weak forces can be easily broken. 38Introduction to fibre polymers and fibre properties Such polymer displacement will be seen as wrinkling and distortion of the textile material produced from the fibre. An elastic fibre is one whose polymers can be strained with subsequent recovery following the removal of the strain or applied load, The interpolymer forces are such that they aid the recovery of the strained polymer system (see also Table 1.4). Hygroscopic nature The hygroscopic nature of a fibre is directly related to the polarity of its polymers and the ratio of its amorphous and crystalline regions. A hygroscopic or absorbent fibre tends to have a predominantly amorphous polymer system consisting of polar polymers. These attract water molecules, while the amorphous nature allows entry of the water molecules into the polymer system. Highly crystalline polymer systems do not permit ready entry of water molecules even if the polymers are distinctly polar, as is the case with nylon. The hydrophobic nature of the highly oriented or crystalline synthetic fibres gives rise to static electricity. This can be a considerable nuisance during yarn and fabric manufacture, as well as during garment making and subsequent wearing of the apparel item. The absence of static electricity in the more amorphous fibres is usually due to their moisture absorbency. It is for this reason that the amorphous fibres are blended with the more crystalline fibres to make the latter more comfortable to wear. Thermal properties The most important thermal property of a textile fibre or filament is the temperature at which it may soften and begin to melt. This temperature is a relative measure of the fibre’s heat resistance. It indicates to what temperature the fibre may be safely heat- processed during finishing, pressed during garment manufacture, hot laundered, ironed and/or pressed after dry cleaning. ‘The softening and melting point temperatures of a fibre are related to the crystallinity of its polymer system, the length of its polymers, and the type and number of interpolymer forces of attraction holding its polymer system together. The greater the crystallinity of the polymer system, the longer (usually) are the polymers and the stronger tend to be its interpolymer forces of attraction. Hence more heat or kinetic energy will be required to free the polymers from each other. This would result in the fibre having a greater resistance to heat, as well as to softening and melting at a higher temperature (see also pages 27-30). It should be noted that the above considerations, and those given elsewhere, do not provide a complete explanation for the effect of heat upon fibres. This applies especial- ly to the natural fibres and the regenerated cellulose fibres, neither of which soften or melt when heated, for example by ironing. Chemical properties The general chemical reactivity of individual fibre polymer compositions is given under ‘Intra-polymer bonding’ on pages 8-15. This gives an indication of the extent to which the 39Textile science polymers of a fibre may react with the common degrading agents such as the alkalis of laudering liquors, atmospheric pollution, normal soiling of textiles, sunlight, etc. ‘A fibre’s chemical properties are directly influenced by the ratio of amorphous to crytalline regions in its polymer system. In general, fibres with a more crystalline or more highly oriented polymer system-tend to be chemically more resistant than fibres with a more amorphous polymer system. The more amorphous polymer system, with its greater inter-polymer spaces, can be more readily penetrated by the ions, molecules andlor radicals of degrading agent. Not only can the more crystalline fibres keep out the molecules etc. of degrading agents, but they also make it very difficult for dye molecules to enter their polymer sytem to colour the fibre. 402 The cellulosic fibres Textile fibres composed of pure cellulose are: 1 Natural cellulosic fibres: abaca, coir, cotton, flax, hemp, henequin, jute, kenaf, sisal, etc. 2. Man-made cellulosic fibres: cuprammonium, polynosic, and viscose. Of the very many cellulosic textile fibres, only the commonly used ones — cotton, flax and viscose — will be considered here. Cotton Textile classification ‘The word cotton is derived from the Arabic. Depending upon the arabian dialect, it is pronounced Autan, quin, quiun, etc. As the cotton fibre is obtained from a plant it is classified as a natural, cellulose, seed, mono-cellular, staple fibre. The density of the fibre (referred to from now on as fibre density) is 1.52 g/cm’, which makes cotton a rather heavy fibre. Fibre morphology The macro-structure of cotton Under a microscope, a cotton fibre appears as a very fine, regular fibre. It ranges in length from about 10 mm to 65 mm, depending upon the quality of the fibre. The length of a textile fibre is an important factor in spinning yarn. This is particularly so with cotton, which is a relatively short staple fibre. The longer the cotton fibre, the easier it is to spin into a smoother, stronger yarn. In turn, this results i in a more comfortable, more durable, more attractive fabric and garments. Cotton fibres are amongst the finest in common use. They range in fibre diameter from about 11 4m to 22 wm. Such very fine fibres permit the manufacture of fine, light-weight cotton fabrics and garments, despite the fact that it is a dense fibre. Cotton is a very fine fibre with little variation in fibre diameter; compared with wool for instance, its fibre diameter is not considered as critical a fibre dimension as its length. The fibre length to breadth ratio of cotton ranges from about 6000:1 for the 4Textile science longest and best types, to about 350:1 for the shortest and coarsest cotton types. The greater this ratio, the more readily can the cotton fibres be spun into yarn. Cotton fibres vary in colour from near white to light tan. The colour of cotton fibres depends on its type, environment, soil and climatic conditions under which it is grown. These factors influence the amounts of protein and minerals which will occur in the fibre and, thus, its colour. Sea Island and Egyptian cotton types have a subdued lustre due to their greater fibre length which causes more even reflection of incident light. However, the lustre of these two cotton types is of little significance when compared with lustrous man-made fibres. The microscopic appearance of cotton Under the microscope, the cotton fibre looks like a twisted ribbon or a collapsed and twisted tube. These twists or convolutions identify the cotton fibre under the microscope (see Figs 2.1 and 2.2). ‘The seed end of the fibre is quite irregular, having been torn, during ginning, from the epidermis or skin of the cotton seed. The main part of the fibre, about three- quarfers to fifteen-sixteenths of its length, is quite regular, with a thick fibre wall, a canal along the centre of the fibre called the lumen, and about sixty convolutions per centimetre. The fibre tip is less than one-quarter of the fibre length. At this end, the fibre tapers to a cylindrical, pointed tip, and has no convolutions. The convolutions are a a ee NAY Figure 2.1a _A longitudinal section of raw cotton, Figure 2.1b A cross-section of raw cotton ‘magnified 500 times. Note the convolutions or ‘magnified 500 times, Note the kidney shape of the twist in the fibres, cross-section of the fibres. = Figure 2.28 A longitudinal section of mercerised Figure 2.26 A cross-section of mercerised cotton, magnified 500 times. Note the much cotton, magnified 500 times. Note the oval to reduced prominence of the convolutions compared round shape of the cross-section ofthe fibres. with raw cotton, 42The cellulosic fibres formed after the cotton boll bursts open, When this happens, the limp, sap-filled cotton seed hairs begin to dry out, their cell walls collapse inward, decreasing the size of the lumen. When the cotton seed hairs cease shrinking, twisting and collapsing inward, they become the valuable, convoluted cotton fibres. The convolutions give cotton an uneven fibre surface, which increases inter-fibre friction and enables fine cotton yarns of adequate strength to be spun. ‘The appearance of the cotton fibre’s cross-section under the microscope is referred to as being kidney-shaped, see Fig. 2.1(b). This shape occurs from the inward collapse of the cotton fibre when it dries out, while still attached to its seed. The cross-section varies in its kidney-shape according to where it was cut from the fibre’s length. The cross-section tends to provide an indication of