12.

Synthetic fibres

12.7.1 Introduction
Obtaining more valuable products from cheap materials has always been one of mankinds goals. Enormous interest was therefore aroused when Hilaire Bernigaud de Chardonnet presented the first samples of his rayon at the International Exhibition in Paris in 1889; as shiny and silky as natural silk, this was the first artificial fibre ever made by man. Although as early as 1913, 1931 and 1932 processes to obtain filaments from poly(vinyl chloride) and threads from poly(vinyl alcohol) and polystyrene were patented in Germany, the era of synthetic fibres began in 1935 at the laboratories of the DuPont Experimental Station, Pure Science Section, Wilmington, Delaware, (USA). Here, Gerard Berchet, one of Wallace Hume Carothers assistants, obtained just over 10 g of polyhexamethylene adipamide, subsequently commercialized in 1938 with the name nylon, the first totally synthetic industrial fibre. In theory, all organic polymeric materials consisting of linear macromolecules with a sufficiently high molecular weight can be turned into fibres, in other words long filaments whose axial ratio tends to infinity. However, only a small number of these provide filaments with physical and mechanical properties allowing for practical applications. The arrangements in which the fibres are found, independently of their origin, are the single fibre, a group of several single fibres to form a thread, and the interlacing of numerous threads to form textiles. A characteristic property of any fibre, in addition to its chemical, physical and mechanical properties, is its size perpendicular to its axis or to that of a group of fibres forming a thread. In practice, the radial dimension, and thus the thickness, of all continuous fibres including silk and those made of synthetic

polymeric materials is specified using the count; in other words the mass of the thread relative to a given length of it. The mass in grammes of 9,000 m (1,000 yards) of thread is known as the denier count or denier; another way of describing the thickness of a continuous thread is to specify the tex, in other words the weight in grammes of 1,000 m of yarn (or the decitex, dtex, referring to 10,000 m of yarn). In addition to the fracture load and (percentage) deformation at break, other important mechanical properties of fibres are their tenacity, or better, the maximum energy that they can absorb without breaking, and resilience, or the maximum energy that they can absorb without suffering permanent deformation. The development of synthetic fibres progressed side by side with that of organic chemistry, and especially petrochemistry, which, with some extremely rare exceptions, provides the base compounds for the synthesis of monomers. In 1936, ICI (Imperial Chemical Industries) patented the manufacture of fibres from polyethylene in Great Britain; in 1937 the first polyurethane bristles were made; in 1938 Paul Schlack of IG Farbenindustrie (Germany) synthesized poly(e-caprolactam), whose fibres were commercialized in 1943 with the name Perlon; in 1941, John Rex Whinfield and James Tennant Dickson of the Calico Printers Association of Manchester (Great Britain), synthesized polyethylene terephthalate, whose fibres were commercialized with the names Terylene (ICI, Great Britain), Dacron (DuPont, USA), Terital (Montecatini, Italy); in 1942 it was discovered that N-dimethylformamide was a solvent of polyacrylonitrile, thus making it possible to obtain fibres commercialized by E.I. DuPont de Nemours (USA) with the name Orlon; in 1960 the same company commercialized the new elastomeric polyurethane fibre with the trade name Lycra. Also in

VOLUME II / REFINING AND PETROCHEMICALS

917

POLYMERIC MATERIALS

1960, Polymer of Terni (Montecatini group) perfected the fibres obtained from isotactic polypropylene (Meraklon); in 1971 Kevlar (E. I. DuPont de Nemours, USA) entered the market, the first of the polyaramids, obtained with the interfacial condensation of terephthalic acid and p-phenylenediamine, giving fibres with exceptional mechanical and thermal properties. Today, synthetic fibres are not merely an alternative to natural and artificial fibres, but form classes of high performance materials which play an extremely important role in the field of high technology. The 5 denier of the first nylon filaments have fallen to todays 0.5 for polyamide or polyester monofilaments; fabrics made from these are superior in appearance, softness and sheen to those in natural silk (2 denier). These fibres are known as high added value fibres, as are those used to make special purpose fabrics (thermochromic fabrics which change colour depending on temperature, photochromic fabrics which change colour depending on light, iridescent fabrics which change colour depending on how they are hit by light, etc.). Also worth remembering are the high technology fibres deriving from the application of the latest developments in the science and technology of fibre manufacturing (biodegradable fibres for sutures; fibres which absorb and accumulate solar energy such as Solar-a of 1988, made by the Japanese firm Unitika, and similar products made by Descente of Japan, widely used for sports wear; fibres for haemodialysis, fibres for the oxygenation of blood in the artificial respiration machines known as mechanical lungs; fibres used for fabrics to make space suits for extra-vehicular activities, fibres which absorb humidity and sweat for sports wear, fibres with low friction with air, etc.) and finally superfibres, in other words fibres with exceptional mechanical properties (elasticity coefficient over 55 GPa and tenacity above 2.5 GPa), such as those made of high tenacity polyethylene, para-aramids, and polyacrylonitrile carbon. Natural fibres (and their derivatives) can be considered first generation fibres. Synthetic fibres (aliphatic polyamides, polyesters, polyacrylonitrile, etc.), which appeared between the 1930s and 1960s, are second generation fibres, created to replace first generation fibres. Todays high performance fibres (polyethylene, polyaramide, polyarylate, carbon fibres, etc.), which do not represent an alternative to natural fibres as did those of the second generation, can be classified as third generation fibres. These are used when fibres with low density, excellent mechanical performance and heat resistance are required (in sectors such as sport, transportation, space technology etc.) or to reinforce other materials (composites). It is

not unlikely that third generation fibres, given their better mechanical performance, will replace metals in many of their applications in the not too distant future. Synthetic fibres can be classified according to the polar functional group repeated in their chain (for those made by polycondensation) or on the basis of the structural unit for those made by addition polymerization. They are listed below in chronological order of synthesis: Polyamide fibres, obtained by condensation polymerization and characterized by the regular recurrence along the macromolecular chain of the amide group NHCO. These include aliphatic polyamides such as 66 (Nylon 66), 6 (Nylon 6, Perlon) 11 (Nylon 11, Rilsan) and others of minor interest, and aromatic polyamides (polyaramids). Polyester fibres, obtained by condensation polymerization and characterized by the regular recurrence along the macromolecular chain of the ester group COO. In addition to polyethylene terephthalate (Terylene or Dacron), they include the fibres obtained from wholly aromatic polyesters. Polyvinyl fibres, obtained by addition polymerization and characterized by a structural unit deriving from vinylic or vinylidenic monomers; of these fibres the most important are those made from acrylonitrile (Orlon), from vinyl chloride (Leavin, Thermovil, Movil, etc.) and from tetrafluoroethane. Polyolefin fibres, obtained by addition polymerization, such as polyethylenes from ethylene and polypropylenes (Meraklon) from propylene. Polyurethane fibres, formally obtained by condensation polymerization and characterized by the regular recurrence along the macromolecular chain of the urethane group OCONH (Lycra). Carbon fibres, included in this classification as derivatives of polyacrylonitrile.

