Nonwovens & Technical Textiles

Revolutionary high performance fibres

Conventional fibres may dominate the technical textile markets but the high performance fibres are needed in some specific applications, say Chidambaram Rameshkumar and Dr N Anbumani as they sketch out some of the high performance fibres..

Natural fibres such as cotton, and silk were used by early man when strength and lightweight were critical. In the last four decades, the development of analytical techniques has the reason for the understanding of the properties. Scientists believe that the molecules within the fibres that align themselves along the fibre axis are the main reason for the strength and modulus. Developments in the method of polymer spinning apart from melt and solution spinning, postspinning operations lead in getting improvement in properties. The Figure1 shows the improvement in the fibre tensile strength during recent years. Advances in the fibre performance have come out because of continuous effort on research and development. In earlier 1920s, the first synthetic fibre was produced from cellulose. In 1940, the nylon was produced through melt spinning. This fibre formation process allowed some limited orientation during extrusion. Further fully oriented fibres can now be spun with liquid crystal polymers for increasing strength and modulus. Table1 shows the strength and modulus of a typical polymer in various forms. The strength of injection-moulded polyamide is about 0.08 Gpa, the same polymer if extruded in textile spinneret then the tensile strength is about five times greater than the earlier one. Drawing process results in a fibre ten times stronger than the injection-moulded fibre. In comparison with above cases, the liquid crystal forming polymer like PPTA can develop nearly a perfect orientation and alignment during the fibre formation. A kilogram of fibres formed from rigid polyamide molecules (Poly Phynelene terephalamide -PPTA) is reported as five times stronger than a kilogram of steel and still five times stiff. Since the density of the aramid (1.4) is one fifth of the steel, this new fibre already is an obvious replacement of metal in many applications. This article gives an expose on some revolutionary fibres.

High performance fibres Loyotropic polymer made fibre Loyotropic polymers are whose solutions respond to solvent type and concentration changes. Fibres produced by this polymer are Aromatic polyamides (PPTA), Poly hydrazides, Poly imdes and hetro cyclic polymers. It has chain extending repeat units, out of which the commercially successful fibre is PPTA. The Figure 2 shows the flow diagram of the Loyotropic polymer spinning process Spinning of aromatic polyamides from anisotropic solution leads to fibre of exceptional strength because of minimum or no chain folding. About 85% of their amide linkages are attached directly to two aromatic rings. The Poly Phynelene terephalamide fibre (PPTA) was commercialised by Dupont in1972 under the trade name, 'Kevlar'. This PPTA is synthesised by condensation of terephthaloyl chloride (TCI) and p-phenylene diamine (PPD) in a mixture of hexamethyl phosphoramide (HMPD) and n-methyl pyrrolidine (NMP) solvents. The poly condensation reaction is carried out at 10 - 20C with an intrinsic viscosity of 4 dl/g, measured in sulpurhic acid is preferred for satisfactory fibre production. The polymer is added to concentrated sulpurhic acid to prepare a 20% solution. Liquid crystalline state is achieved at a polymer concentration of 20% at 100% H2SO4. This Polymer extruded through a spinneret (0.05 - 0.1 mm dia) at about 100C for standard fibre and 70 - 90C for high tenacity fibres through 1.0 cm of air gap dry jet wet spinning into the cold water (0 and 5C). This process is shown in the Figure3. The fibre properties can be altered by the Spin stretch factor (The ratio of fibre velocity leaving the coagulating bath to the to the dope velocity emerging from the spinneret), which is commonly less than 10. Fibre precipitation starts at the air gap. The spinning speed is about 50 mpm. At 100% liquid crystalline state, the maximum anisotropy occurs, leading to the molecular orientation in the spin line. Alignment of liquid crystal domains in the dry jet wet spinning is shown in the Figure 4. The molecular chain linearity and hydrogen bonding combine to give polymer network with almost perfect molecular orientations when the filament emerges from the spinneret. Such fibres

need not be stretched to increase polymer chain alignment. In solution form, they are referred as liquid crystals. The Nomex is identical to that of Kevlar, except that the benzene rings are meta substituted. Nomex and Kevlar have a high specific gravity compared with aliphatic polyamides because of the better alignment of the linear polymer chains. Wet spinning of PPTA gives about fibre tenacity of 1.5 GPa and modulus of 12.4 - 62 GPa. The same polymer spun through the dry jet wet spinning results in tenacity range of 1.8 - 3.7 GPa, and modulus of 25 - 124 Gpa.