the relative dimensions of the lumen and fibre walls. The convolutions and kidney-shaped cross-section of the cotton fibre enable it to make only random contact with the skin. This type of contact is more compatible with human skin physiology and therefore more comfortable. The countless minute air spaces which exist because of the convolutions and kidney-shaped cross-section of cotton fibres increase the moisture absorbency of cotton textile materials thus making them more comfortable to wear. It is for these reasons that manufacturers crimp and texture man-made filaments and staple fibres in order to increase fibre moisture absorbency and minimise fibre contact with the skin. The micro-structure of the cotton fibre The cotton fibre is a single plant cell. Its cross-section is oval, compared with the normal hexagonal plant cell. However, like all plant cells, cotton has a distinct cuticle, well developed primary and secondary walls, and a lumen (see Fig. 2.3). ‘The cuticle is the ‘very outside’ or ‘skin’ of the cotton fibre. It is composed of a waxy layer (cotton wax) only a few molecules thick. The waxy nature of the cuticle enables it to adhere tenaciously to the primary wall of the fibre. The inert nature of this cotton wax protects the rest of the fibre against chemical and other degrading agents. Kier boiling and bleaching during cotton finishing removes much of the cuticle or wax. primary call wall layers of secondary cell wall Na mute Figure 2.3. A morphological diagram of the cotton fibre 43Textile science ‘his enables cotton to absorb moisture more quickly. Subsequent laundering will gradually remove most of the remaining cuticle. As the extent of the cuticle is decreased further, deterioration of the cotton textile material increases. The primary cell wall, which is immediately underneath the cuticle, is about 200 nm thick. It is composed of very fine threads of cellulose, called fibrils. These fibrils are about 20 nm thick, but their length is as yet unknown. The fibrils spiral at about 70° to the fibre axis. This spiralling imparts strength to the primary cell wall and, hence, to the fibre. The primary cell wall can be visualised as a sheath of spiralling fibrils. Beneath the primary cell wall lies the secondary cell wall, which forms the bulk of the fibre. Concentric iayers of spiralling, cellulosic fibrils, not unlike the growth rings of trees, make up the secondary wall. Its fibrils are about 10 nm thick, but of unde- fined length. Near the primary cell wall, the fibrils of the secondary wall spiral at about 20° to 30° to the fibre axis. This spiral angle widens to about 20° to 45° for the fibrillar layers nearer the Jumen. Much of the strength and stability of the cotton fibre and, hence, of the yarns and fabrics may be attributed to these spiralling fibrils. Whenever the fibrils change the direction of their spirals, a weak area exists in the secondary wall structure. It is at these weak areas that the convolutions of the fibre also alter the direction of their twist. ‘The hollow canal, running the length of the fibre, is called the lumen. Its walls are the innermost, concentric layers of spirals of the secondary cell wall. The lumen was once the central vacuole of the growing cotton fibre. It was full of cell sap, which was composed of a dilute, aqueous solution of proteins, sugars, minerals and cell-waste products. When the sap evaporated, its constituents remained behind to contribute to the colour of the cotton fibre. Further, as the sap evaporated, the pressure inside the fibre became less than the atmospheric pressure on the outside. This caused the fibre to collapse inward resulting in the characteristic kidney-shaped cross-section of the cotton fibre. The polymer system The cotton polymer The cotton polymer is a linear, cellulose polymer. The repeating unit in the cotton polymer is cellobiose which consists of two glucose units (see Fig. 2.4). It is not fully understood how cellulose is formed or polymerised by plants. It is therefore better to refer to cellobiose as the repeating unit of the cotton polymer rather than as its monomer. The cotton polymer consists of about 5000 cellobiose units, that is, its degree of polymerisation is about 5000. It is a very long, linear polymer, about 5000 nm in Iength and about 0.8 nm thick, (See also page 2.) The most important chemical groupings on the cotton polymer are the hydroxyl groups or -OH groups. These are also present as methylol groups or -CH,OH. Their polarity gives rise to hydrogen bonds between the OH-groups of adjacent cotton polymers. Van der Waals’ forces also occur but compared with the hydrogen bonds, the van der Waals’ forces are of little significance. 44The cellulosic fibres glucoside oxygen atom OH-group ‘methyl group P i HO HOH TO OH HO | [Link] Oo} é—¢ é—o. jo| »¢— C—O, 0 wo SZ by a Zi Nf NZ bu ihe ay i NY ~ 1 Qu nL LT AN 14 NEN a N07 Yo \f 4 H | t i 1 4 i L CH;OH HHO _L CH;OH JH HO ccollobiose unit glucose unit Figure 2.4 The chemical formula of the cellulose polymer. Its thought that the cotton cellulose polymer is composed of 5000 cellobiose units, while the flax cellulose polymer is thought to contain 18 000 cellobiose units. The polymer system of cotton Cotton is a crystalline fibre. Its polymer system is about 65 to 70 per cent crystalline and, correspondingly, about 35-30 per cent amorphous. Therefore, the cotton polymers are, in the main, well oriented and probably no further apart than 0.5 nm, in the crystalline regions. This is the maximum distance across which hydrogen bonds can form between polymers. Hydrogen bonds are the dominant and most important forces of attraction present in the polymer system of cotton. For this reason, van der Waals? forces which are also present have little relevance. Because the appearance of the cellulose polymer is not unlike a chain of hexagonal units, the polymer system of cotton can be imagined as a roll of wire netting. The crystalline regions are therefore the well ordered lines and rows of hexagonal holes of the wire netting. The amorphous regions are a disarrangement of these orderly lines and rows of hexagons. Physical properties Tenacity ‘The strength of cotton fibres is attributed to the good alignment of its long polymers (that is, its polymer system is about 70 per cent crystalline), the countless, regular, hydrogen bond formations between adjacent polymers, and the spiralling fibrils in the primary and secondary cell walls. It is one of the few fibres which gains strength when wet. It is thought this occurs because of a temporary improvement in polymer alignment in the amorphous regions of the polymer system. The improved alignment when wet results in an increase in the number of hydrogen bonds, with an approximate 5 per cent increase in fibre tenacity. Elastic-plastic nature The cotton fibre is relatively inelastic because of its crystalline polymer system, and for this reason cotton textiles wrinkle and crease readily. Only under considerable strain will cotton polymers give and slide past one another. They are usually prevented from doing so by their extreme length and countless hydrogen bonds, which tend to hold them within their polymer system. Bending or crushing of cotton textile materials 45Textile science places considerable strain on the fibres’ polymer systems. It will probably cause polymer fracture since the crystallinity of the polymer system makes it difficult for cotton polymer to be displaced by bending or crushing forces. Polymer fracture results in polymer disarrangements. These become weak points in the polymer system, and hence weak areas in the cotton fibre structure. Such weakening of the polymer system, and therefore fibre structure, causes cotton textile materials to crease and wrinkle readily. Hygroscopic nature ‘The cotton fibre is very absorbent, owing to the countless polar —OH groups in its polymers; these attract water molecules, which are also polar. However, the latter can only enter the polymer system in its amorphous regions, as the inter-polymer spaces in the crystalline regions are too small for the water molecules. Aqueous swelling of the cotton fibre is due to a separation or forcing apart of polymers by the water molecules in the amorphous regions only. The general crispness of dry cotton textile materials may be attributed to the rapidity with which the fibres can absorb moisture from the skin of the fingers. This rapid absorption imparts a sensation of dryness which, in association with the fibres’ inelas- ticity or stiffness, creates the sensation of crispness. The hygroscopic nature ordinarily