12.7.2 Polyamide fibres

Polyamide fibres are generally known as nylon, the trade name of the first wholly synthetic textile fibre of industrial importance. They are obtained with the condensation polymerization of aliphatic or aromatic diamines and aliphatic or aromatic organic diacids, or with the ring-opening polymerization of w-aminoacids (Nylon 11 and Nylon 6). Polyamides are conventionally named according to the number of carbon atoms in the diamine and the diacid, or the w-aminoacid alone, and appear as corneous solids, non-transparent, with a melting temperature over

918

ENCYCLOPAEDIA OF HYDROCARBONS

SYNTHETIC FIBRES

200C. Their density ranges between 1.00 and 1.20 g/cm3. They are all insoluble in water, and can be dissolved cold in anhydrous acids (formic, sulphuric, glacial acetic acid) and phenols (phenol, p-cresol) at 80C and above. They can be hydrolysed by hot mineral acids in an aqueous solution. The high stability of aliphatic polyamide fibres, obtained by cold drawing, and their insolubility are due to the formation of hydrogen links between the amide groups of the polymeric chains. Introducing aromatic rings (polyaramids) to these leads to a raising of the melting point. Among the numerous polyamide fibres on the market, we will mention only those of greatest interest, and specifically polyhexamethylene adipamide or Nylon 66, poly(e-caprolactam) or Nylon 6 (Perlon), and that obtained from 11-aminoundecanoic acid or Nylon 11 (Rilsan). It is important to note that only the first of these has withstood the emergence of new fibres on the market.
Nylon 66

The story of Nylon 66s discovery by the E.I. DuPont de Nemours research group headed by Carothers, and the various stages of its industrialization (synthesis of the monomers and their polymerization, spinning, finishing and weaving of the fibres) marked the beginning of the era of synthetic textile fibres. Early in 1928, Carothers was called to lead DuPonts base organic chemistry research group, and given absolute freedom in terms of which inquiries to pursue. During base research on polyesters, various strategies to obtain polymers with molecular weights above 4,000 using condensation polymerization had been identified. By pure chance, it was discovered that these could be used to obtain flexible fibres which, after cold drawing, turned into extremely robust long threads. However, these fibres had no potential for commercial success due to their solubility in the solvents used for dry cleaning and excessively low melting point, which would have made it impossible to iron any textiles made from them. This led to the idea of studying less soluble materials, with better physical and mechanical properties, and in particular polyamides, which had already been the subject of previous research. In the summer of 1934, polypentamethylene sebacamide (polyamide 5-10) was made, melt spun using the needle of a syringe for injections as a spinneret. In October of the same year, a new synthesis method was developed, based on the principle that if diamine and diacid are mixed in equimolecular ratio, the amine salt of the diacid is obtained even without heating; this in turn polymerizes when heated, creating

a polyamide. In the salt, the two monomers are found in the exact ratio of 1 to 1, an essential condition to obtain high degrees of polymerization. Since the polymers made using this method sometimes had a degree of polymerization too high for them to be spun, at the beginning of 1935 it was discovered that small quantities of acetic acid could be added to the polymerization mixture, regulating it as desired. According to Carothers, among the diaminedicarboxylic acid pairings which could produce polyamides of interest, was pairing 66. Again at the beginning of 1935, Berchet was charged with the preparation of the two monomers and the polymer. The preparation of polyamide 66 was completed (12.5 g of polymer, yield 90%) on 1 March 1935. The polyhexamethylene adipamide appeared as a solid corneous mass which melted at 252-254C from which fibres were obtained; however, its high melting point led to fears that it might decompose during melt spinning. In the spring of 1935, the first polyamide 5-10 filaments were obtained using a stainless steel spinneret and the melt spinning process (a completely innovative technique); these were twisted to turn them into threads, each consisting of 24 filaments and with a count of 123 denier, in other words about 5 denier per filament (compared to 2 denier per filament of natural silk). Using these threads, the first fabric in completely synthetic fibre was made. From the summer of 1935 onwards, Carothers group devoted itself exclusively to polyamide 66, for which industrial production seemed possible, whereas work on polyamide 5-10 was abandoned; this product could not be industrialized since the availability on the market of castor oil, from which sebacic acid was obtained, was limited. In the case of polyamide 66, on the contrary, adipic acid could be synthesized from benzene, obtainable from the petrochemical industry in practically unlimited quantities, even though the technique for the industrial synthesis of hexamethylene diamine was still unknown. Since polyamide 66 had the potential for commercial success as a textile fibre, it was decided to use it to produce high quality yarns which could compete with those in natural silk. The use of polyamide 66 to make a fibre very similar to wool (Fiber W), on the other hand, was abandoned for economic reasons. The industrial synthesis of the monomers turned out to be well-suited to the large-scale production of the polymer, which did not present particular problems on the industrial scale. To transform the polymer into fibres, melt spinning was chosen. However, at the process temperature (above 260C), a small quantity of the polymer decomposed in the melting chamber, with the formation of gaseous products which caused the

VOLUME II / REFINING AND PETROCHEMICALS

919

POLYMERIC MATERIALS

interruption of the filaments. Pressurizing the melting chamber allowed melt spinning to become an industrial process. A pilot plant, about a tenth of the size of a commercial plant (with a production capacity of about 125 kg of yarn per day) came into operation on 11 July 1938. From the day of the first synthesis of polyamide 66, DuPont had maintained absolute secrecy regarding the new fibre and its developments, but word did get out since as early as 1937 bristles made from polyamide 66 scraps and rejects had been marketed (without divulging their chemical composition), sold with the trade name of Exton Bristles and used to make toothbrushes (this was the first use of what was later to become nylon). In September 1938 the first patents were registered. The New York Times reported the new fibre, and wrote in an editorial: A new kind of rayon has been produced []. Because of its impact on the silk trade [] Japan has reason to worry. In October of the same year, during the New York World Fair, in the section of The World of Tomorrow, Charles Stine, vice president of DuPont, presented the new fibre with these words: I am making the first announcement of a brand new chemical fiber. This textile fiber is the first man-made organic textile fiber prepared wholly from new materials from the mineral kingdom. I refer to the fiber produced from nylon []. Though wholly fabricated from such common raw materials as coal, water and air, nylon can be fashioned into filaments as strong as steel, as fine as a spiders web, yet more elastic than any of the common natural fibers. Ten years earlier, he himself had promoted the core research programme which led to its creation, and had warmly supported Carothers employment. Nylon was an instant commercial success, and DuPont had to nearly triple the planned plant, which was not yet fully operational, to meet the requests arriving from all over the world. Womens stockings in nylon (Nylons) were presented by DuPont for the first time at the International Exhibition in San Francisco in February 1939. The following year, more than 1,300 tonnes of nylon were produced (most of which were turned into womens stockings) with a value of about 9 million dollars and providing a profit of about 3 million dollars, amply repaying the costs of research and development. Within the space of two years, more than 30% of the womens stocking market belonged to DuPont Nylons. When the United States entered the war in 1941, nylon became a strategic material, used to reinforce the tires of lorries, cables and parachute silk, in addition to nets, cables and coverings for antiaircraft barrages, items of military apparel (replacing wool and cotton), haulage cables, etc.

