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Textile Fibers Classification Of Textile fibres Nos Name 1 2 wool (1) alpaca, llama, cammel, kashmir, mohair, angora,

vicuna, yak, guanaco, beaver, otter, followed or not by the name 'wool' or 'hair' (1) Fibre description Fibre from sheep's or lambs' fleeces (Ovis aries) Hair of the following animals: alpaca, llama, cammel, kashmir goat, angora goat, angora rabbit, vicuna, yak, guanaco, beaver, otter

animal or horsehair, with or without an indication of the kind of animal (e.g. cattle hair, common goat hair, horsehair) silk cotton kapok

Hair of the various animals not mentioned under 1 or 2

4 5 6

Fibre obtained exclusively from silksecreting insects Fibre obtained from the bolls of the cotton plant Fibre obtained from the inside of the kapok fruit (Ceiba pentandra) Fibre obtained from the bast of the flax plant (Linum usitatissimum) Fibre obtained from the bast of hemp (Cannabis sativa) Fibre obtained from the bast of Corchorus olitorius and of Corchorus capsularis. For the purposes of this Directive, bast fibres obtained from the following species shall be treated in the same way as jute: Hibiscus cannabinus, Hibiscus sabdariffa,

flax

8 9

true hemp jute

Abultilon avicennae, Urena lobata, Urena sinuata 10 11 12 13 14 abaca (Manila hemp) alfa coir (coconut) broom ramie Fibre obtained from the sheating leaf of Musa textilis Fibre obtained from the leaves of Stipa tenacissima Fibre obtained from the fruit of Cocos nucifera Fibre obtained from the bast of Cytisus scoparius and/or Spartium junceum Fibre obtained from the bast of Bohemeria nivea and Bohemeria tenacissima Fibre obtained from the leaves of Agave sisalana Fibre from the bast of Crotalaria juncea Fibre from the bast of Agave Fourcroydes Fibre from the bast of Agave Cantala Cellulose acetate fibre wherein less than 92% but at least 74% of hydroxyl groups are acetylated Fibre obtained from metallic salts of alginic acid Regenerated cellulose fibre obtained by the cuprammonium process A fibre of regenerated cellulose having a high breaking force and high wet modulus. The breaking force (BC) in the conditioned state and the force (BM) required to produce an elongation of 5% in the wet state are: BC (centinewton)>=1,3 sqr(T) + 2T BM (centinewton) >= 0,5 sqr(T) where T is the mean linear density in decitex

15 16 17 18 19

sisal Sunn Henequen Maguey acetate

20 21 22

alginate cupro (cuprammonium rayon) modal

23

protein (1)

Fibre obtained from natural protein substances regenerated and stabilized through the action of chemical agents Cellulose acetate fibre wherein at least 92% of the hydroxyl groups are acetylated Regenerated cellulose fibre obtained by the viscose process for filament and discontinuos fibre Fibre formed of linear macromolecules comprising at least 85% (by mass) in the chain of the acrylonitrilic pattern Fibre formed of linear macromolecules having in their chain more than 50% by mass of chlorinated vinyl or chlorinated vinylidene monomeric units Fibre formed of linear macromolecules made from fluorocarbon aliphatic monomers Fibre formed of linear macromolecules having in their chain more than 50% and less than 85% (by mass) of the acrylonitrilic pattern Fibre formed of linear macromolecules having in their chain the recurring amide functional group Fibre formed of linear macromolecules having in their chain at least 85% (by mass) of an ester of a diol and terephthalic acid Fibre formed of un-substituted aliphatic saturated hydrocarbon linear macromolecules Fibre formed of an aliphatic saturated hydrocarbon linear macromolecule where one carbon atom in two carriers a methyl side chain in an isotactic disposition and

24

triacetate

25

viscose

26

acrylic (1)

27

chlorofibre

28

fluorofibre

29

modacrylic (2)

30

polyamide or nylon (2)

31

polyester

32

polyethylene (2)

33

polypropylene (2)

without further substituition 34 polycarbamide (2) Fibre formed of linear macromolecules having in their chain the recurring ureylene (NH-CO-NH) functional group Fibre formed of linear macromolecules composed of chains with the recurring urethane finctional group Fibre formed of linear macromolecules whose chain is constituted by poly(vinyl alcohol) with differing levels of acetilization Fibre formed of acrylonitrile terpolymer, a chlorinated vynil monomer and a third vinyl monomer, none of which represents as much as 50% of the total mass Elastofibre composed of natural or synthetic polyisoprene, or composed of one or more dienes polymerized with or without one or more vinyl monomers, and which, when stretched to three times its original length and released, recovers rapidly and substantially to its initial length Elastofibre composed of at least 85% (by mass) of a segmented polyurethane, and which, when stretched to three times its original length and released, recovers rapidly and substantially to its initial length Fibre made of glass Fibres obtained from miscellaneous or new materials not listed above

35

polyurethane (2)

36

vinylal (m)

37

trivinyl (2)

38

elastodiene (2)

39

elastane

40 41

glass fibre name corresponding to the material of which the fibres are composed, e.g. metal (metallic, metallized), asbestos, paper, followed or not by the word 'yarn' or 'fibre'

(1) The name 'wool' in item 1 of this Annex may also be used to indicate a mixture of fibres from sheep's or lambs' fleeces and the hairs listed in the third column of item 2. This provision is applicable to the textile products listed in Articles 4 and 5 and to those referred to in Article 6, provided that the latter are partly composed of the fibres listed in items 1 and 2. (2) The 'word' fibre is understood.

Essential Requirements Of Fibre Forming Polymers Polymer Fundamentals: Fiber Applications Polymer science addresses the chemistry and physics of large, chain-like molecules. As with the molecules themselves, this technical pursuit is diverse and complicated. The following discussion provides an introduction to the manufacture and use of synthetic organic polymers for those with some knowledge of basic science. More advanced tutorial information on polymers is contained in the links displayed at the end. What is a Polymer? The term polymer is derived from the Greek poly, meaning many, and mer, meaning parts thus polymers are substances made of many parts. In most cases the parts are small molecules which react together hundreds, or thousands, or millions of times. A molecule used in producing a polymer is a monomer mono is Greek for single, thus a monomer is a single part. A polymer made entirely from molecules of one monomer is referred to as a homopolymer. Chains that contain two or more different repeating monomers are copolymers. The resulting molecules may be long, straight chains, or they may be branched, with small chains extending out from the molecular backbone. The branches also may grow until they join with other branches to form a huge, three-dimensional matrix. Variants of these molecular shapes are among the most important factors in determining the properties of the polymers created. The size of polymer molecules is important. This is usually expressed in terms of molecular weight. Since a polymeric material contains many chains with the same repeating units, but with different chain lengths, average molecular weight must be used. In general, higher molecular weights lead to higher strength. But as polymer chains get bigger, their solutions, or melts, become more viscous and difficult to process. Proteins and Carbohydrates Life as we know it could not exist without polymers. Proteins, with large numbers of amino acids joined by amide linkages, perform a wide variety of vital roles in plants and animals. Carbohydrates, with chains made up of repeating units derived from simple sugars, are among the most plentiful

compounds in plants and animals. Both of these natural polymers are important for fibers. Proteins are the basis for wool, silk and other animalderived filaments. Cellulose as a carbohydrate occurs as cotton, linen and other vegetable fibers. The properties of these fibers are limited by the form provided in their natural state. Some, like linen and silk, are difficult to isolate from their sources, which makes them scarce and expensive. There are, of course, many other sources of proteins and cellulose, such as wood pulp, but natural polymers tend to be very difficult to work with and form into fibers or other useful structures. The inter-chain forces tend to be strong because of the large number of polar groups in the molecular chains. Thus, natural polymers usually have melting points that are so high that they degrade before they liquefy. The most useful molecules for fibers are long chains with few branches and a very regular, extended structure. Thus, cellulose is a good fiber-former. It has few side chains or linkages between the sugar units forcing its chains into extended configurations. However, starches, which contain the same basic sugar units, do not form useful fibers because their chains are branched and coiled into almost spherical configurations.

Synthetic Polymers Synthetic polymers offer more possibilities, since they can be designed with molecular structures that impart properties for desired end uses. Many of these polymers are capable of dissolving or melting, allowing them to be extruded into the long, thin filaments needed to make most textile products. Synthetic polymer fibers can be made with regular structures that allow the chains to pack together tightly, a characteristic that gives filaments good strength. Thus, filaments can be made from some synthetic polymers that are much lighter and stronger than steel. Bullet-proof vests are made from synthetic fibers. There are two basic chemical processes for the creation of synthetic polymers from small molecules (1) condensation, or step-growth polymerization, and (2) addition, or chain-growth polymerization.