prevents cotton textile materials from developing static electricity. The polarity of the water molecules, attracted to the hydroxyl groups on the polymers, dissipates any static charge which might develop. Thermal properties Cotton fibres have the ability to conduct heat energy, minimising any destructive heat accumulation. Thus they can withstand hot ironing temperatures. There is no satisfactory explanation for this. Excessive application of heat energy causes the cotton fibre to char and burn, without any prior melting. This is an indication that cotton is not thermoplastic, which may be attributable to the extremely long fibre polymers and the countless hydrogen bonds they form. These prevent the polymers from assuming new positions when heat is applied, as would be the case with the shorter polymers of thermoplastic fibres. When sufficient heat, that is, kinetic energy, is applied to the cotton fibre, its polymers will begin to vibrate or become so excited as to disintegrate. This in conjunction with the large quantity of kinetic energy present results in violent chemical reactions observed as fibre combustion. Chemical properties Effect of acids Cotton fibres are weakened and destroyed by acids. Acidic conditions hydrolyse the cotton polymer at the glucoside oxygen atom, which links the two glucose units to form the cellobiose unit (see Fig. 2.4 and page 12). Mineral or inorganic acids, being stronger than organic acids, will hydrolyse the cotton polymer more rapidly. 46The cellulosic fibres Effect of alkalis Cotton fibres are resistant to alkalis and are relatively unaffected by normal laundering. The resistance is attributed to the lack of attraction between the cotton polymers and alkalis. Mercerising without tension, or slack mercerising, causes the cotton fibres to swell; that is, increase in thickness and contract in length. The swelling is thought to be due to alkali molecules, or radicals, entering the amorphous regions of the fibres’ polymer system. In so doing, they force the cotton polymers further apart, which can be seen as swelling of the fibres. This results in somewhat greater inter-polymer spaces, permitting poorly aligned polymers to orient themselves more satisfactorily, as well as forming additional hydrogen bonds. This explains the increase in fibre strength on mercerising. There is no satisfactory explanation for the contraction of the fibre. With mercerising under tension, which can only be carried out on cotton yarn or fabric, little swelling or fibre contraction occurs. The fibre emerges with increased tenacity and with a distinct, though subdued lustre. Tensioning the cotton yarn or fabric in the aqueous, alkaline liquor assists the fibre polymers to align themselves further, leading to an increase in hydrogen bond formation. This explains the increase in tenacity achieved during mercerising under tension. Mercerising under tension also causes the fibre surface to become smooth and more regular, enabling it to reflect incident light more evenly. This is responsible for the subdued lustre that is associated with tension mercerised cotton textile materials. (See Fig. 2.2.) Either type of mercerising swells the fibres sufficiently to alter their normal kidney- shaped cross-section to a more circular one. In addition, mercerising improves the dye-uptake of the cotton. This means that mercerised cotton fibres dye and print a deeper hue, that is a hue with more chroma, than equivalent unmercerised fibres, when using the same quantity of dye. No satisfactory explanation for this is currently available. Effect of bleaches ‘The most common bleaches used on cotton textile materials are sodium hypochlorite and sodium perborate. Sodium hypochlorite (NaOCl) is a yellowish liquid, smelling of chlorine. Sodium perborate (NaBO7H,02,3H,0) is a white powder, contained in most commonly available domestic laundry detergents. Sodium hypochlorite bleaches cotton textile materials at prevailing room temperatures. However, bleaching with sodium perborate is more effective when the laundry solution exceeds 50°C in temperature. These two bleaches are examples of oxidising bleaches, which is the class of bleaches used most frequently on cotton textile materials. They bleach most effectively in alkaline conditions to which cotton textile materials are resistant. Oxidising bleaches are so called because they liberate oxygen which does the actual bleaching. The reactions between the oxygen libeéated by the bleach and the molecules on the fibre surface responsible for the cotton’s discolouration are not known in any detail. In general it is considered that the oxygen forms water-soluble compounds with the molecules of the fibre surface contaminants. These water-soluble products are rinsed off the fibre during bleaching. 47Textile science Careful bleaching leaves the fibre polymer system largely intact. Careful bleaching will restrict the chemical attack of bleaches to the fibre surface polymers of cotton. Effect of sunlight and weather The ultraviolet rays of sunlight provide photochemical energy whilst the infrared rays provide heat energy necessary to degrade the cotton polymers in the presence of atmospheric oxygen, moisture and air pollutants. Atmospheric moisture (humidity) significantly contributes to the breakdown of the polymers on the surface of the cotton fibres through various hydrolytic reactions. Initially, such degradation, or polymer hydrolysis, is noticed as a slight fibre discolouration. In due course, the reactive nature of the hydrolytic compounds formed acceler- ates the breakdown of the fibre. The weakening of the fibre and breakdown of the cotton textile material is, of course, a clear indication that the polymer system of the fibre has broken down completely. In general, air pollutants are acidic and may rapidly accelerate fibre breakdown through acid hydrolyis to which cotton polymers are not resistant. Fading of coloured cotton textiles is partly due to a breakdown of the dye molecules in the fibres’ polymer systems. This is explained in Chapter 6, ‘Dyeing and printing’. Colour-fastness Cotton is considered to be a relatively easy fibre to dye and print. The classes of dye which may be used to colour cotton are azoic, direct, reactive, sulphur and vat dyes. ‘The ease with which cotton takes up dyes, and other colouring matter, is due to the polarity of its polymers and polymer system. This polarity will readily attract any polar dye molecules into the polymer system. In fact, dye molecules which can be dispersed in water will be absorbed by the polymer system of cotton. However, as with all other textile fibres, the dye molecules can only enter the amorphous regions of the polymer system of cotton. The small inter-polymer spaces in the crystalline regions of the polymer system prevent the entry of the relatively large and bulky dye molecules. Azic dyes ‘Azoic dyeing or printing occurs when two relatively small, water-soluble molecules are made to react within the amorphous regions of the polymer system to form the comparatively much larger, water-insoluble azoic dye molecules. (See also pages 137-139.) The very good to excellent light-fastness of azoic dyed and printed cotton textile materials is due to the resistance of the azoic dye molecules to the potential photo- chemical degradation of the ultraviolet radiation of sunlight The very good to excellent wash-fastness of azoic dyed and printed cotton textile materials is due to the relatively large azoic dye molecules. These are trapped and entangled in the amorphous regions of the polymer systems of the cotton fibres. The azoic dye molecules are attracted to the fibre polymer by van der Waals’ forces. As these forces of attraction are very weak, it is the water-insolubility, relatively large size and entanglement in the polymer system of the azoic dye molecules which account for the very good to excellent wash-fastness properties. 48The cellulosic fibres Direct dyes ‘The attraction between fibre polymers and dye molecules is called substantivity. Be- cause of the very great substantivity direct dyes have for cotton, they have also been given the name of cotton colours. Direct coloured cotton textile materials have only a moderate light-fastness. This may be attributed to the fact that direct dye molecules are affected by the photo- chemical degradation due to the ultraviolet radiation of sunlight, as well as by atmospheric pollutants, ‘The poor wash-fastness of direct dyed and printed cotton textile materials is attributed to the good water-solubility of direct dye molecules. As the direct dye molecules are only attached to the cotton polymers by hydrogen bonds and van der Waals’ forces, any aqueous solution will break these forces of attraction. The cotton fibre will swell in water, enabling some of the direct dye molecules to be removed from the amorphous regions of the cotton polymer system. direct dye molecule attached to the -OH group of two methylol {groups by hydrogen bonds yx net outs onsen OH gr Snel groups Figure 2.5 A possible arrangement of cellulose polymers in the polymer system of a cotton fibre. Note that the dye molecules, represented by shading, occur only in amorphous regions. 