The chemical structure and schematic diagram of Kevlar fibre is shown in the Figures 5 & 6. This Para substituted phenyl rings of Kevlar forms a rigidly linear polymer chain resulting in a rod like structure and high degree of inter-chain hydrogen bonding. The ordered structure along the fibre axis is in the form of highly ordered fibril structure. Some of the properties of Kevlar grade fibres are shown in the Table 2. Kevlar 29 Grade is used in belting and Kevlar 49, 149, 981 Grades are used in composite purpose and in protective apparels. Table2: Properties of some aromatic polyamide fibres

Fibre Kevlar 29 Kevlar 49 Kevlar 149 Kevlar 981

Tensile Modulus strength (GPa) (Gpa) 58 2.76 120 2.76 166 2.2 120 3.5

Extension to break (%) 3.7 1.9 1.2 2.8

Thermotropic liquid crystal polymer made fibre Vectran is the known fibre through the liquid crystal polymer made fibre. Liquid crystals have flowable, optically anisotropic structure above a certain temperature and lack in this region sufficient energy for individual molecules to rotate freely in the liquid and domains formed parallel-arranged molecules. Inter-molecules interaction formed in this liquid. Thermotropic liquid crystal polymers allow the molecules to be oriented subjected to orientation relaxation time. The relaxation stress lasts for few seconds whereas the relaxation of orientation can be a matter of several minutes. Molecules orient at higher degree and oriented structure manifold during cooling time due to high relaxation orientation time. Die swell does not occur during the extrusion. The aromatic fibres can be spun at 100 - 200 mpm. The spinning conditions are: Intrinsic viscosity: 1.5 - 3 dl/g Spinning temp: 280 - 400C

Number of filaments: 50 - 500 The LC polymer spinning process is shown in the Figure 7. Random co-polymerisation of HBA (phydrtoxy benzoic acid) and HNA 2.6 (Hydroxy naphtoic acid) results the aromatic thermotropic polyester. The hydroxyl groups are acetylated to facilitate the polymerisation. As a result, the HBA is converted in to p-acetoxy benzoic acid (ABA) with a melting temperature of 230C,while the HNA is converted in to acetoxy naphtoic acid (ANA). The components are taken in the desired ratio and polymerised through the condensation to yield the polymer, which has the random sequence of distribution of two components. Thermotropic polymer attenuates just about 10 cm from the distance of orifice. PET will take 30 cm for attenuation. Heat treatment is necessary to enhance the properties and crystallinity is increased by 20%. The molecular chain structure of the LCP in comparison with the conventional polyester is shown in the Figure 9. Table 3: Properties of some thermotropic liquid crystal polymer made fibres.

Fibre Vectran HS Vectran M

Modulus (GPa) 65-72 53

Tensile strength (Gpa) 2.84-3.21 1.11

Extension to break (%) 3.3.-3.7 2.0

The Vectran fibre properties are shown in the Table 2. It is produced by Celanese acetate Inc, North Carolina. It is established as commendable fibre in terms of high performance applications. The density is about 1.4. It is used as ropes and cables, heat resistant belting, abrasion and chemical resistant conveyors. In aerospace, it is used in a number of application (utilised by NASA). Outstanding cut resistance and vibration damping characteristics are also reported positively. Gel spun fibre High molecular weight Polyethylene (the only flexible chain fibre) could be successfully spun in to fibre through gel spinning system to get high strength and high modulus. The ultra high molecular weight polyethylene cannot be spun through melt spinning due to this polymer has to process high number of chain entanglements/molecules (molecular weight of 6*106). It has very long chains and cannot pass through each other in the time scale of deformation. This will lead to extremely high melt (shear) and elongational viscosities. In gel spinning, controls of molecular-chain entanglements are through appropriate polymer dilution in the solution and morphological control in crystalline process. Solvents used in HMWPE are tetalin, decalin, naphthalene, mineral oil and paraffin oil. PAN and PVA are also spun through the gel spinning system. The flow scheme of Polyethylene solution in gel spinning with effect of