Industrial production of the polymer

Weighed in stoichiometric quantities, hexamethylene diamine and adipic acid are sent to a boiler where hexamethylene diamine adipate (salt 66) is formed. It is dissolved in water and sent to an evaporator, where the water is removed and polymerization begins. The contents are then sent to a boiler where polymerization proceeds at low pressure, first at 180C and then at 250-275C. The polymerized mass is extruded from the lower part of the boiler, passed over a moulding roller, cooled with jets of water and reduced to small chips.
Industrial production of fibres

Nylon 66 fibres are made by melt spinning. The polymer is melted on a silver grid in the presence of very pure nitrogen and the molten mass is then pushed through a spinneret in perfectly controlled quantities by a metering pump. The yarn, soaked in antistatic oils, is cooled in a cold air column and wound around bobbins. It is then subjected to cold drawing (drawing ratio of 1 to 4 or above, depending on the tenacity required) to confer on it the desired mechanical properties. Most of the continuous filament is subjected to a texturizing process. If, rather than a continuous thread, it is desired to produce staple, the tow is drawn, crimped and then cut into the desired lengths. Nylon 66 is commercialized as multifilament, monofilament and staple, with a vast range of counts. The fibres may be opaque, semi-opaque or shiny, and their section may be either circular or a variety of other shapes (star-shaped, trilobed etc.) whenever it is desired to give the textiles a particular appearance.
Properties and uses of the fibres

The tenacity of the fibres when dry ranges from 3.7-4.1 g/dtex (for staple; g refers to the gramme force) to 4.2-5.3 g/dtex (for continuous filament), and reaches 8.1-8.5 g/dtex for high tenacity fibres. When damp, tenacity decreases by 10-20%. The elongation at break ranges between 19 and 32% for continuous filament and reaches 40% for staple. Elasticity is high and the recovery from deformation is total as long as the limit of elasticity is not exceeded. Resistance to abrasion is extremely good, and hygroscopicity (4%) is high compared to other synthetic fibres (polyacrylonitrile 2%, polyesters 0.4%). The fibres can be used at up to 150C (after 6 hours at this temperature they begin to yellow) and are flammable (though less so than those of cotton or artificial silk). Nylon 66 fibres are resistant to alkalis, soluble in cold formic acid and sulphuric acid, are not damaged by the solvents used in dry cleaning and have a good affinity with numerous classes of dyes (acid,

920

ENCYCLOPAEDIA OF HYDROCARBONS

SYNTHETIC FIBRES

premetallized, chrome, etc.), which provide colours which remain fast despite light and washing. Among the numerous finishing operations, thermosetting is important to shape and set the fabrics; by eliminating any residual retraction, it ensures that their size remains stable with use and washing. Nylon 66 fabrics are very resistant to crumpling and, where necessary, can be ironed at temperatures lower than 150C. Given their high elasticity, appearance, feel, resistance to abrasion and repeated folding, and low hygroscopicity, Nylon 66 fibres are ideal for durable and comfortable fabrics for windproof jackets and sports wear, womens wear, underwear, hosiery and socks made of blends with wool or cotton.
Nylon 6

for staple, on the other hand, is hot drawn, worked with warm water to eliminate any traces of monomer, crimped and cut into the required lengths. The texturing of continuous filaments and product types are similar to those of Nylon 66. The properties of Nylon 6 fibres and textiles, and their uses, are basically identical to those of Nylon 66, with the difference that the former are easier to dye and that, since they melt at lower temperatures, greater caution is required when ironing. Nylon 6 acquired commercial importance (especially in Germany) in the early 1950s, and later vanished almost completely from the market.
Nylon 11

From 1930 onwards, Carothers had researched the polymerization of e-aminocaproic acid with Berchet, and together they had obtained, alongside a polymer with a low molecular weight, a cyclic compound which was named lactam. Considering their research complete, Carothers and Berchet published a study concluding that e-caprolactam did not polymerize. In the spring of 1937, DuPont, in negotiations to exchange patents, informed IG Farbenindustrie about obtaining polyamide 66 (the future nylon), certain that its patents would be unassailable. IG Farbenindustrie researchers, and especially Schlack, immediately reread Carothers publications on e-caprolactam, and in 1938 heated it obtaining poly(e-caprolactam), or Nylon 6, later known as Perlon in Germany. The polymerization of e-caprolactam takes place by heating at 250-270C in an autoclave in an aqueous solution, in the presence of Nylon 66 salt or e-aminocaproic acid as initiators. Acetic acid or other process terminators may be added to control the degree of polymerization. In continuous polymerization, a concentrated aqueous solution, which may contain an initiator, is sent into a tube reaction chamber, consisting of a single tube or a battery of tubes, heated to 250-270C. In this way, the reagents are heated gradually as they run through the tubes. The polyamide thus produced is then turned into granules. Nylon 6 melts at 215-217C and is more stable than Nylon 66 when exposed to heat; melt spinning thus presents fewer difficulties. In general terms, the process is identical to that used for Nylon 66. Another melt spinning process involves melting in an extruder, whose screw channels the melt into the spinning head, where a metering pump pushes it through the spinneret. The filaments are cooled in air to 18-20C (relative humidity 45-55%) and then cold drawn (ratio of 1 to 4) at 15C (relative humidity 60-70%). The tow

This polyamide, known as Rilsan, was created by Organico SA (France) in collaboration with SNIA Viscosa and produced, as well as in France, in India, Brazil, and the ex-Soviet Union. The polymerization of 11-aminoundecanoic acid, made from castor oil, is similar to that of e-caprolactam, and it is melt spun at 215-220C. Usually, polymerization and spinning are continuous, without an intermediate granule stage. Nylon 11 melts at 189-190C, and this represents its major drawback in many applications, since it cannot be ironed. It is produced as a continuous filament, as staple and as monofilament. The fibres are similar in appearance to the other polyamides; the same can be said of their mechanical properties. Nylon 11s resistance to oxidation is higher than that of the other Nylons (it yellows at 150C in air). Given its low absorption of water, Nylon 11 is not easy to dye; this may also be done in the bulk during spinning. Like the polyamides examined above, Nylon 11 is used for knitwear.
Polyaramids

Polyaramids (or aramids) are totally aromatic polyamides, obtained from diamines and aromatic diacids. The introduction of aromatic rings into the polymeric chains of polyamides leads to a raising of their melting point (polyaramids usually decompose before melting); they can therefore only be spun from solutions in strong acids (sulphuric, nitric) and the fibres obtained are strongly heat-resistant. The first polyaramid fibre, poly(m-phenylene isophthalamide) was commercialized in 1967 by E.I. DuPont de Nemours with the name Nomex. Nomex is obtained by the interfacial polymerization of m-phenylene diamine with isophthalic acid dichloride. The fibres, which can resist temperatures of 300C for a considerable time, are used for fire-fighting equipment (to provide flame resistance) or to make clothes which must resist high temperatures. In the

VOLUME II / REFINING AND PETROCHEMICALS

921

POLYMERIC MATERIALS

early 1970s, Teijin in Japan marketed Conex or Konex, a fibre with a composition similar to Nomex. During the same years, the Soviet Union began to produce Fenilon, similar to Nomex, for civilian and military purposes and as a material suitable for the aerospace industry. The studies by E.I. DuPont de Nemours researchers continued, and in 1970 another fibre with a very high elasticity modulus was introduced on the market, to be used as a reinforcement for tires: poly( p-benzamide), initially given the trade name Fiber B. In 1975 poly(p-phenylene terephthalamide) was commercialized, with mechanical properties similar to Fiber B; from this it was possible to obtain fibres for use in rigid compounds. Poly( p-phenylene terephthalamide), obtained by the interfacial polymerization of p-phenylene diamine with terephthalic acid dichloride, was sold with the trade name Kevlar. Kevlar fibres are obtained by dry or wet spinning from solutions in sulphuric acid, in which the extremely rigid chains of the polymer (all fully in the trans-conformation, since the cis-conformation is sterically hindered) form a lyotropic mesophase in which the liquid crystals orient themselves parallel to the axis of the fibre when they are extruded, making drawing to increase tenacity pointless. Kevlar fibres decompose without melting at over 500C and have extremely high resilience and tenacity (25 g/denier, seven times stronger than a steel wire, with the advantage that their specific weight is 1/5 that of steel). They are used to reinforce radial tires and above all for advanced composite materials, widely used in aeronautical and space technologies. Other uses mainly concern special clothing (bullet-proof vests, helmets, protective gloves), sports wear, etc. The fibres previously known as Arenka and subsequently as Twaron, made in the Netherlands by Akzo NV, are identical to Kevlar in terms of chemical structure and properties.