9li Textile science Increasing the molecular size of direct dye molecules, as described on pages 143, 144 results in a slight improvement in wash-fastness. Reactive dyes As their name implies, these dyes react chemically with the fibre polymer. The reactive dye molecules form a covalent bond with the hydroxyl groups on the cotton polymers. The great strength and relative inertness of the covalent bond to most common degrading agents securely anchors the reactive dye molecules to the polymers of the cotton fibres. It is for this reason that cotton textile materials which have been dyed or printed with reactive dyes have good wash-fastness properties. The molecules of reactive dyes are also very resistant to the degradative effects of the ultraviolet radiation of sunlight and air pollutants. This means that cotton textile materials coloured with reactive dyes have very good light-fastness. However, some reactive dyes are degraded by chlorine bleaches and chlorinated water, such as in swimming pools. The presence of chlorine may result in a breakdown of the covalent bond which is formed between the dye molecule and the cotton polymer, resulting in a removal of colour from the fibre. It must be emphasised that only some reactive dyes are affected by chlorine. Sulphur dyes Cotton textile materials coloured with sulphur dyes have good wash-fastness. This is attributed to the relatively large sulphur dye molecules which become entangled and trapped within the amorphous regions of the polymer system of the cotton fibres. In conjunction with this is the dye molecules’ water-insolubility. This makes it difficult for aqueous solutions to remove the sulphur dye molecules from the fibre. Sulphur dye molecules tend to form only van der Waals’ forces with cotton polymers. It is thought, however, that these forces of attraction contribute little towards the good wash-fastness properties of sulphur dyed cotton goods. Sulphur dyed cotton textile materials have only fair light-fastness. This is attributed to the lack of resistance by the sulphur dye molecules to the degrading photo-chemical effects of the sunlight’s ultraviolet radiation. After-treatments, as explained in Chapter 6, improve somewhat the light-fastness of sulphur dyed cotton textile materials. Vat dyes Excellent wash-fastness is achieved with vat dyed and printed cotton textile materials. This is because of the comparatively large vat dye molecules. Their physical size causes them to become trapped and entangled within the amorphous regions of the polymer system of the cotton fibres. This and the water-insolubility of vat dye molecules make it extremely difficult for any aqueous solutions to remove the dye molecules from the fibres’ polymer systems. The vat dyes, being non-polar, can only form van det Waals’ forces, These are not considered to contribute significantly towards the wash-fastness properties. Vat dyed and printed cotton textile materials have excellent light-fastness. The chemical composition of the vat dye molecules provides them with the excellent resistance against the degrading photo-chemical effects of the ultraviolet radiation of sunlight and air pollutants. There are, however, some exceptions to this, e.g. indigo. 50The cellulosic fibres Flax Textile classification ‘The word flax is derived from the Old English fleax. The Teutons referred to it as flakso, coming from the teutonic root fleh, to plait. Linen is the term applied to the yarn spun from the flax fibres, and to the cloth or fabric woven from this yarn. ‘The flax fibre is classified as a natural, cellulose, bast, multi-cellular fibre. It has a fibre density of 1.50 g/cm, and is considered to be a heavy fibre. It is for this reason that most linen textile materials are of light construction. Thick linen textile materials would be uncomfortably heavy to wear Fibre morphology The macro-structure of flax The flax fibre is a thick, regular fibre with a subdued lustre. It ranges in length from about 10 cm to 100 cm, averaging about 50 cm in length. As the flax fibre is a strand of cells, it thickness depends upon the number of these cells in any one fibre cross- section. It seems that about 3 to 6 cells constitute a fibre cross-section. The flax cells are about 25 mm long and 10 ym to 20 um thick. This would give an average fibre thickness ranging from about 40 wm to 80 um. ‘The value of flax is directly proportional to its fibre length. Its fibre length to breadth ratio is, therefore, of considerable significance. For the longest and the best flax this tends to about 15 000:1. Short flax fibres may have a fibre length to breadth radio of 1500:1, or less. ‘The colour of flax varies from light blond to grey blond, the particular shade resulting from the agricultural and climatic conditions under which it was grown and the quality of retting. The subdued lustre of flax is due to its long regular fibre surface, which is coated with a film of wax. This enables a significant amount of the incident light to be reflected, resulting in the subdued lustre. However, when compared with that of the lustrous man-made fibres the subdued lustre of flax is insignificant. Figure 2.6 A longitudinal section of bleached Figure 2.66 A cross-section of bleached flax or flax or linen fibre, magnified 200 times. Note the linen fibres, magnified 200 times. Note the ‘cross-markings or nodes. polygonal or many-sided cross-section of the fibres. 51Textile science Microscopic appearance of flax The cross markings, known as nodes, on flax fibres give them their characteristic microscopic appearance. There may be up to 800 nodes in a single flax fibre cell. The length of the node indicates the width or thickness of the fibre cell. The nodes are thought to be fissures in the cell walls. Wherever a node occurs, it indicates a change in the spiral direction of the fibrils which constitute the cell walls. As with the cotton fibres, such spiralling imparts strength to the cell and, hence, to the flax fibre. The polygonal cross-section of the flax fibre cell is typical of most plant cells. (See Fig. 2.6.) The micro-structure of flax Although the flax fibre cell is covered with a wax film, this does not constitute as distinct a cuticle as in the case of cotton. The cell walls of flax are constructed of spiralling fibrils composed of cellulose polymers. On the whole, the flax cell is more sturdily constructed that the cotton cell, as indicated by the former’s thicker cell walls. This explains, in part, the greater tenacity of flax compared with cotton The polymer system The flax polymer and its polymer system Chemically, the flax polymer is the same as the cotton polymer; both are celluose polymers. Physically, the flax polymer differs from the cotton polymer, in that it has a degree of polymerisation of about 18 000. This means the flax polymer is made up of about 18 000 cellobiose units (see Fig. 2.4). The flax polymer is about 18 000 nm long, and about 0.8 nm thick. This makes it the longest known, linear textile polymer. The polymer system of flax is more crystalline than that of cotton, because of its longer polymers. These spiral about each other at approximately 6° to the fibre axis, thereby contributing towards the tenacity and durability of the fibre. The greater crystallinity of flax fibres is demonstrated by the fact that they are stronger, crisper and stiffer to handle, and textile materials wrinkle more readily than those of cotton fibres. Physical properties Tenacity Flax is a very strong fibre because its very crystalline polymer system permits its extremely long polymers to form more hydrogen bonds than cotton polymers. The reasons given to explain the increase in wet tenacity of cotton fibres apply also to flax fibres. Elastic-plastic nature The very inelastic nature of flax is due to its very crystalline polymer system. It tends to lock its polymers into position with the aid of the countless hydrogen bonds which 52The cellulosic fibres form between the polymers. Hence, the