flow rate is shown in the Figure10. The breaking of clusters, discontinuity and fibril formation took place during the fibre formation. Commercial names of HMWPE are Spectra, Dyneema, Tekmilon and Hoechst celanese high performance fibres. The gel spinning and drawing process is schematically shown in the Figure 11. This is carried out in the three stages: 1. Dissolution: a homogeneous solution of ultra high molecular weight HDPE is prepared at elevated temperatures with stirring. This forms a solution with minimum chain ends, which is capable of gelation with optimum number of entanglements. 2. Spinning: A gel like as spun fibre is obtained by spinning the solution at 130 - 140C with controlled crystallisation and minimum number of entanglements. 3. Drawing: High draw ration can be achieved with minimum amorphous phase. The tensile strength of the HDPE is about 7 Gpa and modulus of about 200 Gpa could be produced. The cost of solvent recovery and the controlled low speed spinning and drawing increases the cost of fibre to a level comparable with the other polymeric fibres. This lightweight, high strength, high modulus fibre has high toughness but a low melting point. Some of its applications are marine ropes and cables, sail cloth, concrete reinforcement, fish netting, sports equipment and medical implants. Optical fibres Alexander Graham Bell invented telephone in1880. This invention was not commercialised because of the non-availability of fibre with high intensity light and low transmission efficiency. High intensity of light are available in 1960s.At the same time, research on manufacturing technology of glass fibre lead to significant increase in the transmission of light through the fibre. Glass fibre has considerable advantage over the copper wires as a communication medium at optical frequencies. This unique property is based on the principle of total internal reflection. In smooth surfaces, there is little loss of light at the repeated reflections and little absorption, so light can be transmitted over long distance with little loss in the intensity. Optical fibres are bundles of small diameter, flexible light pipes and comprises of a fibre of transparent material of relatively higher refractive index coated with material of lower refractive index to achieve total internal reflection. Alternatively, optical fibres can also be made with gradually decreasing refractive index from core to sheath. The fibre of first category is termed as step index optical fibres and the second category is

termed as Grade index optical fibres. The absorption loss has been substantially reduced by decreasing the concentration of optically absorbing impurities to below one part by billion. The Figure 13 shows that the light is guided through the optical fibre. Incident rays, which fall with in the acceptance cone of the fibre, will be transmitted, whereas those fall outside of the acceptance cone are last in the sheath. For Plastic Optical Fibres (POF), Polystyrene and Poly Methyl Metha Acralate (PMMA) are used as core material. Polystyrene core resulted in 5,000 dB/km-transmission losses. Poly Methyl Metha Acralate (PMMA) core material if used results in a transmission loss up to 1,000 dB/km. Silicon, and polycarbonate are also used as core and fluor plastics, Teflon, fluorinated methacrylate and fluorinated polycarbonate are used as sheath material for getting low transmission loss. Inorgonic fibre The fibres consisting of essentially carbon are termed as inorganic fibres. Glass, asbestos and carbon fibres are well known inorganic fibres. They are extensively used because of their unique characteristics, out of which, the carbon fires production and applications are discussed here. Carbon fibres The carbon fibres can be produced with PAN, rayon and meso phase pitch. Pyrolysis of acrylic based fibres and removal of the impurities enhances the carbon content and prevents the nucleation and growth of graphite crystals. The production of PAN based carbon fibre also involves three stages, namely oxidative stabilisation (at 200 C - 300C), carbonisation up to 1,500C and graphitation between 1,500C to 2,700C, based on the fibre required.

Carbon fibres with different structures also made from meso phase pitch .The graphite planes in PAN based fibres are arranged parallel to the fibre axis rather than perpendicular as is the case of pitch based carbon fibres.

For the production of carbon fibres from rayon, the oxidative stabilisation is at 400 C, the carbonisation is up to 1,500C, and graphitation is above 2,500 . In the carbonisation stage, that graphite like layers start forming; however, during this process the originally preferred orientation of the cellulose structure is lost. Therefore, stretch up to 50% is applied at higher temperature particularly during the graphitation. The properties of the carbon fibres are: Density: 1.7 - 2.1g/cm3 Carbon component weight (%): 92 - 99.9 Tensile modulus: 220 - 250 GPa

Tensile Elongation: 1.2 - 2.4% Tensile Strenght: 2.5 - 7 Gpa The higher modulus achievement is at the cost of toughness. The modulus in the fibre's axis direction is highly orientation-dependent. In PAN-based fibre the degree of order and the modulus increase with increase in graphitation temperature, while the tensile elongation decreases significantly. The meso phase pitch based carbon fibre can be produced with high modulus. The carbon fibres are electrical conductors. However, the ability to conduct the electricity has one potential hazard that they are air borne during the manufacturing or service, with the result they can settle on electrical equipment and cause short-circuiting. The high specific strength and stiffness of the carbon fibres are the basic characteristics, which are useful in almost all applications. The other properties such as temperature resistance, chemical and biological inertness, electrical conductivity, good vibration, damping ability and fatigue resistance may be useful in specific applications. The main shortcomings are: 1) Low impact strength and 2) Very expensive. Ultra fine fibres Fibres with less than 0.5 deniers are termed as ultra fine fibres. The ultra fine fibres can be spun through the modified orifice and or the mechanical and chemical treatments. These are classified as continuous type and random type. In continuous type, the conventional extrusion and conjugate spinning methods are used. In random type flash spinning, melt blowing, fibrillation types are used to produce ultra fine fibres. Characteristics of these fibres are softness, fine textile structure, micro pockets in fibres, high filament density in textile stands, small radius of curvature (results in luster), quick inter-penetration capability and quick stress release. Direct spinning In the direct spinning, process the ultra fine fibre production is a difficult process. Problem with direct spinning are high breakdown (Dripping), variation in filament thickness, spinneret clogging and denier variation. To minimize this problem the following steps have to be taken: 1.Optimisation of polymer viscosity (high spinning tension and reduced viscosity-about 950poise). 2. Spinneret optimisation (holes should be arranged such that to ensure homogeneous cooling). 3. Optimisation of quenching.4.Optimisation of spinning assembly. (Assembly shout be kept near the spinneret. Conjugate spinning Islands in a sea type fibres