12.7.3 Polyester fibres

These are polymeric synthetic fibres consisting at least 85% of an ester of terephthalic acid with a glycol. Despite enormous amounts of research, polyethylene terephthalate (PET) fibres are still unequalled, and are more widely used than those in Nylon. The history of PET fibres also begins with Carothers research on these polymers immediately following his employment by E.I. DuPont de Nemours. One of the very first polyesters synthesized by Carothers as early as 1929 was that by condensation between phthalic acid and ethylene

glycol. The results were not encouraging; a vitreous resin with low molecular weight (about 4,000) was obtained, leading to the abandonment of this research after publication of the results. Even today, it is unclear why Carothers and his assistants did not try replacing phthalic acid (carboxylic group in ortho position) with terephthalic acid (carboxylic group in para position). During this research, by reacting an organic dicarboxylic acid with 16 carbon atoms with propylene glycol, a polyester had been obtained with a molecular weight of about 12,000, from which extremely robust long filaments could be made by cold drawing. Although possessing far better mechanical properties, especially elasticity, than rayon and natural silk, these fibres were soluble in all liquids used for dry cleaning, deteriorated if treated with water, and had a melting point below 100C. For these reasons, they could not be used to make textiles, since these would have been neither washable nor ironable. As early as October 1934, Edgar Spanagel, also a member of Carothers group, had prepared PET, but this research was not pursued for various reasons. First, polyamides seemed far more promising as fibres; second, the melting point of PET was considered too low for potential use as a fibre; and finally, it seemed too easily hydrolysable. In 1940, the Englishmen Whinfield and Dickson of Calico in Manchester made PET from terephthalic acid and ethylene glycol, patenting the procedure the following year. This research was then continued by ICI, which had purchased the patent from Calico with exclusive worldwide rights for twenty years (with the exception of the United States). In 1945, ICI researchers completed the development of the process for making PET and its fibres, which were marketed in 1947 with the trade name Terylene. Fibres identical to Terylene were produced almost immediately in the major industrialized countries on licence from ICI; these were known as Trevira in Germany (Hoechst), Terital in Italy (Montecatini) and Tergal in France (Rhodiaceta) to mention only European countries. Although a Patents and Processes Agreement was in force between E.I. DuPont de Nemours and ICI, the latter, due to the safety measures called for by the war, had not informed DuPont about Whinfield and Dicksons discovery. In 1944, rumours had reached DuPont regarding the development in Great Britain of a new fibre, Terrylite. Within a few weeks, DuPont technicians had obtained a sample which, based on the name, they assumed to be PET. In October 1944, with great scepticism but hoping that Carothers patents of 1930 would cover its expenses, DuPont resumed research on PET. Using Carothers polymerization

922

ENCYCLOPAEDIA OF HYDROCARBONS

SYNTHETIC FIBRES

technique, a polymer with high intrinsic viscosity and high melting temperature was synthesized, which could easily be turned into fibres with excellent mechanical properties after cold drawing. In early 1945 a meeting took place between English and American patents experts, called by ICI and DuPont. At the end of this meeting, the English agreed that Carothers basic patents covered those for Terylene, but that this had not stopped Whinfield and Dickson obtaining their own patents. As a result, ICIs patents were not valid in the USA, and DuPont was able to commercialize its PET with the name Dacron. Thanks to the experience matured in the field of synthetic fibres with Nylon and Orlon, DuPont acted far more decisively than ICI in developing this new fibre, Fiber V. Although the two giants continued to exchange information about it, DuPont developed Fiber V at far higher speed than Terylene; this increased further after 1948, the year in which the Patents and Processes Agreement ceased to be renewed. The use of Fiber V to reinforce the frameworks of car tires did not provide good results, though it had all the mechanical prerequisites. In March 1947 it was decided to abandon this market, and Fiber V was developed as a textile fibre, potentially in competition with Nylon and Orlon. Given the numerous similarities between the properties of Fiber V and those of wool, a small amount of a fibre identical to the latter was produced. Through external companies, in February 1948, a gabardine was made with extremely encouraging results, since it had properties identical to those of wool, and was very resistant to creasing thanks to the extremely high resilience of PET fibres. Having resolved the problems linked to the supply of raw materials and monomers (in particular those relating to the production of dimethyl terephthalate), to polymerization and spinning (the continuous process, without the intermediate granule stage, turned out to be economically preferable), to the reduction of static electricity in the articles made and finally to pilling (in other words the formation of small bobbles on the surface of articles due to friction, resolved by using filaments with a non-circular section or anti-pilling fibres), Fiber V was put on the market in 1953 with the trade name Dacron.
Industrial production

transferred to an autoclave heated to 290C where, under vacuum, the glycol gradually formed as polymerization takes place is eliminated. The process ends when the PET has reached a molecular weight of about 18,000. At this point the polymer can be extruded, cooled with water and reduced to chips. Melt spinning is used, heating the polymer chips until they melt and channelling the melt into the spinnerets (holes about 0.3 mm in diameter) using a metering pump. Another way of carrying out the polymerization involves the elimination of water, starting directly from terephthalic acid and ethylene glycol in cascade reactors up until the final condensation, after which the molten polymer passes directly on to spinning (continuous process). This type of process, as well as avoiding the need to melt the polymer a second time, presents numerous other advantages, both technical and economical. As they exit the spinneret, the filaments are solidified by cooling in air, gathered on rollers at extremely high speed (1,000-1,500 m/min) and then subjected to hot drawing (70-90C). For production as staple, after cooling, the filaments exiting the spinnerets are gathered in tows and placed in purpose-built containers; they are then removed from these to be subjected to steam drawing. The drawn tow is then crimped and finally cut into the desired lengths.
Properties and uses of the fibres

The dimethyl ester of terephthalic acid is made to react with an excess of ethylene glycol in the presence of very small quantities (0.01-0.015%) of lithium or magnesium salts in a nitrogen stream to entrain the methanol formed, heating to 200C until the latter is completely eliminated. The product of the reaction is

If cooled suddenly, molten PET does not crystallize (density 1.34 g/cm3) and can easily be oriented by drawing. It crystallizes when heated to temperatures above 80C, with a maximum crystallization velocity at 180C. Consequently, reheating immediately after drawing has the effect of creating highly crystalline fibres (crystallinity above 40%, density 1.38-1.39 g/cm3) with high tenacity (from 5.8-7.2 g/dtex for continuous high tenacity filaments to 2.3-5.0 g/dtex for staple). The possibility of intervening during the transformation into fibres makes it possible to obtain yarn with different properties: these range from high tenacity continuous filament for tire coverings or other industrial uses, to a staple very similar to wool for use in knitwear, from fibres for crease-proof textiles to those used for curtaining, etc. PET fibres can be made with sections of different shapes, in addition to circular, producing yarns with different appearances. The continuous filaments can easily be texturized, making it possible to use these, in wool or cotton blends, in textile applications for which staple is indispensable. The mechanical properties of PET fibres are not affected by humidity. The elongation at break ranges