polymers cannot yield, and they resist being displaced from their positions in the polymer system. The unyielding nature of the very crystalline polymer system gives the flax fibre its stiff handle. Flax will resist being flexed or bent. As with cotton the crispness of its handle is due to its ability to absorb moisture rapidly. ‘The ready wrinkling and creasing which occurs with linen textile materials is also due to the very crystalline polymer systems of the flax fibres. When these are bent or flexed, their polymers are liable to break leading to fractures in the polymer system. These fractures become weak areas on the fibre structure, leading to wrinkling and creasing in the linen textile material. Hygroscopic nature ‘The reasons given above to explain the hygroscopic nature of cotton apply also to flax. Thermal properties Flax has the best heat resistance and conductivity of all the commonly used textile fibres. No satisfactory explanation can be offered for this. With regard to other thermal properties of flax, the reasons given for cotton apply equally to flax. Chemical properties Owing to the similar chemical constitution of cotton and flax, the explanations offered for the chemical properties of cotton may also be applied to flax. However, it needs to be remembered that linen textile materials are not mercerised. Normal laundering will result in alkaline hydrolysis of the waxes and gums bonding the cells forming the flax fibre together. This results in cell ends projecting above the surface of the linen textile material, and is referred to as cottonising of linen. Severe | cottonising will cause a noticeable weakening of the linen textile material. Viscose Textile classification Viscose is a man-made, natural polymer, cellulosic or regenerated cellulose filament or staple fibre. There are two other man-made regenerated cellulose fibres, namely cuprammonium or cupro and polynosic or modal. ‘The International Organisation for Standardisation, in its standard ISO 2076-1977 (B), defines these three man-made, regenerated cellulose fibres as follows: Cuprammonium or cupro regenerated cellulose obtained by the cuprammonium process. The name cuprammonium is obtained from the aqueous cuprammonium hydroxide solvent in which the cellulose is dissolved to form the spinning solution, The International Organisation for Standardisation prefers the name cupro. Polynosic or modal regenerated cellulose obtained by processes giving a high tenacity and a high wet modulus, In other words, polynosic or modal is a regenerated 53Textile science cellulose fibre which, when wet, remains stronger and distorts less than either cuprammonium or viscose. Polynosic means many fibrils, whilst modal is derived from modulus. The International Organisation for Standardisation prefers the name modal. Viscose regenerated cellulose obtained by the viscose process. The name ose was derived from the word viscous, which describes the liquid state of the spinning solution. A viscous solution is as thick as, and/or flows like, honey. The above three regenerated cellulose fibres are sometimes still referred to collective- ly by the generic name rayon. The International Organisation for Standardisation does not use the name rayon because, as it states in ISO 2076-1977(B), ‘this name, used generically for regenerated cellulose fibres in some countries, does not have the same meaning everywhere.’ The Organisation also suggests that each country should determine whether or not to use the name ‘rayon’. If it finds such use desirable, then it should define ‘rayon’ in one of its national standards. In the case of Australia, the name ‘rayon’ is not defined in a national standard; but the name is written into all textile labelling legislation. In this legislation, rayon is used generically for the above three regenerated cellulose fibres. The names ‘cuprammonium’ and ‘polynosic’ are used instead of ‘cupro’ and ‘modal’, respectively. The fibre density of viscose is 1.49 g/cem*, which makes it a heavy fibre, similar to cotton and flax. However, its availability as fine filament yarns enables the manufacture of light weight viscose textile materials. Fibre morphology The macro-structure of viscose Viscose is a fine, regular filament or staple fibre. The staple fibre is usually manufactured in a crimped configuration. This overcomes to a large extent the very regular, even, smooth and slippery nature of the uncrimped equivalent. Crimping viscose staple fibre increases the inter-fibre friction, resulting in better fibre cohesion during and after spinning of its yarns. On the whole, crimped viscose staple fibre spins into yarns of slightly improved texture and bulk, with sufficient irregularity to make the crimped staple fibre yarn aesthetically more pleasing compared with its uncrimped equivalent. The length of staple fibre cut from viscose filaments depends upon the required end-use. Usually they are cut to lengths similar to those of cotton, flax and wool fibres. In contrast, the length of the viscose filament is only restricted to the number of kilometres which can be wound upon the particular yarn package being used. Viscose is extruded in fibre diameters ranging from 12 ym to 22 ym, depending upon end-use requirements, These give a fibre length to breadth ratio in excess of 2000:1, ensuring that even the shorter staple fibres will spin satisfactorily into yarn The colour of the extruded viscose filaments tends to be slightly off-white. This is attributed to their translucency which permits some light to pass through the filaments before it is reflected. Therefore some of the incident light is absorbed, with the effect that the light reflected is off-white in colour. 54The cellulosic fibres ‘Most of the incident light upon viscose is reflected with considerable intensity from the filaments’ or staple fibres’ smooth and regular surface. This results in a harsh and bright lustre. Hence, a delustring agent, usually titanium dioxide, may be added to the spinning solution. Titanium dioxide is a white powder, with a particle size of about 0.8 ym. When these are present in the filaments, they make the viscose appear white. As the titanium dioxide particles also scatter the reflected light, it will be less intense and make the viscose filaments appear to have a subdued lustre. The degree to which the lustre is subdued depends upon how much titanium dioxide is added to the spinning solution of viscose. (See also Table 1.5.) ‘Man-made fibres, more so than natural fibres, tend to be translucent. Translucency of a fibre means that it is partially transparent; that is, that its fibre structure and polymer system permit some incident light to pass completely through the fibre. It also means that translucent fibres are more uniform in their micro-structure. Fibres, such as cotton, wool and flax, which are not translucent but are opaque have quite an intricate fibre microstructure, as well as more involved polymer configurations in theit polymer systems. These fibres tend to contain more impurities, even after thorough cleaning, compared with the man-made fibres and silk. Thus, the fibre micro-structure of cotton, flax and wool is more likely to absorb any light entering the fibre. On the other hand, viscose, the other man-made fibres and silk lack a discernible fibre micro- structure and impurities, thus permitting some light to pass through the fibre, which makes them translucent. Microscopic appearance of viscose Viscose filaments and staple fibres have many longitudinal striations (tiny grooves) which give them their characteristic microscopic appearance. These are responsible for the irregularly serrated perimeter of their nearly round to oval cross-section. See Fig. 2.7. The striations are formed by irregular contractions of the freshly extruded viscose filaments as they solidify in the coagulation bath. Figure 2.7 Bright lustre viscose. Note the characteristic striations on the filament atthe left. These striations are due to the irregularly serrated cross-section of the filament, or staple fibre, shown al the right. Both sections are magnified 400 times. 