Step-Growth Polymerization In step-growth polymerization, monomers with two reactive ends join to form dimers (two parts joined together), then trimers (three parts),

and so on. However, since each of the newly formed oligomers (short chains containing only a few parts) also has two reactive ends, they can join together; so a dimer and a trimer would form a pentamer (five repeating parts). In this way the chains may quickly great length achieve large size. This form of step-growth polymerization is used for the manufacture of two of the most important classes of polymers used for textile fibers, polyamide (commonly known as nylon), and polyester. There are many different commercial versions of polyester in a wide variety of applications, including plastics, coatings, films, paints, and countless other products. The polymer usually used for textile fibers is poly(ethylene terephthalate), or PET, which is formed by reacting ethylene glycol with either terephthalic acid or dimethyl terephthalate. Antimony oxide is usually added as a catalyst, and high vacuum is used to remove the water or methanol byproducts. High temperature (>250oC) is necessary to provide the energy for the reaction, and to keep the resultant polymer in a molten state. PET molecules are regular and straight, so their inter-chain forces are strong but not strong enough to prevent melting. Thus, PET is a thermoplastic material; that is, it can be melted and then solidified to form specific products. Since its melting point is high, it does not soften or melt at temperatures normally encountered in laundering or drying. Another important property of PET is its Tg, or glass transition temperature. When a polymer is above its glass transition temperature, it is easy to change its shape. Below its Tg, the material is dimensionally stable and it resists changes in shape. This property is very important for textile applications because it allows some fibers, and the fabrics made from them, to be texturized or heat-set into a given shape. This can provide bulk to the yarn, or wrinkle resistance to the fabric. These set-in shapes remain permanent as long as the polymer is not heated above its Tg. Because its chains are closely packed and its ester groups do not form good hydrogen bonds, polyesters are also hydrophobic (i.e., they do not absorb water). This property also requires special dyeing techniques. There are also many important classes of synthetic polyamides (nylons) and they have a wide variety of commercial uses. These are usually distinguished from each other by names based on the number of carbon atoms contained in their monomer units. As with polyesters, polyamides are formed by stepgrowth polymerization of monomers possessing two reactive groups. Here, the reactive functions are acids and amines. The monomers used may have their two reactive functions of the same chemical type (both acids, or both amines), or of different types. Thus, nylon 6,6 a very common fiber polymer is made by reacting molecules of adipic acid (containing six

carbons in a chain, with an acid function at each end) with hexamethylene diamine (also six carbon atoms, with amine functions at each end). In another variant the diamine contains ten carbons atoms, the product designated nylon 6,10. The other common polyamide fiber polymer is nylon 6. Its monomer has six carbons in the chain, with an amine at one end and an acid at the other. Thus only one form of monomer is needed to conduct the reaction. Commercial production of nylon 6 makes use of caprolactam, a derivative which provides the same result. As with the polyesters, nylons have regular structures to allow good interchain forces that impart high strength. Both nylon 6 and nylon 6,6 have melting points similar to PET but they have a lower Tg Also, since the amide functions in nylon chains are good at hydrogen bonding, nylons can be penetrated by water molecules. This allows them to be dyed from aqueous media, unlike their polyester counterparts. In addition to nylon, there is another commercially important group of synthetic polyamides. These are the aramids, which contain aromatic rings as part of their polymer chain backbone. Due to the stability of their aromatic structures and their conjugated amide linkages, the aramids are characterized by exceptionally high strength and thermal stability. Their usefulness for common textile applications is limited by their high melting points and by their insolubility in common solvents. They are expensive to fabricate, and they carry an intrinsic color that ranges from light yellow to deep gold. Other step-growth polymers the polyurethanes are produced by the reaction of polyols and polyisocyanates. For fiber purposes, this class of linear polymers is formed from glycols and diisocyanates. Usually, the reactions are carried out to form block copolymers containing at least two different chemical structures one rigid, and the other flexible. The flexible segments stretch, while the rigid sections act as molecular anchors to allow the material to recover its original shape when the stretching force is removed. Varying the properties of the segments, and the ratio of flexible to rigid segments controls the amount of stretch. Fibers made in this way are classified as spandex and they are used widely in apparel where stretch is desirable.

Chain-Growth Polymerization Chain-growth polymerization occurs when an activated site on a chemical, such as a free radical or ion, adds to a double bond, producing a new bond and a new by activated location. That location then attacks another double bond, adding another unit to the chain, and a new reactive end. The process may be repeated thousands, or millions, of times, to produce very large molecules. This is usually a high energy process and the intermediate species are so reactive that, in addition to attacking available monomer, they also may attack other chains, producing highly branched structures. Since these branches prevent the molecules from forming regular structures with other molecules, their inter-chain forces are weak. The resulting polymers tend to be low-melting and waxy. The breakthrough in making chain-growth polymers useful for fibers and for most commercial plastics came with the development of special selective catalysts that drive the production of long, straight polymer chains from monomers containing basic carbon-to-carbon double bonds. Ethylene and propylene form the simplest chain-growth polymers. Since their polymer chains contain no polar groups, these polyolefins must rely on close contact between the molecular chains for strength. Thus, the physical characteristics of polyethylene are very sensitive to even a small number of chain branches. Very straight chains of polyethylene can form strong crystalline structures which exhibit exceptional strength. Protective fabrics made from this type of highly structured polyethylene are virtually impossible to penetrate or cut. Polypropylene is more complicated. Even without chain branching, each monomer unit adds one methyl group pendant to the chain. The arrangement of these side groups is described as the tacticity of the polymer. A random arrangement is considered atactic, or without tacticity. Regular arrangement with all side groups on one side of the chain is isotactic, and a regular alternating structure is syndiotactic. Polypropylene molecules can only pack closely in an isotactic arrangement. Synthesis of these polymers was a major challenge, but several stereoselective catalysts are now available, and high-density polypropylene has become a commodity product. Fibers made from it are lightweight, hydrophobic and highly crystalline. Their resistance to wetting gives them good moisture wicking and anti-staining properties. This also makes them virtually undyeable, except when the dye is applied to the polymer in its molten state a process know as solution dyeing.

By contrast, the pendant nitrile functions in polyacrylonitrile are sufficiently polar to produce very strong inter-chain forces. Pure homopolymers from acrylonitrile are non-thermoplastic and difficult to dissolve or dye. Thus, for most commercial acrylonitrile polymers, small amounts of other monomers with bulky side chains are introduced to force the chains apart, to reduce the inter-chain forces. Common co-monomers for these fiber applications include vinyl chloride, vinyl acetate, acrylic acid, and methyl acrylate. Specialty fiber polymers There are also a number of complex, specialty fiber polymers with methods of synthesis that are not easily classified. These materials are occasionally used in high performance materials where the complex structures impart exceptional strength, thermal stability, electrical conductivity, and others desirable properties. They include (polybenzimidazole)and Their chemistry is beyond the scope of this introductory discussion.

Wool Wool The most important of the fibres of animal origin is wool, the hair of the sheep (Ovis ales). The characteristics of wool fibres differ depending on the breed and general condition of the sheep.

Wool, the hair of various breeds of sheep, is a warm springy fibre. Its scaly structure led in the past to unwanted felting(matting of fibres) and shrinkage in laundering but modern finishing treatments have now overcome these difficulties; similarly, attack by the clothes moth is no longer a problem.

Wool has a natural crimpiness, which gives it good elasticity, bulk, creaseresistance and durability. Its strength when wet is less than when it is dry. Important properties of wool are a dry strength of 11.5 to 13 cN/tex, a breaking elongation of 30 to 40% and a moisture regain of 16 to 18%. Technologically, the diameter, or fineness, of the wool fibre is probably the most important property. It is determined to a large extent by the grade assigned to a lot, or batch, of wool. Diameters range from 16 microns in the finest Merinos to over 40 microns in the coarsest long-wool types. Staple length generally increases with increasing fibre diameter, ranging from four to eight centimetres for fine Merino up to 35 centimetres for coarse Cotswold wool. Staple length is lower than mean fibre length because of the crimp that results in a helical configuration in an individual fibre and an uni-planar wave in the staple. Wool fibres are hygroscopic, absorbing water from a moist atmosphere in a reversible way. Because most fibres are dependent on moisture content, this characteristic is extremely important, especially in numerous processing steps, including carding, combing, spinning and weaving.Relative humidity in the processing plants must be controlled for optimum processing conditions. Upon uptake of water , the fibre swells anisotropically (unequally), increasing up to 16% in diameter while the change in length is only about 1.2 to 1.5%. The ability of wool fibres to absorb and release moisture contributes to wearing comfort in garments made of wool. In the UK alone there are 34 main breeds of sheep and a further 43 rare breeds and hybrids. When wool fibres have been processed it is not possible to say with confidence from what breed of sheep or country they have originated because wool fibres from several breeds have the same microscopical appearance. There are four main types of wool fibre: fine,

coarse, outercoat and kemps. Each type has a characteristic scale pattern so that it is possible to distinguish between types, although it is not possible to assign a type to a breed of sheep. Wool fibres are generally white, with the finer fibres having a circular cross section and the coarse fibres being more irregular in contour. Kemp fibres are usually chalky white in appearance, very coarse and brittle, with a long tapering tip and a taper over a short distance to the root end. An important aspect of the environmental impact of wool processing is the use of pesticides on sheep. Although the problem has been minimised over recent years with the introduction of tighter restrictions or even bans on the use of some formulations, this is still a major concern since these toxic chemicals make their way into rivers. Another impact at this early stage which is maybe less obvious, is the methane generated globally by the many hundreds of millions of sheep. Methane is a powerfulgreenhouse gas and contributes to the effect of global warming. Again, as with cotton there is also the effect of transporting huge quantities of textiles across the globe with the associated fuel usage and fume generation problems. The scouring of the raw wool, the next stage, is a process which produces a liquid effluent with a very high organic load and solids content and varying levels of pesticide contamination. The highly polluting nature of this waste and the strict discharge consents associated with the process means that scourers have to treat their effluent on-site. Another environmental problem is that many of the dyestuffs available for obtaining good dark shades on woollen fabric or yarn are mordant dyes containing chromium. The discharge of chromium is strictly controlled and so companies are being forced into using alternatives or consider on-site effluent treatment. In the carpet industry permethrin, another pesticide, is added to the yarn that goes into making contract carpets, this is a quality requirement to protect the wool from moth attack. The effluent from this process must therefore be treated and continually monitored.

Silk Silk In Old English, silk was sioloc. The name is thought to have originated from the Greek seres, meaning the people from Eastern Asia i.e. the Chinese. The term sericulture derives from this Greek root.

Silk has a long and fascinating history, starting over 4000 years ago with the development by the Chinese of the art of rearing silkworms to make a textile fibre. Since that time silk has remained highly valued for its luxurious qualities but, because its main uses have been in very expensive apparel and other luxury goods, demand has been considerably more variable than for many other fibres. There are several species of silk producing worms but most of the worlds silk results from the worm of the mothBombyx mori which lives exclusively on the leaves ofMorus alba the white mulberry tree. Other silkworms include the wild or semi-wild varieties, such as Atlas, Eri, Tussah and Muga, which are found mainly in India and Asia. The silkworms are reared in large numbers at silk farms, where plantations of bush-like mulberry trees are cultivated to provide leaves which are fed to the worms in special rearing rooms. From the day it hatches to the time it stops feeding, a period of 25 to 30 days, the worm gains in weight about 10,000 times. During this time it eats some 22g of leaves and converts more than 70% of its intake of nitrogenous material into silk. To produce 1kg of raw silk about 6.25 kg of fresh cocoons are necessary, while for raising 6.25 kg of cocoons about 104 kg of mulberry leaves containing 26 kg of solid matter are required. On average 75% of the fresh green cocoon, by weight is chrysalis. The outer layer of floss and the inner layer are collected as silk waste and used in spun silk manufacture. Wild silks such as Tussah are also generally used for spun silk as the cocoons are seldom in a reelable condition.