VOLUME II / REFINING AND PETROCHEMICALS

923

POLYMERIC MATERIALS

from 8-11% for high tenacity filaments to 20-50% for staple. The elasticity modulus one of the characteristics of PET fibres is high (from 100-130 g/dtex for continuous high tenacity filaments to 30-70 g/dtex for staple). The crystalline structure of PET prevents viscous flow under stress; creep is therefore extremely limited and the fibres cannot be deformed. The absorption of water by PET fibres is very limited (0.4-0.5%), their melting temperature is 260C and they retract at around 230C; as such, these fibres can be ironed at temperatures up to 200C, more than sufficient to add or remove creases. PET fibres have excellent resistance to chemical agents, especially those used for dry cleaning. Since their hydrolysis velocity is low, they resist well both to water and to acids and bases; they also present good resistance (better than that of polyamides) to sunlight and can be dyed using dispersed dyes. As already mentioned, PET fibres are used both on their own and in blends with wool or cotton. In some cases they may be prone to pilling, as is the case for other fibres. PETs strong points are the silk-like textiles used for womens clothing and furnishings, sports fabrics (the use of microfibres makes it possible to make items which are at once breathable and waterproof), curtaining, safety belts for cars, padding, clothing of cotton type, etc.
Totally aromatic polyesters

altered by humidity, they have excellent resistance to impact (much appreciated when they are used for advanced composite materials), excellent resistance to abrasion, good resistance to high temperatures (240C for constant use, 340C for brief periods) and high chemical stability (to acids in particular). For these reasons they are widely used for cordage, work gloves, protective clothing, acid-resistant filters, materials for friction, advanced composite materials, etc.

12.7.4 Polyvinyl fibres

These are synthetic fibres obtained by addition polymerization from vinylic and vinylidenic monomers. Poly(vinyl chloride) was the first vinyl polymer from which fibres were obtained (1913), but these achieved little success. The most important are the polyacrylic fibres obtained from polymers based on acrylonitrile; of secondary importance are those obtained from polymers of vinyl chloride and vinyl alcohol.
Polyacrylic fibres

Like aromatic polyamides, aromatic polyesters form liquid crystals. However, unlike the former, which form these in solution (lyotropic liquid crystal polymers), the latter form liquid crystals when molten (thermotropic liquid crystal polymers); whereas the former must be spun from a solution (their melting point is close to that of decomposition), the latter can be turned into fibres by melt spinning. The first aromatic polyester to be developed commercially was Xydar, by Dartcore, USA (December 1984), which derived from Carborundum, USAs EKKCEL (1972). Vectra (plastics and fibres) and Vectran (fibres only) are two totally aromatic polyesters commercialized in 1986 by the then Celanese, now Ticona GmbH (Germany). All these materials are prepared by condensation between p-hydroxybenzoic acid, terephthalic acid, and 4, 4-dihydroxy diphenyl. Given the low viscosity of the melt resulting from its liquid crystal structure, spinning does not present particular problems. Spinning is followed by thermal treatment at 300C or above, thus obtaining an improvement of mechanical properties due in part to further polymerization. Vectran fibres, like Kevlar fibres, have high tenacity and elasticity modulus; they do not absorb water, their physical and mechanical properties are not

Currently, not all polyacrylic fibres consist of homopolymers of acrylonitrile, but of its copolymers with other vinylic monomers, introduced into the polymeric chains to avoid problems with production and dyeing. If the content in structural units deriving from acrylonitrile is equal to at least 85% in weight, the fibres are described as acrylic, the most important; if the content is between 85% and 50% they are known as modacrylic. The first polyacrylonitrile (PAN) fibres appeared in 1942, when in DuPonts laboratories it was discovered that this polymer is soluble in dimethylacetamide (DMAC) and in dimethylformamide (DMF). PAN could not be turned into fibres using melt spinning like nylon, since it decomposes before melting. The first PAN fibres (Fiber A) obtained from solutions in DMF by dry spinning from a solution or wet spinning from a solution immediately showed very interesting characteristics, such as a high melting point and good chemical stability. When not drawn, or only slightly drawn, they had properties similar to those of wool, whereas when drawn their properties were similar to silk; they also had excellent resistance to light, chemical products and bacteria. The significant drawback of Fiber A was that it could not be dyed, and non-dyeable fibres have no commercial potential. A further factor which contributed to slowing down its development was that Vinion N (a 50% acrylonitrile-50% vinyl chloride copolymer) commercialized by the Carbide and

924

ENCYCLOPAEDIA OF HYDROCARBONS

SYNTHETIC FIBRES

Carbon, which seemed economically more viable, had shown that DMF was strongly toxic. Due to the war, it was also difficult to find the raw materials for production (those used for strategic materials such as nylon had precedence). It was pointed out to the military that Fiber As excellent resistance to light, chemical products and bacteria could resolve many of their problems in the jungle (such as tents, laces and tarpaulins in cotton, which deteriorated rapidly) and this allowed DuPont to obtain raw materials more easily. Vinion N turned out to be inferior to Fiber A due to its lower melting point and greater solubility in solvents. The problem of DMFs toxicity was resolved by adopting the dry spinning from solution process, carried out in closed chambers. At the end of 1944 the problem of dyeing remained unresolved; this is considered the Achilles heel of all hydrophobic fibres (nylon and polyesters). After exhausting all attempts to find suitable dyes, it was decided to render Fiber A dyeable by modifying its chemical structure. It was discovered that a 95% acrylonitrile-5% 2-vinylpyridine copolymer (Orlon A-3) could be dyed. However, 2-vinylpyridine was not available in large quantities, and was also extremely expensive. At the end of 1948, then, the problem of the dyeability of Orlon had not been fully resolved, and it was unclear whether it was better to produce modified or non-modified Orlon, since the latter could be widely used to replace cotton for tents and tarpaulins. Since Orlon as a continuous filament did not become a successful product, attempts were made to produce it as staple Orlon A-4, a copolymer of acrylonitrile with 5-methyl-2-vinylpyridine, easier to dye than Orlon A-3. Since the presence of cuprous ions in the dye bath increased the reactivity of PAN with acidic dyes, and the problem of dyeing thus appeared to have been resolved without modifying the polymer, the production of staple (Orlon Type 41) consisting of homo-PAN began. Orlon Type 41 was a failure due to the difficulty of weaving caused by static electricity, the non-uniformity of the fibrils and unpleasant odours when blended with wool. A solution to the problems presented by PAN came from the rapid development of the 94% acrylonitrile-6% methyl acrylate copolymer, Orlon A-6 (Orlon type 42 yarn). The staple turned out to be ideal for sweaters and wool blend worsteds; by the end of 1951 sales had reached and superseded 50,000 tonnes per year, and Orlon became a great commercial success.
Industrial production

in its monomer, so that bulk polymerization creates enormous problems), the most widely used is that of radical polymerization in a solution, using highly polar organic compounds (DMF or dimethyl sulphoxide) or aqueous solutions of inorganic salts (60% zinc chloride, 44-50% sodium thiocyanate, calcium thiocyanate and perchlorates) as solvents. The advantage of this process lies in the fact that the polymer solution can be spun directly. In the dry spinning process (generally used to produce continuous filaments) a 20-30% solution of the polymer in DMF is extruded at 80-150C in a vertical tube, in which a stream of hot air (230-260C) causes the evaporation of the DMF (which is recovered) and the solidification of the filaments which are gathered on bobbins. The fibres, which still contain 10% DMF, are then washed with water and subjected to drawing at 80-110C in hot air, or at 70-100C in water. In wet spinning (used to produce staple) the polymer dissolved in DMAC or in DMF is extruded into water, in which the filaments coagulate forming a bundle which is washed, drawn in hot water, crimped and cut into the desired lengths.
Properties and uses of the fibres