58Figure 2.8 Delustred viscose. Note the specks of delustrin photograph. Both sections are magnified 400 times. [ fi) RRR mime aes [| PO i I ||] ieee } j | \ Figure 2.10 A cross-section of bright-ustre polynosic or modal, magnified 500 times. The near-circular or very swollen kidney shape of the cross-section provides a featureless longitudinal section, 56The cellulosic fibres A speckled longitudinal appearance identifies viscose, and ali other man-made fibres of similar appearance, as delustred man-made fibres (see Fig. 2.8). As cuprammonium and polynosic are coagulated much more slowly during extrusion, their filaments and staple fibres do not develop any striations (see Figs 2.9 and 2.10). The minute striations are countless tiny grooves which cause the filaments or staple fibres to make random contact with the skin. Such skin contact feels more comfortable than the much more intimate contact of the non-striated fibres. The micro-structure of viscose The viscose filament is a fine, coagulated stream of regenerated cellulosic solution, which displays no discernible micro-structure. However, as its name implies, polynosic does show, under the electron microscope, a distinct fibrillar structure. This fibrillar structure is a distinct remnant of its natural cellulosic origins, and of significance with regard to its properties, which are somewhat superior to those of the other two regenerated cellulose fibres. The polymer system The viscose polymer It is a linear, cellulose polymer, similar to that of cotton (see Fig. 2.4). However, the viscose polymer does not have the spiral configuration of the cotton polymer. The significant physical differences between the regenerated cellulose and cotton polymers are listed in Table 2.1. As the chemical groupings and forces of attraction of the viscose and other regener- i ated cellulose polymers are very similar to those of the cotton polymer, reference should be made to the section on cotton for further details. The polymer system of viscose The polymer system of viscose is rather similar to that of cotton. However, there are some differences. The viscose polymer system is very amorphous, being about 35-40 per cent crystalline and about 65-60 per cent amorphous. Its relatively short polymers make it difficult to achieve a more crystalline polymer system without producing dis- advantageous fibre properties. Table 2.1 Significant physical difference between regenerated cellulose and cotton polymers Approx. Approx. Approx. Approx. number of polymer polymer degree of ara cellobiose length thickness polymerisation units (am) (am) Viscose 175 180 08 175, Polynosic or modal 300 310 08 300 Cuprammonium or eupro 250 260 08 250 Cotton 5000 5000 08 5000 37Textile science ‘The polymer system of polynosic is considered to be somewhat more crystalline than that of viscose, as borne out by the former’s physical and chemical properties. Physical properties Tenacity Because the polymer system of viscose is very amorphous, its filaments or staple fibres are weaker than cotton and have only a fair tenacity. The shorter, more poorly aligned viscose polymers give rise to fewer hydrogen bonds than would otherwise be possible. When wet, viscose is only half as strong as when dry. The reason for this is again the very-amorphous nature of its polymer system which readily permits the entry of water molecules. These push the polymers apart, breaking a significant number of hydrogen bonds, resulting in the weaker fibre when wet. The somewhat more crystalline nature of polynosic or modal permits fewer water molecules to enter its polymer system. Therefore, fewer hydrogen bonds are broken, and polynosic will not weaken as much when wet as its viscose equivalent. Elastic-plastic nature Viscose is a limp handling fibre because its polymer system is so very amorphous. Its polymers are not sufficiently long for a more satisfactory alignment, and so do not allow the formation of more hydrogen bonds which would result in a more rigid polymer system and thus a crisper handle to the viscose fibre and its textile materials. The very amorphous nature and fewer hydrogen bonds of viscose, when compared with cotton, enable the polymers to slide past each other when the filament, or staple fibre, is put under strain. When the strain is removed, the polymers do not return to the original position they occupied in the polymer system. Thus, the polymer systems of the filaments will be disarranged and the viscose textile material will become dis- torted, stretched, wrinkled and/or creased. By comparison, the handle of polynosic is somewhat less limp, and is somewhat less plastic than viscose. This is because its polymers are slightly longer and better aligned within the polymer system. Viscose, and the other regenerated cellulose fibres, become more plastic when wet, for reasons similar to those given to explain its reduced wet tenacity. Hygroscopic nature ‘The very amorphous polymer system of viscose, as well as its polar polymers, make viscose the most absorbent fibre in common use. The slightly more crystalline polynosic rayon is somewhat less absorbent than viscose. With regard to other hygroscopic properties (that is, static electricity and crispness), the explanations given for cotton apply also to viscose and the other two regenerated cellulose fibres. Thermal properties Viscose and the other two regenerated cellulose fibres have somewhat similar thermal properties to cotton. The explanations offered. for the thermal properties of cotton, 58The cellulosic fibres therefore, also apply to these fibres. However, no satisfactory explanation can be given for the fact that the regenerated cellulose fibres have a lower heat resistance and poorer heat conductivity than cotton, Viscose is the most common man-made fibre which is not thermoplastic. The reason for this is its hygroscopic nature, which enables it to absorb water molecules very readily. Thus the polymer system of viscose always tends to contain a considerable number of water molecules, which tend to break a significant number of hydrogen bonds. (See also ‘Tenacity’ of viscose.) Broken hydrogen bonds prevent the retention of any heat-set. (See also pages 109 and 116. Chemical properties The chemical properties of cotton and the regenerated cellulose fibres are similar, so the explanations given for the chemical properties of the former apply also to viscose and the other two regenerated cellulose fibres. However, the shorter polymers and the very amorphous nature of the regenerated cellulose fibres are responsible for the much greater sensitivity of these fibres to acids, alkalis, bleaches, sunlight and weather, when compared with cotton. With regard to dyeing and printing, the regenerated cellulose fibres will generally colour more brightly, even when delustred, than even their mercerised cotton equivalents. This is due to the greater amount of incident light reflected by viscose, even when delustred. The reflected light brightens, or increases the value and chroma of, the dyed or printed viscose. (See also Chapter 8.) 593 The ester-cellulose fibres Textiles fibres which are composed of ester-cellulose are called acetate fibres. There are two types: acetate and triacetate, Because the acetate fibres have very similar properties, they are considered together here. Acetate fibres Fibre classification The term acetate is derived from acet and ate. The former comes from acetic acid (the acid of vinegar), whilst the latter denotes a chemical salt. Acetate means a salt of acetic acid. To make acetate fibres, cellulose is treated to form cellulose acetate; that is, the cellulose salt of acetic acid. In organic chemistry, a salt is known as an ester. As a result acetate fibres are at times referred to as cellulose ester or ester-cellulose fibres. There are two types of acetate fibres, namely: 1 Acetate, a man-made, natural polymer based, secondary cellulose acetate filament or staple fibre. 2. Triacetate, a man-made, natural polymer based, primary cellulose acetate filament or staple fibre. These two fibres are described further in the section called “The acetate polymers’ on page 62. The acetate fibres are medium weight fibres, their fibre density being 1.32 g/cm? Fibre morphology The macro-structure of acetate fibres The macro-structure of acetate fibres is very similar to that of viscose so what is said about the macro-structure of viscose fibres (pages 54-55) applies also to the acetate fibres. The microscopic appearance of the acetate fibres Under a microscope, the longitudinal sections of the two acetate fibres look very similar. Both acetate and triacetate have one or two heavy striations. These striations result 60Figure 3.12 A longitudinal section of bright-ustre Dicet, a secondary cellulose acetate fibre, ‘magnified 500 times, Note the heavy striations, The ester-cellulose fibres Figure 3.1b_ A cross-section of bright-lustre Dicel, magnified 500 times. Note the irregularly lobed cross-sections of the fibres which give the heavy striations to the longitudinal appearance igure 3.2a A longitudinal section of delustred Dicel, a secondary cellulose acetate fibre, ‘magnified 500 times. Note the heavy striations. SS Figure 3.3 A longitudinal section of bright lustre Tricel, a primary cellulose acetate fibre, magnified 1500 times. Note the heavy striations. Figure 3.2b A cross-section of delustred Dicel, magnified 500 times. Note the irregularly lobed ‘cross-sections of the fibres which result in the heavy striations of the longitudinal section. Figure 3.3b A cross-section of bright lustre Tricol, magnified 500 times. Note the irregularly lobed cross-sections of the fibres and how similar these are to those of Dicel (Fig. 3.2b) from the irregular contraction of the extruded filament during the coagulation stage in manufacture. The striations are also responsible for the irregularly lobed cross-section of both acetate and triacetate filaments, as well as the staple fibres. (See Figs 3.1, 3.2 and 3.3.) 