Tussah, a kind of wild silkworm, comes in two varieties monovoltine and bivoltine. It lives and multiplies wherever oak trees or leaves of the Mongolian oak, rubber trees or Chinese toon trees are available. There is one main type of tussah silkworm, Antheraea pernyi, and one general type of oak tree on which it feeds, Quercus serrata. Tussah Moth The Tussah chrysalis and cocoon are larger than those of the mulberry silkworm, but the cocoon shell is thinner, has a lower layer ratio and yields less silk. The Tussah cocoon is reddish-brown in colour, while the mulberry cocoon is white. Tussah silks seracin or protein content, is 13.3%, which is lower than that of mulberry silk. The fibroin, or fibre itself, accounts for the remaining 86.7% and is composed of 15 amino acid residues. Silk is a fairly strong fibre and although it does not compare with nylon and polyester in this respect its strength makes it suitable for use in sewing thread in high quality articles, particularly those made from silk. Silk absorbs more moisture from the surrounding air than do most of the synthetic fibres, and this property confers considerable advantages; it prevents a clammy feeling where fabric is in contact with the skin, since moisture can be absorbed without the fibre becoming noticeably damp, and transmitted through the material and into the atmosphere. Silk has a fairly high natural resistance to creasing. Attempts to improve on this and also to apply easy-care treatments have not been very successful, as they impair the unique handle, or feel, of silk which is one of its most valuable properties.

The environmental impact of silk processing is relatively minor in its initial stages when compared to cotton or wool. The cocoons are cooked to kill off the insects and then the fibre is washed in synthetic detergents to remove most of the sericin (gum) in readiness for dyeing.> Subsequent processing, through spinning, weaving, dyeing and finishing have an impact on the environment similar to most of the other fibres. Noise and dust is produced in weaving and a complex effluent with variable BOD/COD, pH and solids content is produced in finishing.

Cotton Cotton Cotton fibres are the seed hairs of the plantGossypium. They are usually off-white in colour although some varieties have been bred to incorporate a natural colour. Each fibre is formed by the elongation of a single cell from the surface of the seed. The word cotton is derived from its Arabic name pronounced kutan, qutn or qutan depending on the dialect.

Under a microscope , a cotton fibre appears as a very fine, regular fibre, looking like a twisted ribbon or a collapsed and twisted tube. These twists are called convolutions. Almost half of the worlds requirements for textile fibres are met by cotton. It is grown in many parts of the world where a hot dry climate is to be found, the main producers being USA, the former USSR, China, India, Egypt, Africa and South America.

Cotton consists typically of between 88 to 96% cellulose with the rest being protein, pectic substances (congealed gum-like carbohydrates), ash and wax. After scouring and bleaching, cotton is then about 99% cellulose. The fibres are weakened and destroyed by acids but are resistant to alkalis. The fibre length varies with the type and quality, within the range 10 to 65mm; the fibre diameter ranges from 11 to 22 m. Cotton is a relatively strong fibre with a strength of 25 to 35 cN/tex and a breaking elongation of 7 to 9%. It is stronger when wet. Cotton also absorbs moisture readily, which makes cotton clothes comfortable to wear in warm weather (water retention of 50%, moisture regain of 7%). Cotton fibre burns readily and is not inherently resistant to oxidising agents, and biodegradation, as well as acids. Despite these shortcomings cotton has a good wear life. Its properties can also be readily modified by chemical finishes which provide enhanced performance, e.g. crease resistance and flame resistance. It is used in both 100% form and in blends with other fibres for household textiles and apparel. Synthetic fibres have largely replaced its use in industrial textiles. The environmental impact of the cotton manufacturing process starts in the field with the fertilisers and insecticides used in the growing of the cotton plant. These have a direct impact on the land and the local flora and fauna. The US alone spends about 500 million dollars a year on pesticides for protection against the bollworm and other harmful bugs. These pesticides also have an effect on people living in the viscinity of cotton fields. Nausea, diarrhoea and throat irritation being the most common complaints. It is also interesting to note that the gas leak at Bhopal , India which killed over 3,000 people came from a pesticide used in the spraying of cotton crops. The ginning or separation of the seed from the fibre is a dusty process that has serious health implications on cotton workers in developing countries, where the separation is carried out using traditional methods. The fibre is then packaged and transported across the globe. The production of natural fibres is conducted in many separate locations, transportation of the cotton bales has therefore a significant impact on the environment. The spinning process introduces another set of significant impacts, producing more dust, noise and waste fibre and is also a relatively large consumer of electricity (as much as 2 tonnes of oil per tonne of yarn). Relative humidity in the processing plant must also be controlled to minimise breakages, another consumer of energy. Weaving creates a similar set of impacts plus

the added effect of using size and biocides has to be considered on the aqueous environment. Sizes are either natural, like starches or synthetic such as polyvinyl alcohol. The new sizes make weaving on the faster modern machinery a lot easier, but they have the drawback of being harder to biodegrade from the waste water. Cotton preparation, that is singeing, desizing, scouring, bleaching and mercerising impacts on both the air and water. Singeing produces a dusty odorous emission, whilst the other preparative processes are the major contributors to BOD/COD in a textile effluent. There is also the problem of pentachlorophenol (pcp) on imported fabric which is washed out during preparation. This is an eco-toxic rot-proofing chemical with a very low discharge consent (maximum allowable concentration). Cotton is by far the most popular fibre in use today, at least in terms of volume of production. The most widely used class of dyestuff on cotton are reactive dyes, which unfortunately are also the most poorly exhausted, producing a more coloured effluent. Colour consents on discharges have therefore been enforced in certain areas where there are significant numbers of cotton dyers. The main pollution problem associated with cotton finishing processes is that of formaldehyde emissions from resin and other finishes. Low formaldehyde formulations have improved over the past few years but not far enough to eliminate the need for abatement on many stenters. Attempts have been made to reduce the impact of cotton growing by eliminating pesticide use and by growing coloured strains of cotton so that the preparation and dyeing of the cotton is minimised. The bollworm can be eliminated by imposing a three month fallow period at the end of the growing season, and certain short fibre coloured cottons used by Indians in Central America have been cross bred with long fibre strains by a company in the US called Foxfibre. However, the amount of organic cotton grown in the US is still only a tiny fraction of the global output ( by the mid-1990s, 80 cotton growing countries were producing about 85 million bales of cotton).

Bast fibre Bast fibre (fiber) or skin fibre is fibre collected from the Phloem (the "inner bark" or the skin) or bast surrounding the stem of a certain, mainly

dicotyledonic, plants. Most of the technically important bast fibers are obtained from herbs cultivated in agriculture, as for instance flax, hemp or rhamie, but also bast fibers from wild plants, as stinging nettle, and trees as the lime tree, have been used to some extent. Since the valuable fibers are located in the phloem, they must often be separated from the xylem material ("woody core"), and sometimes also from epidermis. The process for this is called retting, and can be performed by microoganisms either on land (nowadays the most important) or in water, or by chemicals (for instance high pH and chelating agents) or by pectinolytic enzymes. In the phloem bast fibers occur in bundles that are glued together by pectin and calcium ions. More intense retting separate the fiber bundles into elementary fibers, that can be several cm long. The bast fibres have often higher tensile strength than other kinds, and are therefore used for textiles (not seldom very exclusive textiles, sometimes in blends with cotton or synthetic fibers) ropes, yarn, paper, composites and burlap. A special property of bast fibers are that the fiber contain a special structure, the fiber node, that represents a weak point. Fiber nodes seems not to be present in seed hairs as cotton. Examples are:

Jute Industrial hemp Flax (Linen) Ramie Kenaf Roselle Hemp Rattan Soybean fibre Okra fibre Vine fibre Banana fibre

Use of bast fibre Bast fibres are processed for use in carpet yarn, rope, geotextile (netting or matting), traditional carpets, hessian or burlap, paper, sacks, etc. Bast fibers are also used in the non-woven, moulding, and composite technology industries for the manufacturing of non-woven mats and carpets, composite boards as furniture materials, automobile door pannels and headliners, etc. From prehistoric times through at least the early 20th century, Bast shoes were woven from bast strips in the forest areas of Eastern Europe.

Process of viscose Viscose is a viscous organic liquid used to make rayon andcellophane. Cellulose from wood or cotton fibres is treated with sodium hydroxide, then mixed with carbon disulfide to form cellulose xanthate, which is dissolved in more sodium hydroxide. The resulting viscose is extruded into an acid bath either through a slit to make cellophane, or through a spinneret to make rayon. The acid converts the viscose back into cellulose.

Cellulose is treated with alkali and carbon disulfide to yield viscose. Viscose was created by French scientist and industrialist Hilaire de Chardonnet (1838-1924), inventor of the first artificial textile fiber, artificial silk) in chirolles in 1884, then the process for manufacturing viscose was patented by three British scientists, Charles Frederick Cross, Edward John Bevan and Clayton Beadle, in 1891. Industrial applications Viscose was first used for coating fabrics, a purpose for which it is quite suitable. However, when Cross and his partners tried to make solid objects like umbrella handles they were found to be much too brittle.