Among the various ways of polymerizing acrylonitrile (remembering that it is soluble in water, whilst polyacrylonitrile is insoluble both in water and

PAN fibres are essentially amorphous and soften above 225C. They are very stable when heated and tend to yellow if exposed for long periods to temperatures over 130C; their tenacity decreases by less than 4% after 100 hours at 150C. Since they generally consist of copolymers of acrylonitrile in addition to homo-PAN, they present a broad spectrum of properties, depending on their chemical composition and the way they have been treated. The shape of their section is circular for continuous filaments and dog bone for staple. Staple has a tenacity of between 2 and 3 g/dtex whilst continuous filament, which is less used, is more tenacious (4-4.2 g/dtex). Elasticity is not high (recovery of 50-60% for a deformation of 10%). The absorption of humidity (above 2% at 20C) is among the highest for synthetic fibres. Despite this, it dries very rapidly and can be used for wash and wear clothing; it also has good resistance to sunlight and to chemical agents (dilute acids and bases, liquids for dry cleaning, etc.). Dyeing is carried out using either basic dyes, which provide fibres with solid and brilliant colours, or with acid dyes. The articles produced cannot be ironed, since they would become deformed. Worldwide production of acrylic fibres is extremely high (millions of tonnes per year); they are used both alone and in blends with wool for outer knitwear, sports socks and exterior curtaining.

VOLUME II / REFINING AND PETROCHEMICALS

925

POLYMERIC MATERIALS

Modacrylic fibres

Poly(vinylidene chloride) fibres

These are acrylic fibres which contain less than 85% acrylonitrile. Among the numerous types, it is worth mentioning Verel and Dynel, both of which have good flame-retardant properties. Verel (Tennessee Eastman, USA) contains acrylonitrile (about 60%) and vinylidene chloride and is produced only as staple (including a high retraction type) by wet spinning from a solution. Easy to dye with basic, dispersed and premetallized dyes, it is mainly used in blends with other fibres (natural, artificial or synthetic); it has modest mechanical properties (tenacity 1.7-2.3 g/dtex, deformation at break 35-40%), softens at around 200C and resists ageing better than other synthetic fibres, wool and cotton. It dissolves in hot acetone. Dynel (Union Carbide, USA) is a 40% acrylonitrile-60% vinyl chloride copolymer. The fibres (including a high retraction type), obtained by wet spinning from a solution, are thermoplastic and retract even in boiling water; they are dyed at temperatures below 100C in the presence of swelling agents. Their tenacity is low (2-3.8 g/dtex) and their elongation at break ranges from 14-40%. They are used for carpets, industrial textiles, protective clothing and furnishings in places covered by fire regulations (cinemas, theatres, etc.).
Poly(vinyl chloride) fibres

Fibres of poly(vinylidene chloride), or more accurately of copolymers of vinylidene chloride/vinyl chloride (Saran, 20% vinyl chloride) are melt spun at about 180C and are almost dyed in bulk. They are non-flammable, have low tenacity, soften between 120 and 160C and are basically used for industrial textiles.
Poly(vinyl alcohol) fibres

Poly(vinyl alcohol) fibres, obtained from the partial hydrolysis of poly(vinyl acetate), are wet spun from aqueous solutions, coagulated in a sodium sulphate solution and treated at 240C to render them more compact. They are then made insoluble in water by acetylation (30-40% in moles) and partial crosslinked with formaldehyde. Poly(vinyl alcohol) fibres are shiny and irregular in section, have high tenacity (up to 8 g/dtex), good heat resistance (they retract 10% at 220C), soften at 250C, resist ageing well and can be dyed easily. They are used almost exclusively in Japan (Kurashiki Rayons Kuralon), in blends with cotton or rayon, to make textiles for umbrellas, awnings, carpets, etc.
Polytetrafluoroethylene fibres

Poly(vinyl chloride) (PVC) fibres were the first synthetic fibres ever made, in 1913. In 1934 IG Farbenindustrie (Germany) presented the PC fibre (post-chlorinated PVC, to render it soluble in acetone) and in 1941 Rhodiaceta made PVC filaments spun from a mixture of carbon sulphide and acetone. Montefibre (Montedison, Italy) produced Leavin, crystalline fibres from syndiotactic PVC (spinning from solutions in cyclohexanone), far more resistant to heat than atactic PVC. PVC fibres have low tenacity (3 g/dtex), are produced as continuous filaments and as staple, are thermoplastic (they soften at around 80C) and are not attacked by acids and bases, but are particularly sensitive to ketones; they are dyed in baths with azoic developing dyes or using dispersed or solution dyes (for black). Furthermore, these fibres are strongly flame-retardant; they dehydrochlorinate and brown when exposed to heat. Their flame retardant properties make them ideal for furnishings and industrial textiles, thanks in part also to their resistance to acids and bases. Different types of more or less modified PVC fibres can be found on the market; these include thermoretracted fibres (Thermovil, Movil T), which resist temperatures of up to 100C and those obtained from chlorinated PVC (Clevil).

Polytetrafluoroethylene (PTFE) is insoluble in all solvents and decomposes before melting; its fibres are therefore obtained by extruding a dispersion of extremely tiny particles of the polymer in a coagulant bath of water and hydrochloric acid. The filaments thus obtained, made of particles separate from one another, are then heated rapidly to 390C, so that the particles syntherize to form a continuous filament. They can also be melt spun from copolymers of tetrafluoroethylene with propylene, perfluoro propylene or perfluorovinyl ethers. PTFE fibres have an extremely low frictional coefficient, total resistance to all chemical agents and excellent heat resistance (they can be used between 70C and 280C), but have low tenacity (1.3 g/dtex). Their value lies in their high chemical inertia and heat resistance; for this reason they are used for industrial and space applications.

12.7.5 Polyolefin fibres

Polyolefin fibres derive from olefin (basically ethylene and propylene) polymers, and include polyethylene and polypropylene fibres.
Polyethylene fibres

Polyethylene fibres have never had particular commercial importance, given their poor mechanical

926

ENCYCLOPAEDIA OF HYDROCARBONS

SYNTHETIC FIBRES

and textile properties, which have led to their use only for special applications. Even the synthesis, at the beginning of the 1960s, of polyehtylene with a high molecular weight (2106), named UHMWPE (Ultra High Molecular Weight PolyEthylene) and characterized by physical and mechanical properties far superior to those of conventional polyethylene (molecular weight 104) did not bring any changes, since the product could not be spun due to the extremely high viscosity of its melt. In 1976 the gel spinning process was finally discovered at the DSM laboratories (Netherlands); this involved drawing (drawing ratio of 1 to 30) fibres from a diluted solution of UHMWPE in xylene or decaline, with a tenacity and elasticity modulus close to the theoretical values for planar zigzag chains. Among the various high tenacity fibres in UHMWPE of commercial interest spun from a gel are Allieds Spectra 900 and 1000 (USA, 1984) and Dyneemas Dyneema SK90 (Netherlands, 1986). These fibres are chemically stable, have melting points between 145 and 155C (depending on the drawing ratio) and preserve their mechanical properties up to temperatures close to their melting point. They are ten times more robust (free breaking length 336 km) than those of steel and are used either as such, or in composites, or to reinforce other polymers (in loud speaker cones, bows, bows for musical instruments, helmets, etc.). Due to their low density (1 g/cm3), high tenacity, high resistance to impact and atmospheric agents, resistance to abrasion, high stability in the presence of ultraviolet light and excellent insulating and water-repellent properties, high tenacity UHMWPE fibres are used for cordage and cables, bullet-proof vests, protective clothing, parachutes and construction materials.
Polypropylene fibres