61Textile science The micro-structure of the acetate fibres Acetate and triacetate filaments, and their staple fibres, are fine, coagulated lengths of ester-cellulose, which display no discernible micro-structure. The polymer system The acetate polymers Both the acetate and triacetate polymers are cellulose polymers, whose -OH groups have been acetylated to form the ester of acetic acid, or acetate (see Figs 3.4 and 3.5). In the manufacture of ester-cellulose fibres, triacetate is produced first; hence, it is also known as primary cellulose acetate fibre. It is meant to be fully acetylated; that is in place of the six -OH groups of the cellobiose unit, six acetate groups (-OCOCH;) are formed (see Fig. 3.4). To obtain the secondary cellulose acetate fibre, the primary cellulose acetate is hydrolysed, that is reacted with water, so that, theoretically, only 2.3 to 2.4 acetyl or acetate groups per glucose unit occur. This is normally shown as two acetate groups per glucose unit, or four acetate groups per cellobiose unit (see Fig. 3.5). It should be noted that, with the secondary cellulose acetate polymer, it is the methylol -OH group that is acetylated and one of the other -OH groups (see Fig. 3.5). acetate 4 aap pene ey. oc — SE OunO | docer, KM An NZ ~ OoccH, 4 \ a Ai / \ Lo AY Ae —o¢ f I éH,00ccH, H-Hyecoo , aceiale Figure 3.4 The chemical formula of the repeating unit of the triacetate or primary cellulose acetate fibre polymer. The degree of polymerisation, n, is about 225, i Soe CHeOOCCHs 0. Cc A — 0 oO Pr fi ABH \ OY) Yo INS \/ H hydroxyl on H BS oi a Lo Ai vy fs § 5 I CH200CCH; H HCCOO In Figure 3.5 The chemical formula of the repeating unit of the acetate or secondary cellulose acetate fibre polymer. ‘The degree of polymerisation, n, is about 130. 62The ester-cellulose fibres Both acetate and triacetate polymers are linear, but the acetyl groups form bulky side groups (see pages 25 and 65). The acetate or secondary cellulose acetate polymer is about 160 nm long and about 2.3 nm thick, whilst the triacetate or primary cellulose acetate polymer is about 240 nm long and about 2.6 nm thick. Their degrees of polymerisation range from about 130 for the acetate polymers to about 225 for the triacetate polymers, based upon the cellobiose unit. ‘The important chemical groupings of the secondary cellulose acetate polymers are the hydroxyl and acetate groups (see Fig. 3.5). The hydroxyl groups tend to indicate the occurrence and presence of hydrogen bonds. However, these hydrogen bonds would be relatively few in number and, hence, not very significant in the acetate fibre polymer system. The acetate groups of the secondary cellulose acetate polymer are essentially non-polar and outnumber the hydroxy! groups. This explains the lack of polarity of secondary cellulose acetate polymers. The definition of triacetate (see also “Table 1.1) requires that its polymers have less than 8 per cent of hydroxyl groups. Such a small number of hydroxyl groups cannot form any significant hydrogen bonds. Be- cause of the presence of at least 92 per cent of acetate groups (see also definition in Table 1.1), the triacetate polymer lacks polarity. It is for the above reasons that both acetate and triacetate fibres rely mostly upon van der Waals’ forces for their polymer cohesion. The polymer systems of the acetate fibres The secondary cellulose acetate polymer system is estimated to be about 40 per cent crystalline and about 60 per cent amorphous, whilst that of triacetate or primary cellulose acetate is considered to be somewhat more crystalline. Both fibres are very amorphous fibres. The polymer systems of both types of acetate fibres are held together mainly by van der Waals’ forces. However, some hydrogen bonds contribute towards inter-polymer cohesion in the polymer system of the secondary cellulose acetate fibres: Since both types of acetate fibres have a polymer ‘backbone’ of hexagonal units, their polymer systems could be visualised as a disarranged roll of chicken wire, the disarranged portions being in the majority and representing the amorphous regions, whilst the more orderly sections are the crystalline regions of the polymer systems. Physical properties Tenacity Both types of acetate fibres are weak due to the amorphous nature of their polymer systems, which limits the number of inter-polymer forces of attraction which can occur. In addition, the predominant forces of attraction between the polymers are the weak van der Waals’ forces. ‘Acetate and triacetate become weaker when wet. This is because water molecules enter the amorphous regions of the fibres’ polymer systems. The ingress of water molecules pushes the fibre polymers somewhat further apart. This may be noticed as a slight swelling of the fibres. As the fibre polymers move further apart, the cohesive 63Textile science effect of the van der Waals’ forces is sufficiently reduced to cause a loss in tenacity of the filament or staple fibre. Elastic-plastic nature Both acetate and triacetate are plastic. This is because of their amorphous polymer systems and the predominantly weak van der Waals’ forces that occur between their polymers. With such weak forces of attraction in these very amorphous polymer systems, polymer slippage occurs readily, even under only slight strains. Hence, acetate and triacetate textile materials readily distort and/or wrinkle. Both acetate and triacetate fibres become more plastic when wet as sufficient water molecules can enter their amorphous polymer systems to break a significant number of inter-polymer forces of attraction. The rupture of these inter-polymer forces of attraction makes it even easier for polymers to slip past each other, under the slightest strain. Hence, acetate and triacetate textile materials are more likely to distort and/or wrinkle when wet or just damp. Secondary cellulose acetate filaments and staple fibres are the softest handling of all textile fibres in common use, this being due to the very amorphous nature of the polymer system and the occurrence of predominantly van der Waals’ forces holding the polymer system together. When pressure, such as handling, is applied to acetate textile material, the inter-polymer forces present little resistance and a resulting soft handling sensation is experienced. Triacetate or primary cellulose acetate fibres tend to have a stiffer handle, particularly after heat setting. It is considered that, after heat setting, the triacetate polymers move closer together (see also ‘Thermal properties’ below), providing a more rigid polymer system, which offers greater resistance to any pressure such as handling. Hygroscopic nature Despite their very amorphous polymer system, both acetate and triacetate fibres have only a fair moisture absorbency. This is mainly because of the relatively low polarity of the acetate and triacetate polymers. Secondary cellulose acetate polymers contain about two -OH groups per cellobiose unit (see Fig. 3.4), which makes these polymers slightly more polar, and the filaments and staple fibres of acetate more absorbent than those of triacetate. The latter’s polymers are fully acetylated; that is each cellobiose unit contains six ester groups, which impart very little, if any, polarity to the primary cellulose acetate polymer. Hence, triacetate is more hydrophobic than acetate. It becomes even more hydrophobic on heat setting, when the triacetate polymers are thought to move closer together, thereby reducing the size of the inter-polymer spaces. This reduction in the size of the inter- polymer spaces permits considerably fewer water molecules to enter the polymer system of heat set triacetate filaments and staple fibres. In effect, heat setting reduces the moisture absorbency of the triacetate polymer system by about half, making it then even less absorbent than nylon. (See also ‘Thermal properties’ below.) Finally, the limited hygroscopic nature of both types of acetate fibres makes them prone to develop static electricity in dry conditions. The limited hygroscopic nature being due, of course, to a lack of polymer polarity which could otherwise attract water molecules and dissipate any static charge which could develop. 