Further development led to viscose being spun into thread for embroidery and trimmings. Eventually, after Samuel Courtauld & Co. had taken over in 1904, Viscose manufacture became big business. By the twenties and thirties it had almost completely replaced the traditional cotton and wool for womens stockings and underwear. Similar changes occurred in the US and in Europe, too. Viscose was also being used for linings and furnishing fabrics; providing the staple for towels and table-cloths and was being made into high tenacity yarn for tires. Yet other uses included the manufacture of sponges and absorbent cloths. Making viscose film had been tried by Cross in the 1890s but it was in Switzerland and France that major successes were achieved. By 1913 C.T.A. established La Cellophane SA. Ten years later DuPont Cellophane Co. was set up in the USA and in 1935 British Cellophane Ltd was established in Bridgwater,Somerset. Viscose is a soft material, used in mostly tops, coats and jackets. Viscose is currently becoming less common because of the polluting effects of carbon disulfide and other by-products of the process, forcing the Bridgwater factory to close in 2005

Synthetic Fibre Synthetic fibers are the result of extensive research by scientists to improve upon naturally occurring animal and plant. In general, synthetic (manmade) fibers are created by forcing, usually through extrusion, fiber forming materials through holes (called spinnerets) into the air, forming a thread. Before synthetic fibrers were developed, artificial (manufactured) fibers were made from cellulose, which comes from plants. The first artificial fiber, known as artificial silk from 1855 onwards, became known as viscose around 1894, and finally rayon in 1924. A similar product known as cellulose acetate was discovered in 1865. Rayon and acetate are both artificial fibers, but not truly synthetic, being made from wood. Although these artificial fibers were discovered in the midnineteenth century, successful modern manufacture began much later (see the dates below). Nylon, the first synthetic fiber, made its debut in the United States as a replacement for silk, just in time for World War II rationing. Its novel

use as a material for women's stockings overshadowed more practical uses, such as a replacement for the silk in parachutes and other military uses. Common synthetic fibers include:

Rayon (1910) (artificial, not synthetic) Acetate (1924) (artificial, not synthetic) Nylon (1939) Modacrylic (1949) Olefin (1949) Acrylic (1950) Polyester (1953) PLA (2002)

Specialty synthetic fibers include:


Vinyon (1939) Saran (1941) Spandex (1959) Vinalon (1939) Aramids (1961) - known as Nomex, Kevlar and Twaron Modal (1960's) PBI (Polybenzimidazole fibre) (1983) Sulfar (1983) Lyocell (1992) Dyneema/Spectra (1979) M-5 (PIPD fibre) Orlon Zylon (PBO fibre) Vectran (TLCP fiber) made from Vectra LCP polymer

Other synthetic materials used in fibers include:

Acrylonitrile rubber (1930)

Modern fibers that are made from older artificial materials include:

Glass Fiber is used for: o industrial, automotive, and home insulation (Fiberglass) o reinforcement of composite and plastics o specialty papers in battery separators and filtration

Metallic fiber (1946) is used for: o adding metallic properties to clothing for the purpose of fashion (usually made with composite plastic and metal foils) o elimination and prevention of static charge build-up o conducting electricity to transmit information o conduction of heat

in the horticulture industry synthetics are often used in soils to help the plants grow better. exampes are expanded polystyrene flakes urea-formaldehyde foam resin polyurethane foam phenolic resin foam

Spinning Processes

Synthetic and Cellulosic Fiber Formation Technology Most synthetic and cellulosic manufactured fibers are created by extrusion forcing a thick, viscous liquid (about the consistency of cold honey) through the tiny holes of a device called a spinneret to form continuous filaments of semi-solid polymer.

In their initial state, the fiber-forming polymers are solids and therefore must be first converted into a fluid state for extrusion. This is usually achieved by melting, if the polymers are thermoplastic synthetics (i.e., they soften and melt when heated), or by dissolving them in a suitable solvent if they are non-thermoplastic cellulosics. If they cannot be dissolved or melted directly, they must be chemically treated to form soluble or thermoplastic derivatives. Recent technologies have been developed for some specialty fibers made of polymers that do not melt, dissolve, or form appropriate derivatives. For these materials, the small fluid molecules are mixed and reacted to form the otherwise intractable polymers during the extrusion process (if you are interested in the latest information on extrusion, The Spinneret

The spinnerets used in the production of most manufactured fibers are similar, in principle, to a bathroom shower head. A spinneret may have from one to several hundred holes. The tiny openings are very sensitive to impurities and corrosion. The liquid feeding them must be carefully filtered (not an easy task with very viscous materials) and, in some cases, the spinneret must be made from very expensive, corrosion-resistant metals.

Maintenance is also critical, and spinnerets must be removed and cleaned on a regular basis to prevent clogging. As the filaments emerge from the holes in the spinneret, the liquid polymer is converted first to a rubbery state and then solidified. This process of extrusion and solidification of endless filaments is called spinning, not to be confused with the textile operation of the same name, where short pieces of staple fiber are twisted into yarn. There are four methods of spinning filaments of manufactured fibers: wet, dry, melt, and gel spinning.

Wet Spinning Wet spinning is the oldest process. It is used for fiber-forming substances that have been dissolved in a solvent. The spinnerets are submerged in a chemical bath and as the filaments emerge they precipitate from solution and solidify. Because the solution is extruded directly into the precipitating liquid, this process for making fibers is called wet spinning. Acrylic, rayon, aramid, modacrylic and spandex can be produced by this process. Dry Spinning Dry spinning is also used for fiber-forming substances in solution. However, instead of precipitating the polymer by dilution or chemical reaction, solidification is achieved by evaporating the solvent in a stream of air or inert gas. The filaments do not come in contact with a precipitating liquid, eliminating the need for drying and easing solvent recovery. This process may be used for the production of acetate, triacetate, acrylic, modacrylic, PBI, spandex, and vinyon. Melt Spinning

In melt spinning, the fiber-forming substance is melted for extrusion through the spinneret and then directly solidified by cooling. Nylon, olefin, polyester, saran and sulfar are produced in this manner.

Melt spun fibers can be extruded from the spinneret in different crosssectional shapes (round, trilobal, pentagonal, octagonal, and others).

Trilobal-shaped fibers reflect more light and give an attractive sparkle to textiles. Pentagonal-shaped and hollow fibers, when used in carpet, show less soil and dirt. Octagonal-shaped fibers offer glitter-free effects. Hollow fibers trap air, creating insulation and provide loft characteristics equal to, or better than, down.

Detailed production flowcharts: Acrylic Nylon(Polyamide) Polyester Gel Spinning Gel spinning is a special process used to obtain high strength or other special fiber properties. The polymer is not in a true liquid state during extrusion. Not completely separated, as they would be in a true solution, the polymer chains are bound together at various points in liquid crystal form. This produces strong inter-chain forces in the resulting filaments that can significantly increase the tensile strength of the fibers. In addition, the liquid crystals are aligned along the fiber axis by the shear forces during extrusion. The filaments emerge with an unusually high degree of orientation relative to each other, further enhancing strength. The process can also be described as dry-wet spinning, since the filaments first pass through air and then are cooled further in a liquid bath. Some high-strength polyethylene and aramid fibers are produced by gel spinning. Stretching and Orientation While extruded fibers are solidifying, or in some cases even after they have hardened, the filaments may be drawn to impart strength. Drawing pulls the molecular chains together and orients them along the fiber axis, creating a considerably stronger yarn.

Cryatallization Crystals are grown in many shapes, which are dependent upon downstream processing or final product requirements. Crystal shapes can include cubic, tetragonal, orthorhombic, hexagonal, monoclinic, triclinic, and trigonal. In order for crystallization to take place a solution must be "supersaturated". Supersaturation refers to a state in which the liquid (solvent) contains more dissolved solids (solute) than can ordinarily be accomodated at that temperature.

As with any separation method, equilibrium plays an important role. Below is a general solubility curve for a solid that forms hydrate (a compound that has one or more water molecules attached) as it cools.

In Figure 1, X may be any solid that can form hydrates such as Na 2S2O3. The number of hydrate molecules shown in Figure 1 is strictly arbitrary and will vary for each substance. So how do you grow crystals? Let's consider an example that is fairly easy to envision. Take a pot of boiling water and add table salt while stirring to make a water-salt solution. Continue adding salt until no more salt will

dissolve in the solution (this is a saturated solution). Now add one final teaspoon of salt. The salt that will not dissolve will help the first step in crystallization begin. This first step is called "nucleation" or primary nucleation. The salt resting at the bottom of the pot will provide a site for nucleation to occur. Primary nucleation is the first step in crystallization. Simply defined, it's the growth of a new crystalA On an industrial scale, a large supersaturation driving force is necessary to initiate primary nucleation. The initiation of primary nucleation via this driving force is not fully understood which makes it difficult to model (experiments are the best guide). Usually, the instantaneous formation of many nuclei can be observed "crashing out" of the solution. You can think of the supersaturation driving force as being created by a combination of high solute concentration and rapid cooling. In the salt example, cooling will be gradual so we need to provide a "seed" for the crystals to grow on. In continuous crystallization, once primary nucleation has begun, the crystal size distribution begins to take shape. Think about our salty water, as you look at Figure 2 describing the progression of crystallization.

Figure 2: Progression of Crystallization The second chief mechanism in crystallization is called secondary nucleation. In this phase of crystallization, crystal growth is initiated with contact. The

contact can be between the solution and other crystals, a mixer blade, a pipe, a vessel wall, etc. This phase of crystallization occurs at lower supersaturation (than primary nucleation) where crystal growth is optimal. Secondary nucleation requires "seeds" or existing crystals to perpetuate crystal growth. In our salt example, we bypassed primary nucleation by "seeding" the solution with a final teaspoon of salt. Secondary nucleation can be thought of as the workhorse of crystallization. Again, no complete theory is available to model secondary nucleation and it's behavior can only be anticipated by experimentation. Mathematic relationships do exist to correlate experimental data. However, correlating experimental data to model crystallization is time consuming and often considered extreme for batch operations, but can easily be justified for continuous processes where larger capital expenditures are necessary. For batch operations, only preliminary data measurements are truly necessary. We've discussed how crystallization occurs once supersaturation is reached, but how do we reach supersaturation? We have already covered one such method in our salt crystallization example. Since the solubility of salt in water decreases with decreasing temperature, as the solution cools, its saturation increases until it reaches supersaturation and crystallization begins (Figure 3). Cooling is one of the four most common methods of achieving supersaturation. It should be noted that cooling will only help reach supersaturation in systems where solubility and temperature are directly related. Although this is nearly always the case, there are exceptions. In Figure 3, you'll note that Ce2(SO4)3 actually becomes less soluble in water at higher temperatures.