The conjugate spinning type is used to produce fibres with ultra fine denier fibres by using solvents and by mechanical means to separate fibre components. The methods are Islands-insea type, Separation or Splitting type and Multilayer type. In islands-in-a-sea type, the sea component is removed by dissolving in a solvent. No drawing is required. Micro fibrillation is done in the form of fabrics. The islands are commonly polyester, nylon, polypropelene, polyethylene and poly-phenylene sulfide. The sea components are polystyrene, 2-ethylhexyl acralate co-polymer and co-polymer of ethylene terephalate. The fires produced by this type are with range of denier 0.00009. Around 4.16 grams of such filament is enough to cover distance from earth to moon. Spinning nozzle for conjugate spinning Splitting type/separation type spinning This is two-component fibre in the final product (eg, PET/Nylon). Splitting of the two components has done mechanically. This is of combination and separation of two components. Petal shaped, star shaped cross section of fibres can be produced. These are shown in the Figure 15. Multilayer conjugate fibres These are produced with layers are shown in the Figure 15. Liquids can be multilayer by static mixtures, which have been applied to multilayer type spinning. Filaments of 0.2 to 0.3 denier micro fibrillated filaments are produced. Random type spinning Melt spinning is used to produce fibres of random shape and diameter, used for the production of nonwoven. After the extrusion, die is used with air stream to get the required fibre fineness. Flash spinning is used to get the fibre network by spreading the single stream of fibre spun from one spinneret hole. The diameter varies in the range from 0.10 to 0.15 denier. The filament is of non-circular cross section and some fibres contain micro bubbles. Polymer blend spinning In this method the conjugate fibres are produced by extruding and drawing a blend of two components. The arrangement of the dispersed and non-dispersed matrix components is determined by the mixing ratio of the components, and their melt viscosities. The other random spinning methods used top produce ultra fine fibres are fibrillation and burst spinning. The ultra fine fibres are not of speciality fibres, but they are considered as one of the fundamental materials today. This opens up new fields of fibre application. The ultra fine fibres

are used in wiping, filtrations, absorbent, water repelling medium, reinforcing material, suedelike materials, chemical and environment sensitive material and used in high fashion and good appearance. Summary Conventional fibres may dominate the technical textile markets, but the high performance fibres are needed in some specific applications. Certainly, the textiles growth will depend on greater realisation of technological and financial benefits that the fibre-based structures could bring to the traditional and high performance applications. Issues such as recycling, environment and biodegradability are the subjects of concern of the public, which will further influence the growth in the use of technical textiles. Reference 1. J M G Cowie: Polymers: Chemistry Physics of Modern Materials, Second Edition, CRC publication 1991. 2. A R Bunsell: Sixth European Conference on Composite Materials, EECM, European Association for Composite Materials, Woodhead Publishing, England. Publication,Year 1993. 3. S T Peters: Handbook of Composites, Springer Publication, 2nd Edition 1998. 4. Menachem Lewin, Jack Preston, High Technology Fibres, Handbook of Fibre Science and Technology, Volume 3, 1993. 5. A R Hrrocks and S C Anand: Handbook of Technical Textiles, Woodhead Publishing Limited, England 2000. 6. V B Guptha and V K Kothari: Manufactured Fibre Technology, Chapman Hall, London 1997. 7. Mastura Raheel: Protective Clothing Systems and Materials, Marcel Dekker Inc, New York, 1994. 8. Nakajima: Advanced Fibre Spinning, Woodland Publishing Limited, England, 1994. 9. Handbook of Vectron, Engineering Data and Liquid Crystal Technology, Cleanse Acetate LLC, North Carolina, 1999. 10. Culshaw: Optical Fibre Sensing and Signal Processing, IET, Amazon .com, 1999. Note: For detailed version of this article please refer the print version of The Indian Textile Journal January 2008 issue. Mr Chidambaram Rameshkumar Senior Lecturer Bannari Amman Institute of Technology, Sathyamangalam, Tamil Nadu. E-mail: crktex@gmail.com.

Dr N Anbumani Asst Professor with the PSG Collage of Technology, Coimbatore.