The fibres are highly crystalline, melt at between 170 and 174C, and have low density (0.90 g/cm3). They can be prepared with varying degrees of tenacity (up to 9 g/dtex), have good mechanical properties and resistance to viscous flow, present good resistance to acids and alkalis and many chemical products (they swell in hydrocarbons), are not easy to dye (dyeing, as mentioned above, is done in solution with thermostable pigments) and have low resistance to light (stabilizers are also used for purposes which do not require long exposure to sunlight). Given their lack of sensitivity to water, resistance to abrasion and cyclical bending stresses, lightness and tenacity, these fibres are used for manufacturing fishing nets, cords, industrial filters, in the automobile industry, as a geotextile (synthetic grass for sports fields), carpets and rugs (characterized by their ease of cleaning, brilliant colours, resilience and resistance to decay). On their own or in wool blends they are used for knitwear, underwear and sports wear (double layered garments with an inner layer in polypropylene and outer layer in natural fibre, ensuring the rapid removal of sweat by capillary action, keeping the skin dry).

12.7.6 Polyurethane fibres

Today, polyurethane fibres are the elastomeric fibres (Spandex) commercialized by E.I. DuPont de Nemours (USA) in 1962 (Lycra) after twenty years of research aimed at obtaining synthetic elastomeric fibres to replace those in natural rubber covered with cotton. As early as 1942, DuPonts researchers had observed that N-substituted (Type 8 Nylon) Nylon could be turned into filaments with elastomeric properties. During this research, it emerged that to obtain elastomeric fibres it was necessary to make block copolymers consisting of flexible segments (to give elasticity) and rigid segments (to confer high melting temperatures). The preparation of these block copolymers was made possible by the discovery of the interfacial polymerization method. At the beginning of 1954, by extruding a prepolymer of Adiprene (an elastomeric polyurethane made by Orchem, USA) in a diamine solution, fibres were obtained with excellent elastomeric properties. Later, a poly(ether-urea-urethane) was obtained (Type 80), with even better properties, which could be dry spun or wet spun from solutions in dimethylformamide or dimethylacetamide. After resolving the problems relating to their sensitivity to ultraviolet light and proneness to yellowing, these polyurethane fibres were commercialized (1962) with the names Lycra for multifilaments

The discovery of isotactic polypropylene by Giulio Natta (1954) led to research on the potential for making fibres from it; these were produced on an industrial scale from 1960 onwards by the Polymer (Montecatini Group, Terni, Italy, now Meraklon) with the trade name Meraklon. Before spinning, antioxidants and sometimes, given the difficulties presented by dyeing, pigments, colorants and granules (granules are more stable than powder) are added to the isotactic polypropylene in powder form. For melt spinning, special types of spinnerets are used to avoid the rupture and deformation of the fibres, due to their high tixotropy when molten. The fibres (with a circular section) are produced either as continuous filaments (drawn at 120C through a die) or as staple (the tow is drawn in steam, crimped, thermoset and cut into the desired lengths).

VOLUME II / REFINING AND PETROCHEMICALS

927

POLYMERIC MATERIALS

and Vyrene for monofilaments. Within the space of two years, these fibres had become one of DuPonts most profitable products, with a return on investments of over 30% net of taxes. Synthesizing Spandex is fairly complex, and involves preparing a prepolymer (polyester or polyether with a low degree of polymerization with hydroxy terminals which later form the rigid blocks in the polymeric chain), reacting this with a diisocyanate (forming isocyanic chain terminals), and then with a diamine or a glycol which form the flexible blocks. Spinning is done using the methods outlined above before the final crosslinking which can also be obtained by simple heating (to be such, an elastomer must be partially crosslinked). Lycra has allowed for the preparation of very fine elastic textiles with a high compression force (not obtainable using rubber fibres); they are easy to dye using acid or plastosoluble dyes. Unlike rubber fibres (minimum count 150 denier), Spandex fibres may have far lower counts (down to 40 denier); Lycras do not break when sewn (unlike monofilaments of rubber), since the needle passes easily between filaments. Given an identical elongation, Spandex has a higher tenacity and elasticity modulus than rubber fibres; this means that, for an identical count, they have a higher (3-6 times) compression force or, in other words, that given an equal compression force they can have a lower count. This property represents the key to their success. Their elastic properties are also good, only slightly inferior to those of rubber. Polyurethane fibres are never used on their own, but always in combination with other fibres (especially polyamides) to confer elasticity on the articles produced (elastic tights, swimsuit, stockings etc.).

fishing nets and lines, as a reinforcement for cement, as cords for tennis rackets, etc.

12.7.8 Carbon fibres

This paragraph will deal with carbon fibres; though not synthetic, they do derive from polyacrylonitrile (PAN). The first carbon fibres were made in the USA by pyrolysis of viscose rayon, but were short-lived; they were soon supplanted by those obtained from the pyrolysis of PAN, which appear in the form of continuous filaments and consist of graphitic carbon. Their high crystallinity confers upon them exceptional qualities: they are extremely tenacious, highly heat resistant and very light (density 1.8-2 g/cm3) and are widely used as a reinforcement in advanced composites. Among the major producers of carbon fibres is Courtaulds (Great Britain). Carbon fibres are made by graphitizing a precursor fibre which may be either rayon viscose or PAN. The continuous fibres of PAN are heated in air (oxidation) at about 300C so as to form ladder structures which, when further heated to temperatures up to 3,000C, loose ammonia and hydrocyanic acid, creating structures containing over 95% carbon. These are then turned into graphitic carbon by treatment in an argon stream at 2,200-2,300C. Carbon fibres have excellent mechanical properties and are practically incombustible (they can be heated until they are cherry red, about 800C, without suffering damage). They are black in colour and are basically used in composite materials, especially when high mechanical performance and low density are required, alongside good fatigue resistance and dimensional stability. The aerospace industry (missiles, artificial satellites, civilian and military aircraft, helicopters etc.) is one of the major markets for carbon fibres and their composites. This is because their use leads to a significant reduction in weight which translates into lower fuel consumption or a larger paying cargo. Carbon fibres and their composites are widely used in the nautical industry (hulls, sails, masts etc.) and in the automobile industry, various sports sectors (tennis, fishing rods, cycling), for conductive materials (electrodes), in textiles (Orlon black) for protection against high temperatures, etc.