Figure 3: Solubilities of Several Solids The four most common methods of reaching supersaturation in industrial processes are: 1. Cooling 2. 3. 4. Chemical Reaction (with Solvent some exceptions) Evaporation Drowning

In an industrial setting, the solute-solvent mixture is commonly referred to as the "mother liquor". Drowning describes the addition of a nonsolvent to the solution which decreases the solubility of the solid. A chemical reaction can be used to alter the dissolved solid to decrease its solubility in the solvent, thus working toward supersaturation. Each method of achieving supersaturation has its own benefits. For cooling and evaporative crystallization, supersaturation can be generated near a heat transfer surface and usually at moderate rates. Drowning or reactive crystallization allows for localized, rapid crystallization where the mixing mechanism can exert significant influence on the product characteristics. Equipment Used in Crystallization 1.Tank Crystallizers

This is probably the oldest and most basic method of crystallization. In fact, the "pot of salt water" is a good example of tank crystallization. Hot, saturated solutions are allowed to cool in open tanks. After crystallization, the mother liquor is drained and the crystals are collected. Controlling nucleation and the size of the crystals is difficult. The crystallization is essentially just "allowed to happen". Heat transfer coils and agitation can be used. Labor costs are high, thus this type of crystallization is typically used only in the fine chemical or pharmaceutical industries where the product value and preservation can justify the high operating costs. 2.Scraped Surface Crystallizers An example may be the Swenson-Walker crystallizer consisting of a trough about 2 feet wide with a semi-circular bottom. The outside is jacketed with cooling coils and an agitator blade gently passes close to the trough wall removing crystals that grow on the vessel wall. 3.Forced Circulating Liquid Evaporator-Crystallizer Just as the name implies, these crystallizers combine crystallization and evaporation, thus the driving forces toward supersaturation. The circulating liquid is forced through the tubeside of a steam heater. The heated liquid flows into the vapor space of the crystallization vessel. Here, flash evaporation occurs, reducing the amount of solvent in the solution (increasing solute concentration), thus driving the mother liquor towards supersaturation. The supersaturated liquor flows down through a tube, then up through a fluidized area of crystals and liquor where crystallization takes place via secondary nucleation. Larger product crystals are withdrawn while the liquor is recycled, mixed with the feed, and reheated.

4.Circulating Magma Vacuum Crystallizer In this type of crystallizer, the crystal/solution mixture (magma) is circulated out of the vessel body. The magma is heated gently and mixed back into the vessel. A vacuum in the vapor space causes boiling at the surface of the liquid. The evaporation causes crystallization and the crystals are drawn off near the bottom of the vessel body.

Glass Transition Have you ever left a plastic bucket or some other plastic object outside during the winter, and found that it cracks or breaks more easily than it would in the summer time? What you experienced was the phenomenon known as the glass transition. This transition is something that only happens to polymers, and is one of the things that make polymers unique. The glass transition is pretty much what it sounds like. There is a certain temperature(different for each polymer) called the glass transition temperature, or Tg for short. When the polymer is cooled below this temperature, it becomes hard and brittle, like glass. Some polymers are used above their glass transition temperatures, and some are used below. Hard plastics like polystyrene and poly(methyl methacrylate), are used below their glass transition temperatures; that is in their glassy state TheirTg's are well above room temperature, both at around 100oC. Rubber elastomers like polyisoprene and polyisobutylene, are used above their Tg's, that is, in therubbery state, where they are soft and flexible. Amorphous and Crystalline Polymers We have to make something clear at this point. The glass transition is not the same thing as melting. Melting is a transition which occurs in crystalline polymers. Melting happens when the polymer chains fall out of their crystal structures, and become a disordered liquid. The glass transition is a transition which happens to amorphouspolymers; that is, polymers whose chains are not arranged in ordered crystals, but are just strewn around in any old fashion, even though they are in the solid state. But even crystalline polymers will have a some amorphous portion. This portion usually makes up 40-70% of the polymer sample. This is why the same sample of a polymer can have both a glass transition temperature and a melting temperature. But you should know that the amorphous portion undergoes the glass transition only, and the crystalline portion undergoes melting only. The Snake Pit Now, to understand just why polymers with no order to them are hard and brittle below a certain temperature and soft and pliable above it, it can help to think of a polymer in the amorphous state as a big room full of slithering snakes. Each snake is a polymer chain. Now as you may remember, snakes are cold blooded animals, so all their body heat has to come from their surroundings. When it's warm, the snakes are happy, and can go on about their business of slithering and sliding with no trouble at all. They will move

all about randomly, over and around each other, and they slither hither and thither, just having a great time, or as good a time as snakes ever have. But when it gets cold, snakes don't move too much. They slow down without any heat, and tend to just sit still. Now they're still all wrapped around, over, and under each other, but as far as motion is concerned, it just doesn't happen. Now imagine trying to drive a bulldozer through this room full of snakes. If it's warm, and the snakes are moving, they can quickly slither out of your way, and the bulldozer moves through the room, causing a minimal amount of snake damage. But if it's cold, one of two things will happen to the motionless snakes. Either (A) the snakes will be stronger than the bulldozer, and the bulldozer won't get through, and the snakes will stay put; or (B) the bulldozer will be stronger than the snakes, and they'll get squashed, still not moving anywhere. Polymers are the same way. When the temperature is warm, the polymer chains can move around easily. So, when you take a piece of the polymer and bend it, the molecules, being in motion already, have no trouble moving into new positions to relieve the stress you have placed on them. But if you try to bend sample of a polymer below its Tg, the polymer chains won't be able to move into new positions to relieve the stress which you have placed on them. So just like in the example of a room full of cold snakes, one of two things will happen. Either (A) the chains are strong enough to resist the force you apply, and the sample won't bend; or (B) the force you apply will be too much for the motionless polymer chains to resist, and being unable to move around to relieve the stress, the polymer sample will break or shatter in your hands. This change in mobility with temperature happens because the phenomenon we call "heat" is really a form of kinetic energy; that is, the energy of objects in motion. It is actually an effect of random motion of molecules, whether they are polymer molecules or small molecules. Things are "hot" when their molecules have lots of kinetic energy and move around very fast. Things are "cold" when their molecules lack kinetic energy and move around slowly, or not at all. Now the exact temperature at which the polymer chains undergo this big change in mobility depends on the structure of the polymer. To see how a small change in structure can mean a big change in Tg, take a look at the difference between poly(methyl acrylate) and poly(methyl methacrylate) on the acrylate page.

Twistin' the Night Away There is a difference between polymers and snakes that we probably should discuss at this point. An individual snake is not only wiggling around, but actually moving from one side of the room to the other. This is called translational motion. When you walk down the street, presuming you're not like most Americans who never walk anywhere, you are undergoing translational motion. While polymers are not incapable of such motion, mostly they are not undergoing translational motion. But they are still moving around, wiggling this way and that, much like little kids in church. To be sure, by the time we get down to the glass transition temperature, it is already too cold for the polymer molecules, tangled up in each other as they are, to move any distance in one direction. The motion that allows a polymer above its glass transition temperature to be pliable is not usually translational motion, but what is known in the business aslongrange segmental motion. While the polymer chain as a whole may not be going anywhere, segments of the chain can wiggle around, swing to and fro, and turn like a giant corkscrew. The polymer samples may be thought of as a crowd of people on a dance floor. While each whole body tends to stay in the same spot, various arms, legs, and whatnot are changing position a lot. When the temperature drops below the Tg, for polymers the party's over, and the long-range segmental motion grinds to a halt. When this long-range motion ceases, the glass transition occurs, and the polymer changes from being soft and pliable to being hard and brittle. See for yourself Now to make sure this is all clear, we made a little movie showing what happens to the polymer chains at the glass transition temperature. Try This! Want to have some fun? First, get your teacher to bring some liquid nitrogen to class. Then put some in a styrofoam cup, and drop in some household objects made from polymers, like rubber bands or plastic wrap. The liquid nitrogen, being nippy as it is, will cool the objects below their glass transition temperatures. Try to bend your rubber band (hold it with a pair of pliers, because you could get frostbite if you try to touch it with your fingers) and it will shatter! Neato, huh? The rubber band will shatter because it's below its glass transition temperature. Measuring the Tg

If you want to know how we measure both melting points and Tg's, plus latent heats of melting, and changes in heat capacity, now there's a wonderful page to tell you all about a technique called differential scanning calorimetry. Go visit it! Where Next? Want to know more about the wonderful glass transition? Read these little segments! Messing Around with the Tg The Tg vs. Melting What Becomes the High Tg Polymer? Messing Around with the Glass Transition Sometimes, a polymer has a Tg that is higher than we'd like. That's ok, we just put something in it called a plasticizer. This is a small molecule which will get in between the polymer chains, and space them out from each other. We call this increasing the free volume. When this happens they can slide past each other more easily. When they slide past each other more easily, they can move around at lower temperatures than they would without the plasticizer. In this way, the Tg of a polymer can be lowered, to make a polymer more pliable, and easier to work with. If you're wondering what kind of small molecule we're talking about, here are some that are used as plasticizers:

Have you ever smelled "that new car smell"? It's not something I smell too often on the money I make, but that smell is the plasticizer evaporating from the plastic parts on the inside of your car. After many years, if enough of it evaporates, your dashboard will no longer be plasticized. TheTg of the polymers in your dashboard will rise above room temperature, and the dashboard will become brittle and crack. The Glass Transition vs. Melting Keywords: first order transition, heat capacity, second order transition It's tempting to think of the glass transition as a kind of melting of the polymer. But this is an inaccurate way of looking at things. There are a lot of important differences between the glass transition and melting. Like I said earlier, melting is something that happens to a crystalline polymer, while the glass transition happens only to polymers in the amorphous state. A given polymer will often have both amorphous and crystalline domains within it, so the same sample can often show a melting point and a Tg. But the chains that melt are not the chains that undergo the glass transition. There is another big difference between melting and the glass transition. When you heat a crystalline polymer at a constant rate, the temperature will increase at a constant rate. The heat amount of heat required to raise the temperature of one gram of the polymer one degree Celsius is called the heat capacity. Now the temperature will continue to increase until the polymer reaches its melting point. When this happens, the temperature will hold steady for awhile, even though you're adding heat to the polymer. It will hold steady until the polymer has completely melted. Then the temperature of the polymer will begin to increase once again. The temperature rising stops because melting requires energy. All the energy you add to a crystalline polymer at its melting point goes into melting, and none of it goes into raising the temperature. This heat is called the latent heat of melting. (The word latentmeans hidden.)