64The ester-cellulose fibres Thermal properties ‘There is no satisfactory explanation as yet for the poor heat resistance and conductivity of acetate and triacetate filaments, and staple fibres. Both fibres are thermoplastic, which means that acetate and triacetate textile materials may be shaped, set, creased or pleated by the application of heat. When acetate textile materials are heated, the inter-polymer forces of attraction within their polymer systems are broken. This permits the acetate or triacetate polymers to assume the configuration required of them by the set which is being applied to their textile material. On cooling, the inter-polymer forces of attraction reform to hold the polymers in their new positions, Secondary cellulose acetate cannot be heat set satisfactorily because it has relatively few hydrogen bonds. As its polymer system is mainly held together by the weak and easily broken van der Waals’ forces, any heat set of acetate textile material soon becomes ineffective, as the acetate polymers can readily be displaced from their positions within their polymer system, when the system is subject to even the slightest of strains. On the other hand, primary cellulose acetate will retain a heat set more satisfactorily than its secondary cellulose acetate equivalent, even though the polymer system is only held together by van der Waals’ forces. The reason for this is as follows. Normally, heat setting of a thermoplastic polymer system is thought to occur through a rearrangement of the system’s polymers resulting in an increase in tenacity, or strength. However, when triacetate textile materials are heat set, the anticipated increase in strength does not occur. A rearrangement of triacetate polymers, however, does occur, for the triacetate textile material will display a stiffer, more paper-like handle, after heat setting. In addition, heat setting reduces the moisture absorbency of triacetate by about half. It is suggested that the more satisfactory heat set of triacetate textile materials over their acetate equivalents occurs through the recrystallisation of the primary cellulose acetate polymer system. This means that the triacetate polymers will, on heating, rear- range their internal polymer bond energies and inter-polymer forces of attraction in such a manner that on subsequent cooling, that is setting, they will not be straining against the heat set configuration of their filaments or staple fibres. In addition, the triacetate polymer system is thought to contract, that is reduce in size, its inter- polymer spaces. This reduction in the size of the inter-polymer spaces explains the reduction in moisture absorbency and the resultant ‘stiffer handle of triacetate textile materials after heat setting. Chemical properties Effect of acids ‘As both types of acetate polymers have essentially a cellulose ‘backbone’, acids hydrolyse them, causing polymer degradation, and resulting in weakening and eventual destruction of their textile materials. Because the triacetate polymer system is somewhat more crystalline than that of acetate, textile materials of triacetate will be more resistant to acid degradation. 65Textile science Effect of alkalis The cellulose ‘backbone’ makes acetate and triacetate polymers more resistant to alkalis than to acids. However, the acetyl, aectate or ester side groups (see pages 13 and 16) will be hydrolysed, or saponified, on exposure to alkaline conditions. The effect of this alkaline hydrolysis, or saponification, is the conversion of acetate groups to their former —OH groups, as are found in the original cellulose polymer (sce Fig. 2.4). Such alkaline hydrolysis occurs, in the first instance, on the surface of the filaments or staple fibres, resulting in the yellowing of white or the dulling of coloured acetate and triacetate textile materials. Effect of bleaches Bleaches in general have the same effect on acetate fibres as they do on cotton fibres (see page 47). Effect of sunlight and weather The relative lack of polarity of the acetate and triacetate polymers is one of the factors responsible for the fair to good sunlight and weather, resistance of their textile materials. The lack of polarity protects the polymers from destruction because it minimises the attraction of polar degrading agents. As the acetate groups are acid resistant and are attached to the sides of the acetate and triacetate polymers, they offer protection to the cellulose ‘backbone’ from acid hydrolysis by the atmosphere, which is usually slightly acidic. Finally, acetate textile materials have fair to good sunlight resistance because the electron arrangements of the acetate and triacetate polymer ‘backbone’ can sufficiently resist the degrading effect of the ultraviolet radiation of sunlight. Colour-fastness The acetate fibres are not easy fibres to dye or print. The disperse dyes, which are the only dyes which will readily dye or print acetate and triacetate textile materials, had to be specifically developed. The relative lack of polarity of the acetate and triacetate polymers is mainly responsible for most other dyes being unsuitable for the colouration for their textile materials. Disperse dyes Because the disperse dyes are relatively non-polar, they are sometimes also known as non-ionic dyes. Their lack of polarity makes them compatible with the relatively non- polar polymer systems of acetate and triacetate. The fair to good light-fastness of disperse dyed and printed acetate and triacetate textile materials is due to the relatively stable electron arrangements of the chro- mophores of the disperse dye molecules which can withstand the degrading effects of the ultraviolet radiation of sunlight. The good wash-fastness of disperse dyed and printed acetate and triacetate textile materials cannot be attributed to the van der Waals’ forces—the only forces of attraction which can be formed between the non-polar disperse dye molecules and the acetate or triacetate polymers, which themselves lack any significant polarity. Rather, the 66The ester-cellulose fibres good wash-fastness has to be attributed to the relatively non-polar, disperse dye molecules. This non-polarity makes them insoluble in water and as a result difficult to wash out of the acetate or triacetate polymer system. 674 The protein fibres alpaca, angora, cashmere, etc. Only the commonly used protein fibres, namely wool and silk, will be considered here. Wool Textile classification The word wool was wull in Old English, wullo in Teutonic, and wha in pre-Teutonic days. Wool is the fibre from the fleece of domesticated sheep. It is a natural, protein, multi- cellular, staple fibre. The fibre density of wool is 1.31 g/cm’, which tends to make woo! a medium weight fibre. Fibre morphology The macro-structure of wool The wool fibre is a crimped, fine to thick, regular fibre. Fine wools may have as many as 10 crimps per centimetre, whilst coarse wools have less than 4 crimps per 10 centi- metres. As the diameter of wool fibres increases, the number of crimps per unit length decreases. The number of crimps per unit length may be taken as an indication of wool fibre diameter or wool fibre fineness. The crimped configuration prevents wool fibres from aligning themselves too closely when being spun into yarn. As a result it is possible to have wool textile materials with air spaces occupying about two-thirds of the volume. The warmth of wool fabrics is due more to the air spaces in the material than to the fibres. The very good resilience of wool fabrics, partly attributable to the elastic nature of the wool fibre, is mainly due to the crimp. It makes the fibre ‘springy’ and enables the wool fibre to return to its crimped configuration. The ‘unruliness’ of the crimp causes wool fibre ends to project above the wool textile material’s surface. These fibre ends cause a prickling sensation, which stimulates the blood circulation of the skin. In warm and temperate climates, the wearer may find this sensation uncomfortable, as it tends to create too much body heat. 68

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