12.7.7 Polyacetal fibres

The only known polyacetal fibres are those derived from Delrin (the polyoxymethylene obtained by E.I. DuPont de Nemours by polymerizing formaldehyde, commercialized in early 1960), whose physical and mechanical properties allow them to be used as substitutes for non-ferrous materials (brass, aluminium) in many of their applications. Filaments of Delrin (Tenac SD, Asahi Chemical Industry, Japan), obtained by superdrawing at high pressure, consist of perfectly oriented chains which confer upon them excellent mechanical properties (better than those of steel wire): excellent resistance to heat, chemical stability and resistance to atmospheric agents. Furthermore, these fibres have high creep resistance and do not absorb water: they are used for

12.7.9 Synthetic fibres for medical use

Threads for sutures, meshes to reinforce the abdominal cavity, vascular replacements and hollow fibres for the treatment of blood (artificial kidneys, mechanical

928

ENCYCLOPAEDIA OF HYDROCARBONS

SYNTHETIC FIBRES

lungs) represent the main uses of synthetic fibres in the field of medicine. For these purposes, in addition to possessing suitable physical and mechanical properties, the fibres must be compatible with the tissues of the human body and with blood, have extremely low histotoxicity, must not be carcinogenic and must behave suitably while they remain in the human body.
Threads for sutures

Vascular replacements

Their specific function is to join the tissues of the human body until healing has occurred, after suturing following surgery, wounds or trauma. They must have good resistance to traction, a low frictional coefficient with tissues and sufficient flexibility and elasticity (since the resistance of the knot depends on this). Non-absorbable suture threads (which remain intact indefinitely in the human body) are obtained from the commonest synthetic fibres (polypropylene, polyethylene and their copolymers, Nylon 66, polyethylene terephthalate). Absorbable suture threads (monofilament and multifilaments) were initially made of poly(glycolic acid) fibres (1970) and later of glycolic acid-dilactide copolymers, poly(p-dioxanone), and glycolic acid-trimethylene carbonate copolymers. After about a month the threads dissolve, since they degrade to monomers by hydrolysis of the ester bonds. Before use, absorbable and non-absorbable suture threads are sterilized with ethylene oxide or with ionizing radiation.
Meshes for the reinforcement of the abdominal cavity

Vascular replacements in polyethylene terephthalate fabric (Dacron) or polytetrafluoroethylene (Teflon) are widely used to replace defective veins or arteries (for example in the case of aneurisms) of 6, 8, 10 mm in diameter. Despite their good biocompatibility, the anticoagulant properties of those in Dacron are not high, whereas those in Teflon have good anticoagulant properties. Currently, there are no vascular replacements for blood vessels less than 3 mm in diameter; in these cases it is therefore preferred to replace them with blood vessels taken from other parts of the body.
Fibres for the treatment of blood

The filter membrane in haemodialysis machines (artificial kidneys) consists of bundles of hollow polyacrylonitrile fibres, through which the molecules contained in blood with a molecular weight up to 20,000 can permeate, but not those (including albumin) with a molecular weight of around 70,000, which are retained. The artificial lung is a gas exchanger which serves to supply O2 to blood and remove CO2 from it using membranes consisting of bundles of hollow microporous polypropylene fibres; due to the hydrophobicity of the fibres, their pores are freely permeated by gas but not by blood.

12.7.10 Microfibres and nanofibres

Microfibres

From 1995 it has become routine to use meshes in polymeric materials to reinforce the abdominal cavity (for example in the case of hernias); these are obtained by weaving a wide variety of synthetic fibres, such as polyamides, polyesters, polypropylene or absorbable fibres such as those of poly(glycolic acid) or lactic acid-glycolic acid copolymers. Polyamide (Nylon 66) meshes, the first to be employed (as early as 1944), are now rarely used, since they cause acute inflammatory responses. Of all the materials used to reinforce the abdominal cavity, the most frequently used today are polypropylene and polyethylene terephthalate (Dacron) meshes. The latter, developed simultaneously with the former, are less widely used since they cause a greater inflammatory response and a more significant reaction to the foreign body than those in polypropylene. Polypropylene and Dacron meshes are obtained by weaving a single filament, a pair of filaments or multiple filaments. Meshes in Dacron are sterilized with ionizing radiation, and those in polypropylene with ethylene oxide.

The development of sophisticated and complex processes to obtain synthetic fibres (especially polyamides and polyesters) with increasingly low counts has led to ultrafine fibres (microfibres) with diameters in the order of micrometres (down to single 0.01 denier fibres, with a diameter of about 0.4 mm) used to make fabric and non-fabrics with specific properties. Ultrafine fibre technology was initially developed in Japan to manufacture artificial leathers such as Torays Ecsaine (Alcantara in Europe, Ultrasuede in the USA), similar to suede (easily dyed, widely used for car seats, to cover sofas and armchairs, etc.), consisting of monofilaments as small as 0.1 denier. A further development of microfibres was the creation of high density water-repellent textiles and non-fabrics, used for clothing and sport (so-called microfibre clothing) and cloths suitable for cleaning lenses, jewels, crystals etc.
Nanofibres

The main characteristics of a polymeric nanofibre are a diameter in the order of

VOLUME II / REFINING AND PETROCHEMICALS

929

POLYMERIC MATERIALS

nanometres, and consequently a high surface area and superior mechanical properties. Among the various techniques for preparing nanofibres (spinning, template synthesis, phase separation, autoassembly), electrospinning is the most commonly used for its efficiency and the great simplicity of the equipment required. This process consists in applying a potential difference either to a molten polymer (polyethylene, polypropylene, polyethylene terephthalate etc.) or to a solution of it (polycarbonates, polystyrene, polyurethanes, polyacrylonitrile, polyethylene terephthalate, Nylon 66, poly(vinyl chloride), etc.), causing the formation of a jet of material which then subdivides itself into extremely thin fibres. Nanofibres are used in composite materials (elasticity modulus and resistance of the matrix material higher than those obtained with common fibres, including carbon fibres and Kevlar), in textiles for protection from chemical agents (thanks to the considerable absorbent capacity due to the high surface area of the nanofibres), in membranes (which can be used as high efficiency filters, given the limited volume occupied by the fibres), in bandages sprayed directly onto wounds by electrospinning (avoiding the formation of scars), to help the regrowth of human tissues in the event of disease (nanofibres, having a diameter lower than that of cells, act as frameworks for the regeneration of the tissue), as replacements for soft human tissues, to transport drugs inside the human body, and cosmetic masks. It is important to stress that hitherto synthetic polymeric nanofibres have not been commercialized; these should therefore still be considered subjects for laboratory research, with a view to promising applications in the future.

Bibliography
Cook J.F. (1984) Handbook of textile fibres, Shildon, Merrow, 2v.; v.II. Hearle J.W.S. (edited by) (2001) High-performance fibres, Boca Raton (FL), CRC; Cambridge, Woodhead. Hermes M.E. (1996) Enough for one lifetime. Wallace Carothers inventor of nylon, Washington (D.C.), American Chemical Society and Chemical Heritage Foundation. Holmes D.F. (1983) History of the DuPont companys textile fibers department, Wilmington (DE), DuPont, Textile Fibers Department. Hongu T., Phillips G.O. (1990) New fibers, New York, Ellis Horwood. Hounshell D., Kenly Smith J. (1988) Science and corporate strategy. DuPont R&D 1902-1980, Cambridge, Cambridge University Press. Huang Z.-M. et al. (2003) A review on polymer nanofibers by electrospinning and their applications in nanocomposites, Composites Science and Technology, 63, 2223-2253. Klein W. (1994) Man-made fibres and their processing, Manchester, The textile institute. Mark H.F. et al. (editorial board), Kroschwitz J.I. (editor in chief) (1985-1990) Encyclopedia of polymer science and engineering, New York, John Wiley, 24v. Mishra S.P. (2000) A text book of fibre science and technology, New Delhi, New Age International. Reader W.J. (1975) Imperial chemical industries. A history, London, Oxford University Press. Trossarelli L., Brunella V. (2002) Linvenzione del nylon tra realt, leggende e misteri, Memorie dellAccademia delle Scienze di Torino. Classe Scienze Fisiche, 26, 117-159.

Luigi Trossarelli Valentina Brunella

Dipartimento di Chimica Inorganica, Fisica e dei Materiali Universit degli Studi di Torino Torino, Italy

930

ENCYCLOPAEDIA OF HYDROCARBONS