Now once the polymer has melted, the temperature begins to rise again, but now it rises at a slower rate. The molten polymer has a higher heat capacity than the solid crystalline polymer, so it can absorb more heat with a smaller increase in temperature. So, two things happen when a crystalline polymer melts: It absorbs a certain amount of heat, the latent heat of melting, and it undergoes a change in its heat capacity. Any change brought about by heat, whether it is melting or freezing, or boiling or condensation, which has a change in heat capacity, and a latent heat involved, is called a first order transition. But when you heat an amorphous polymer to its Tg, something different happens. First you heat it, and the temperature goes up. It goes up at a rate determined by the polymer's heat capacity, just like before. Only something funny happens when you reach the Tg. The temperature doesn't stop rising. There is no latent heat of glass transition. The temperature keeps going up. But the temperature doesn't go up at the same rate above the Tg as below it. The polymer does undergo an increase in its heat capacity when it undergoes the glass transition. Because the glass transition involves change in heat capacity, but it doesn't involve a latent heat, this transition is called a second order transition. It may help to look at some nifty pictures. The plots show the amount of heat added to the polymer on the y-axis and the temperature that you'd get with a given amount of heat on the x-axis.

The plot on the left shows what happens when you heat a 100% crystalline polymer. You can look at it and see that it's discontinuous. See that break? That's the melting temperature. At that break, a lot of heat is added without any temperature increase at all. That's the latent heat of melting. We see the slope getting steeper on the high side of the break. The slope of this kind of plot is equal to the heat capacity, so this increase in steepness corresponds to our increase in heat capacity above the melting point. But in the plot on the right, which shows what happens to a 100% amorphous polymer when you heat it, we don't have a break. The only change we see at the glass transition temperature is an increase in the slope, which means, of course, that we have an increase in heat capacity. We can see a heat capacity change at the Tg, but no break, like we do in the plot for the crystalline polymer. As I said before, there is no latent heat involved with the glass transition. And this, my friends, right before your eyes, is the difference between a first order transition like melting, and a second order transition like the glass transition. What Becomes the High Tg Polymer? Ok, we know at this point that some polymers have highTg's, and some have low Tg's. The question we haven't bothered to ask yet is this: why? What makes one polymer glass transition at 100 oC and another at 500 oC? The very simple answer is this: How easily the chains move. A polymer chain that can move around fairly easily will have a very low Tg, while one that doesn't move so well will have a high one. This makes sense. The more easily a polymer can move, the less heat it takes for the chains to commence wiggling and break out of the rigid glassy state and into the soft rubbery state. So then I suppose we've brought ourselves to another question... What makes one polymer move more easily than another? I'm glad you asked that. There are several things that affect the mobility of a polymer chain. Go look at each one! Backbone Flexibility Pendant Groups Part I: Fish Hooks and Boat Anchors Pendant Groups Part II: Elbow Room

Backbone Flexibility This is the biggest and most important one to remember. The more flexible the backbone chain is, the better the polymer will move, and the lower its Tg will be. Let's look at some examples. The most dramatic one is that of silicones. Let's take a look at one called polydimethylsiloxane.

This backbone is so flexible that polydimethylsiloxane has aTg way down at -127 oC! This chain is so flexible that it's a liquid at room temperature, and it's even used to thicken shampoos and conditioners. Now we'll look at another extreme, poly(phenylene sulfone).

This polymer's backbone is just plain stiff. It's so rigid that it doesn't have a Tg! You can heat this thing to over 500 oC and it will still stay in the glassy state. It will decompose from all the heat before it lets itself undergo a glass transition! In order to make a polymer that's at all processable we have to put some flexible groups in the backbone chain. Ether groups work nicely.

Polymers like this are called poly(ether sulfones), and those flexible ether groups bring the Tg of this one down to a more manageable 190 oC.

Pendant Groups Part I: Fish Hooks and Boat Anchors Pendant groups have a big effect on chain mobility. Even a small pendant group can act as a fish hook that will catch on any nearby molecule when the polymer chain tries to move like corkscrew. Pendant groups also catch on each other when chains try to slither past each other. One of the best pendant groups for getting a high Tg is the big bulky adamantyl group. An adamantyl group is derived from a compound called adamantane.

Click on the adamantane to see it in 3-D! A big group like this does more than just act like a hook that catches on nearby molecules and keeps the polymer from moving. It's a downright boat anchor. Not only does it get caught on nearby polymer chains, its sheer mass is such a load for its polymer chain to move that it makes the polymer chain move much more slowly. To see how much this affects the Tg, just take a look at two poly(ether ketones), one with an adamantane pendant group and one without.

The Tg of the polymer on the top is already decent at 119oC, but the adamantyl group raises even higher, to 225 oC. Pendant Groups Part II: Elbow Room But big bulky pendant groups can lower the Tg, too. You see, the big pendant groups limit how closely the polymer chains can pack together. The further they are from each other, the more easily they can move around. This lowers the Tg, in the same way a plasticizer does. The fancy way to say that there is more room between the polymer chains is to say there is more free volume in the polymer. The more free volume, the lower the Tg generally. We can see this with a series of methacrylate polymers:

You can see a big drop each time we make that pendant alkyl chain one carbon longer. We start out at 120 oC for poly(methyl methacrylate), but by the time we get to poly(butyl methacrylate) the Tg has dropped to only 20oC, pretty close to room temperature.

Nylon-6

Nylon 6 is an awful lot like our friend nylon 6,6. You can look at the picture if you don't believe me.

But making nylon 6 is lot different from nylon 6,6. First of all, nylon 6 is only made from one kind of monomer, a monomer called caprolactam. Nylon 6,6 is made from two monomers, adipoyl chloride and hexamethylene diamine.

If you want to see caprolactam in 3-D, But enough small talk. Let's get on with the business of turning caprolactam into nylon 6. Nylon 6 is made by heating caprolactam to about 250 oC with about 5-10% water thrown in. So what happens to caprolactam when there's water around? The carbonyl oxygen looks around, and sees a water molecule, and sees how easy it would be to steal one of the water's hydrogen atoms. Now as is often the case, a little thing like this that seem harmless enough can grow into something much bigger. If you watch, you'll see that caprolactam's greed is going to get the better of it.

The carbonyl oxygen donates a pair of electrons to the hydrogen atom of water, thus stealing the hydrogen from the water. This gives us a protonated carbonyl, and a free hydroxyl group. Keep this hydroxyl group in mind, because it is going to come back to haunt greedy ol' caprolactam. But first, let's remember that the carbonyl oxygen now has a positive charge. It doesn't like this, so it swipes a pair of electrons from the carbonyl double bond, leaving the positive charge on the carbonyl carbon atom.

But carbocations are not happy critters. Putting a carbocation in a molecule is just begging for some nucleophile to come along and attack it. Nucleophile? Did someone say nucleophile? I think there's one nearby. It's that old hydroxide ion that was left when caprolactam stole the proton from the water molecule. This little hydroxide ion never really worked through the negative emotions of having lost its proton to caprolactam. Still harboring a lot of hostility, it attacks the carbocation.

The molecule formed is now an unstable gem diol. Unstable? Of course. Didn't I tell you that caprolactam's greed would be its undoing? A mad reshuffling of electrons happens next. The nitrogen atom donates a pair of electrons to a hydrogen atom on one of the hydroxyl groups, stealing it away. The electrons that the hydrogen shared with its oxygen shift to form a double bond between the oxygen and the carbon atom. And lastly, the electrons shared by the carbon and the nitrogen shift completely to the nitrogen, severing the carbon-nitrogen bond.

Alas, the circle is broken, and caprolactam is no more! Like many junk bond dealers in the eighties, it has paid dearly for its greed. What we're left with is a linear amino acid. But our story is far from over. You see, that linear amino acid can react with a caprolactam molecule, a lot like the water molecule did. Caprolactam molecules aren't very bright. Witnessing one of their own destroyed by greed doesn't make them any less greedy. They just try to steal what they can from their fallen sibling, like greedy little buzzards. Ever avaricious, a caprolactam molecule will steal the acid hydrogen form the linear amino acid. The carbonyl oxygen donates a pair of electrons to that hydrogen, stealing it away from the amino acid.

And as expected, the electrons rearrange to form the carbocation, just as before:

This carbocation is still an open invitation to any nucleophile around, but this time, there's a new nucleophile on the block. That's the amino acid that just lost its acid hydrogen. It too has a lot of hostility towards the thieving caprolactam, and attacks just like we saw the hydroxide ion attack earlier.

This gives us an ammonium species, and this particular one is very unstable. The electrons play musical chairs. Showing no elemental loyalty, the ring nitrogen steals a hydrogen from the ammonium nitrogen. In addition, the bond joining the carbon and the nitrogen is severed, opening the ring. Another greedy caprolactam molecule bites the dust.

But we're not through yet. That carboxylate group at the end of the molecule is going to sweep around and steal the alcohol hydrogen.

This makes a new carbonyl group in the middle of the molecule, and regenerates the carboxylic acid. (Here's a little secret: No one really knows the order of the last two steps. They might happen in the reverse order. We just know that both of them happen before everything is over.) If you want to see a movie of the whole propagation process, . (Remember, this is a step growth polymerization.) Now that we have an acid again, it is sure to react with another avaricious caprolactam molecule, and then another, and another, until we get long chains of nylon 6.

Polyacrylonitrile Polyacrylonitrileis used for very few products an average consumer would be familiar with, except to make another polymer, carbon fiber. Homopolymers of polyacrylonitrile have been uses as fibers in hot gas filtration systems, outdoor awnings, sails for yachts, and even fiber reinforced concrete. But mostly copolymers containing polyacrylonitrile are used as fibers to make knitted clothing, like socks and sweaters, as well as outdoor products like tents and such. If the label of some piece of clothing says "acrylic", then it's made out of some copolymer of polyacrylonitrile. Usually they're copolymers of acrylonitrile and methyl acrylate, or acrylonitrile and methyl methacrylate:

Also, sometimes we make copolymers of acrylonitrile and vinyl chloride. These copolymers are flame-retardant, and the fibers made from them are called modacrylic fibers.

But the slew of copolymers of acrylonitrile doesn't stop there. Poly(styreneco-acrylonitrile) (SAN) and poly(acrylonitrile-co-butadiene-co--styrene) (ABS), are used as plastics.

SAN is a simple random copolymer of styrene and acrylonitrile. But ABS is more complicated. It's made by polymerizing styrene and acrylonitrile in the presence of polybutadiene. Polybutadiene has carbon-carbon double bonds in it, which can polymerize, too. So we end up with a polybutadiene chain with SAN chains grafted onto it, like you see below.

ABS is very strong and lightweight. It is strong enough to be used to make automobile body parts, but it is so light that Wassana can lift this front bumper fascia over her head with only hand! Using plastics like ABS makes automobiles lighter, so they use less fuel, and therefore they pollute less.

ABS is a stronger plastic than polystyrene because of the nitrile groups of its acrylonitrile units. The nitrile groups are very polar, so they are attracted to each other. This allows opposite charges on the nitrile groups to stabilize each other like you see in the picture on the left. This strong attraction holds ABS chains together tightly, making the material stronger. Also the rubbery polybutadiene makes ABS tougher than polystyrene. Polyacrylonitrile is a vinyl polymer, and a derivative of the acrylate familyof polymers. It is made from the monomer acrylonitrile by free radical vinyl polymerization.

Poly (ethylene terephthalate) Polyethylene terephthalate (sometimes written poly(ethylene terephthalate), commonly abbreviated PET, PETE, or the obsolete PETP or PET-P), is a thermoplastic polymer resin of the polyester family and is used in synthetic fibers; beverage, food and other liquid containers; thermoforming applications; and engineering resins often in combination with glass fiber. It is one of the most important raw materials used in manmade fibers.

Depending on its processing and thermal history, it may exist both as an amorphous (transparent) and as a semi-crystalline (opaque and white) material. Its monomer can be synthesized by the esterification reaction between terephthalic acid and ethylene glycol with water as a byproduct, or the transesterification reaction between ethylene glycol and dimethyl terephthalate with methanol as a byproduct. Polymerization is through a polycondensation reaction of the monomers (done immediately after esterification/transesterification) with ethylene glycol as the byproduct (the ethylene glycol is recycled in production).

The majority of the world's PET production is for synthetic fibers (in excess of 60%) with bottle production accounting for around 30% of global demand. In discussing textile applications, PET is generally referred to as simply "polyester" while "PET" is used most often to refer to packaging applications. Some of the trade names of PET products are Dacron, Diolen, Terylene, andTrevira fibers, Cleartuf, Eastman PET and Polyclear bottle resins, Hostaphan, elinex, and Mylar films, and Arnite, Ertalyte, Impet,Rynite and Valox injection molding resins. The polyester Industry makes up about 18% of world polymer production and is third after polyethylene (PE) and polypropylene (PP).

Chemical structure of polyethylene terephthalate Contents


1 Uses 2 Intrinsic viscosity 3 Drying 4 Copolymers 5 Crystals 6 Degradation 7 Antimony 8 Re-crystallization 9 Processing equipment 10 See also 11 References 12 External links

Uses

soft drink bottle PET can be semi-rigid to rigid, depending on its thickness, and is very lightweight. It makes a good gas and fair moisture barrier, as well as a good barrier to alcohol (requires additional "Barrier" treatment) and solvents. It is strong and impact-resistant. It is naturally colorless with high transparency. When produced as a thin film (often known by the tradename Mylar), PET is often coated with aluminium to reduce its permeability, and to make it reflective and opaque. PET bottles are excellent barrier materials and are widely used for soft drinks, (see carbonation). PET or Dacron is also used as a thermal insulation layer on the outside of the International Space Station as seen in an episode of Modern Marvels "Sub Zero". For certain specialty bottles, PET sandwiches an additional polyvinyl alcohol to further reduce its oxygen permeability. When filled with glass particles or fibers, it becomes significantly stiffer and more durable. This glass-filled plastic, in a semi-crystalline formulation, is sold under the tradename Rynite, Arnite, Hostadur, and Crastin.

Sails are usually made of Dacron, a brand of PET fiber; colorful lightweight spinnakers are usually made of nylon. While most thermoplastics can, in principle, be recycled, PET bottle recycling is more practical than many other plastic applications. The primary reason is that plastic carbonated soft drink bottles and water bottles are almost exclusively PET which makes them more easily identifiable in a recycle stream. PET has a resin identification code of 1. PET, as with many plastics, is also an excellent candidate for thermal recycling (incineration) as it is composed of carbon, hydrogen and oxygen with only trace amounts of catalyst elements (no sulphur) and has the energy content of soft coal. One of the uses for a recycled PET bottle is for the manufacture of polar fleece material. It can also make fiber for polyester products. PET was patented in 1941 by the Calico Printers' Association of Manchester. The PET bottle was patented in 1973. Intrinsic viscosity One of the most important characteristics of PET is referred to as I.V. (intrinsic viscosity). The I.V. of the material, measured in deciliters per gram (dl/g) is dependent upon the length of its polymer chains. The longer the chains, the stiffer the material, and therefore the higher the I.V. The average chain length of a particular batch of resin can be controlled during polymerization. An I.V. of about: 0.60 dl/g: Would be appropriate for fibre

0.65 dl/g: Film 0.76-0.84 dl/g: Bottles 0.85 dl/g: Tire cord Drying PET is hygroscopic, meaning that it naturally absorbs water from its surroundings. However, when this 'damp' PET is then heated a chemical reaction known as hydrolysis takes place between the water and the PET which reduces its molecular weight (IV) and its physical properties. This means that before the resin can be processed in a molding machine, as much moisture as possible must be removed from the resin. This is achieved through the use of a desiccant or dryers before the PET is fed into the processing equipment. Inside the dryer, hot dry air is pumped into the bottom of the hopper containing the resin so that it flows up through the pellets, removing moisture on its way. The hot wet air leaves the top of the hopper and is first run through an after-cooler, because it is easier to remove moisture from cold air than hot air. The resulting cool wet air is then passed through a desiccant bed. Finally the cool dry air leaving the desiccant bed is re-heated in a process heater and sent back through the same processes in a closed loop. Typically residual moisture levels in the resin must be less than 40 parts per million (parts of water per million parts of resin, by weight) before processing. Dryer residence time should not be shorter than about four hours. This is because drying the material in less than 4 hours would require a temperature above 160 C, at which level hydrolysis would begin inside the pellets before they could be dried out. Copolymers In addition to pure (homopolymer) PET, PET modified by copolymerization is also available. In some cases, the modified properties of copolymer are more desirable for a particular application. For example, cyclohexane dimethanol (CHDM) can be added to the polymer backbone in place of ethylene glycol. Since this building block is much larger (6 additional carbon atoms) than the ethylene glycol unit it replaces, it does not fit in with the neighbouring chains the way an ethylene glycol unit would. This interferes with crystallization and lowers the polymer's melting temperature. Such PET is generally known as PETG (EastmanChemical and SKchemicals are the only two manufacturers).

Replacing terephthalic acid (right) with isophthalic acid (center) creates a kink in the PET chain, interfering with crystallization and lowering the polymer's melting point. Another common modifier is isophthalic acid, replacing some of the 1,4(para-) linked terephthalate units. The 1,2-(ortho-) or 1,3-(meta-) linkage produces an angle in the chain, which also disturbs crystallinity. Such copolymers are advantageous for certain moulding applications, such as thermoforming, which is used for example to make tray or blister packagings from PETG film, or PETG sheet. On the other hand, crystallization is important in other applications where mechanical and dimensional stability are important, such as seat belts. For PET bottles, the use of small amounts of CHDM or other comonomers can be useful: if only small amounts of comonomers are used, crystallization is slowed but not prevented entirely. As a result, bottles are obtainable via stretch blow molding ("SBM"), which are both clear and crystalline enough to be an adequate barrier to aromas and even gases, such as carbon dioxide in carbonated beverages. Crystals Crystallization occurs when polymer chains fold up on themselves in a repeating, symmetrical pattern. Long polymer chains tend to become entangled on themselves, which prevents full crystallization in all but the most carefully controlled circumstances. PET is no exception to this rule; 60% crystallization is the upper limit for commercial products, with the exception of polyester fibers. PET in its natural state is a crystalline resin. Clear products can be produced by rapidly cooling molten polymer to form an amorphous solid. Like glass, amorphous PET forms when its molecules are not given enough time to arrange themselves in an orderly fashion as the melt is cooled. At room temperature the molecules are frozen in place, but if enough heat energy is put back into them, they begin to move again, allowing crystals to nucleate and grow. This procedure is known as solid-state crystallization. Like most materials, PET tends to produce many small crystallites when crystallized from an amorphous solid, rather than forming one large single crystal. Light tends to scatter as it crosses the boundaries between crystallites and the amorphous regions between them. This scattering means

that crystalline PET is opaque and white in most cases. Fiber drawing is among the few industrial processes that produces a nearly single-crystal product. Degradation PET is subject to various types of degradations during processing. The main degradations that can occur are hydrolytic, thermal and probably most important thermal oxidation. When PET degrades, several things happen: discoloration, chain scissions resulting in reduced molecular weight, formation of acetaldehyde and cross-links ("gel" or "fish-eye" formation). Discoloration is due to the formation of various chromophoric systems following prolonged thermal treatment at elevated temperatures. This becomes a problem when the optical requirements of the polymer are very high like for example in packaging applications. Acetaldehyde is normally a colorless gas with a fruity smell. It forms naturally in fruit, but it can cause an off-taste in bottled water. Acetaldehyde forms in PET through the "abuse" of the material. High temperatures (PET decomposes above 300 C or 570 F), high pressures, extruder speeds (excessive shear flow raises temperature) and long barrel residence times all contribute to the production of acetaldehyde. When acetaldehyde is produced, some of it remains dissolved in the walls of a container and then diffuses into the product stored inside, altering the taste and aroma. This is not such a problem for nonconsumables such as shampoo, for fruit juices, which already contain acetaldehyde or for strong-tasting drinks, such as soft drinks. For bottled water, low acetaldehyde content is quite important, because if nothing masks the aroma, even extremely low concentrations (10-20 parts per billion parts of resin, by weight) of acetaldehyde can produce an off-taste. The thermal and thermooxidative degradation results in poor processability characteristics and performance of the material. One way to alleviate this is to use a copolymer. Comonomers such as CHDM or isophthalic acid lower the melting temperature and reduces the degree of crystallinity of PET (especially important when the material is used for bottle manufacturing). Thus the resin can be plastically formed at lower temperatures and/or with lower force. This helps to prevent degradation, reducing the acetaldehyde content of the finished product to an acceptable (that is, unnoticeable) level. See copolymers, above. Other ways to improve the stability of the polymer is by using stabilizers, mainly antioxidants such as phosphites. Recently, molecular level stabilization of the material using nanostructured chemicals has also been considered. Antimony

Antimony trioxide (Sb2O3) is a catalyst that is often used in the production of PET. It remains in the material and can thus in principle migrate out into food and drinks. Although antimony trioxide is of low toxicity, its presence is still of concern. The Swiss Federal Office of Public Health investigated the amount of antimony migration, comparing waters bottled in PET and glass: the antimony concentrations of the water in PET bottles was higher, but still well below the allowed maximal concentrations.[1] (report available in German and French only) The Swiss Federal Office of Public Health concluded that small amounts of antimony migrate from the PET into bottled water, but that the health risk of the resulting low concentrations is negligible (1% of the "tolerable daily intake" determined by the WHO). A later (2006) but more widely publicized study by a group of geochemists at the University of Heidelberg headed by William Shotyk found similar amounts of antimony in water in PET bottles.[2] The most recent WHO risk assessment for antimony in drinking water can be found here: [3] Re-crystallization

PETE has SPI resin ID code 1

Recrystallized PET PET can be used to explore the crystallization of amorphous solids. The resin identification code can be used to verify the type of plastic it is made of: many plastic beverage bottles have the letters PET or PETE and a code of 1 on the bottom, near the center. When a flame is held several inches below the bottle and slowly brought closer, part of the material will visibly change. This happens because high temperatures melt the PET. This releases the

tension that was frozen in during the blow molding process and the polymer chains will shift to a more relaxed and disordered state, which results in shrinkage of the softened area. Because of the decreased order of the polymer chains, there are now fewer crystal nuclei. Consequently, when the crystallites re-form upon cooling they grow larger than the original crystallites in the bottle wall. Because the new crystallites are larger than the wave length of light, they will now cause light to scatter, giving the material an opaque white appearance. Processing equipment There are two basic molding methods, one-step and two-step. In two-step molding, two separate machines are used. The first machine injection molds the preform. The preform looks like a test tube. The bottle-cap threads are already molded into place, and the body of the tube is significantly thicker, as it will be inflated into its final shape in the second step using stretch-blow molding. In the second process, the preforms are heated rapidly and then inflated against a two-part mold to form them into the final shape of the bottle. Preforms (uninflated bottles) are now also used as containers for candy. In one-step machines, the entire process from raw material to finished container is conducted within one machine, making it especially suitable for molding non-standard shapes (custom molding), including jars, flat oval, flask shapes etc. Its greatest merit is the reduction in space, product handling and energy, and far higher visual quality than can be achieved by the two-step system.

Nylon-66 This page is all about how to make nylon. We're telling you this as if you can't read the title for yourself. To start off, nylon is made by a reaction which is a step-growth polymerization, and a condensation polymerization. Nylons are made from diacids and diamines. If you want to see what adipic acid and hexamethylene diamine look like in 3-D, .

Of course, there are a few more details to the reaction than you see up there in that little picture.

To make nylon 6,6 on doesn't need a catalyst, but acids do catalyze the reaction, and wouldn't you know it, one of the monomers is itself an acid. A little reaction happens between two adipic acid molecules. One will donate a proton to a the carbonyl oxygen of another.

When this oxygen is protonated the carbonyl oxygen becomes much more vulnerable to attack by the nitrogen of our diamine. This happens because our protonated oxygen bears a positive charge. Oxygen does not like to have a positive charge. So it pulls the electrons it shares with the carbonyl

toward itself. This leaves the carbonyl carbon lacking electrons, and ready for the amine nitrogen to donate a pair to it:

Then the electrons play musical chairs. One of the electron pairs form the carbonyl double bond shifts entirely to the oxygen, taking care of the problem of the positive charge at that atom, but now our nitrogen has a positive charge.

So then we get an even more elaborate game of electron musical chairs. The electrons from the hydrogen oxygen bond go back to the oxygen, freeing the proton, regenerating the acid catalyst. Then the carbonyl oxygen shares its newly regained electrons with the carbon atoms, regenerating the carbonyl double bond. Of course, this isn't enough. The oxygen of the hydroxyl group decides to do a little bit of electron shuffling of its own. It takes the pair it shares with the carbon and hogs them to itself, severing the bond between it and the carbon. It then donates a pair of electrons to a hydrogen connected to the nitrogen. That gets this hydrogen thinking. As it now shares a pair of electrons with the oxygen, it sees no need to keep the pair it shares with the nitrogen, so it lets go of that pair, giving it over to the nitrogen. This shift of electrons breaks the bond between the hydrogen and the nitrogen, and gets rid of the positive charge on that nitrogen. It splits off H2O, and generates the amidecontaining dimer. So what does this dimer do? Look close, and you'll see that it has an acid group at one end, and an amine group at the other. This means that it can react with a molecule of the diacid, or a molecule of the diamine. Either way, you get a trimer.

Wanna know a little secret? Our dimer can also react with other dimers, to make a tetramer if it wants to. Or it can react with a trimer to form a pentamer, and it can also react with bigger oligomers. Eventually, when this happens, dimers will grow into trimers, tetramers, and bigger oligomers, and these big oligomers will react with each other, to form even bigger oligomers. This keeps happening until they become big enough to be called polymers.

For the molecules to grow big enough to be called polymers, we have to do this reaction under a vacuum. When we do this, all that by-product water will evaporate and get sucked away. We need to get rid of the water because of a little rule called Le Chatelier's Principle. Now remember how at the beginning of this little lesson I said that the reaction doesn't need an acid catalyst to take place? The reason we know this is that near the end of the polymerization, when there aren't many acid groups left to be catalysts, the reaction still goes on. You see, the amine can react with the unprotonated carboxylic acids. If this were not so, high molecular weight nylon 66 could not be made without an external catalyst, because the reaction would stop at higher conversions, when there aren't many acid groups left to be catalysts. Wanna know something else? Nylons can also be made from a diamine and a diacid chloride:

This reaction goes by the same mechanism, but you need to add a little bit of acid to act as a catalyst. (When you make nylon the other way, adipic acid acts as the catalyst.) Also, it produces HCl gas as a byproduct rather than water. If you want to see a movie of this method

Polypropylene Polypropylene is one of those rather versatile polymers out there. It serves double duty, both as a plastic and as a fiber. As a plastic it's used to make things like dishwasher-safefood containers. It can do this because it doesn't melt below 160oC, or 320oF. Polyethylene, a more common plastic, will anneal at around 100oC, which means that polyethylenedishes will warp in the dishwasher. As a fiber, polypropyleneis used to make indoor-outdoor carpeting, the kind that you always find around swimming pools and miniature golf courses. It works well for outdoor carpet because it is easy to make colored polypropylene, and because polypropylenedoesn't absorb water, like nylon does. Structurally, it's a vinyl polymer, and is similar topolyethylene, only that on every other carbon atom in the backbone chain has a methyl group attached to it.Polypropylene can be made from the monomer propylene by ZieglerNatta polymerization and by metallocene catalysis polymerization.

This is what the monomer propylene really looks like: Wanna know more? Research is being conducted on using metallocene catalysis polymerization to synthesize polypropylene. Metallocene catalysis polymerization can do some pretty amazing things for polypropylene. Polypropylene can be made with different tacticities. Most polypropylene we use is isotactic. This means that all the methyl groups are on the same side of the chain, like this:

But sometimes we use atactic polypropylene. Atactic means that the methyl groups are placed randomly on both sides of the chain like this:

However, by using special metallocene catalysts, it's believed that we can make polymers that contain blocks of isotacticpolypropylene and blocks of atactic polypropylene in the same polymer chain, as is shown in the picture:

This polymer is rubbery, and makes a good elastomer. This is because the isotactic blocks will form crystals by themselves. But because the isotactic blocks are joined to the atactic blocks, the little hard clumps of crystalline isotactic polypropylene are tied together by soft rubbery tethers of atactic polypropylene, as you can see in the picture on the right. To be honest, atactic polypropylene would be rubbery without help from the isotactic blocks, but it wouldn't be very strong. The hard isotactic blocks hold the rubbery isotactic material together, to give the material more strength. Most kinds of rubber have to be crosslinked to give them strength, but notpolypropylene elastomers.

Elastomeric polypropylene, as this copolymer is called, is a kind of thermoplastic elastomer. However, until the research is completed, this type of polypropylene will not be commercially available. The polypropylene that you can buy off the shelf at the storetoday has about 50 - 60% crystallinity, but this is too much for it to behave as an elastomer.