Aramid fibers are a class of heat-resistant and strong synthetic fibers. They are used in aerospace and military applications, for ballistic-rated body armor fabric and ballistic composites, in bicycle tires, and as an asbestos substitute. The name is a portmanteau of "aromatic polyamide". They are fibers in which the chain molecules are highly oriented along the fiber axis, so the strength of the chemical bond can be exploited.
Aromatic polyamides were first introduced in commercial applications in the early 1960s, with a meta-aramid fiber produced by DuPont as HT-1 and then under the trade name Nomex. This fiber, which handles similarly to normal textile apparel fibers, is characterized by its excellent resistance to heat, as it neither melts nor ignites in normal levels of oxygen. It is used extensively in the production of protective apparel, air filtration, thermal and electrical insulation as well as a substitute for asbestos. Meta-aramid is also produced in the Netherlands and Japan by Teijin under the trade name Conex, in Korea by Toray under the trade name Arawin, in China by Yantai Tayho under the trade name New Star, by SRO Group (China) under the trade name X-Fiper, and a variant of meta-aramid in France by Kermel under the trade name Kermel.
Based on earlier research by Monsanto Company and Bayer, para-aramid fiber with much higher tenacity and elastic modulus was also developed in the 1960s–1970s by DuPont and Akzo Nobel, both profiting from their knowledge of rayon, polyester and nylon processing.
Much work was done by Stephanie Kwolek in 1961 while working at DuPont, and that company was the first to introduce a para-aramid called Kevlar in 1973. A similar fiber called Twaron with roughly the same chemical structure was introduced by Akzo in 1978. Due to earlier patents on the production process, Akzo and DuPont engaged in a patent dispute in the 1980s. Twaron is currently owned by the Teijin company (see Production).
A manufactured fiber in which the fiber-forming substance is a long-chain synthetic polyamide in which at least 85% of the amide linkages, (−CO−NH−) are attached directly to two aromatic rings.
During the 1990s, an in vitro test of aramid fibers showed they exhibited "many of the same effects on epithelial cells as did asbestos, including increased radiolabeled nucleotide incorporation into DNA and induction of ODC (ornithine decarboxylase) enzyme activity", raising the possibility of carcinogenic implications. However, in 2009, it was shown that inhaled aramid fibrils are shortened and quickly cleared from the body and pose little risk.
World capacity of para-aramid production was estimated at about 41,000 tonnes per year in 2002 and increases each year by 5–10%. In 2007 this means a total production capacity of around 55,000 tonnes per year.
- n NH2−Ar−COCl → −(NH−Ar−CO)n− + n HCl
The most well-known aramids (Kevlar, Twaron, Nomex, New Star and Teijinconex) are AABB polymers. Nomex, Teijinconex and New Star contain predominantly the meta-linkage and are poly-metaphenylene isophthalamides (MPIA). Kevlar and Twaron are both p-phenylene terephthalamides (PPTA), the simplest form of the AABB para-polyaramide. PPTA is a product of p-phenylene diamine (PPD) and terephthaloyl dichloride (TDC or TCl).
Production of PPTA relies on a co-solvent with an ionic component (calcium chloride (CaCl2)) to occupy the hydrogen bonds of the amide groups, and an organic component (N-methyl pyrrolidone (NMP)) to dissolve the aromatic polymer. This process was invented by Leo Vollbracht, who worked at the Dutch chemical firm Akzo. Apart from the carcinogenic Hexamethylphosphorous Triamide (HMPT), still no practical alternative of dissolving the polymer is known. The use of the NMP/CaCl2 system led to an extended patent dispute between Akzo and DuPont.
After production of the polymer, the aramid fiber is produced by spinning the dissolved polymer to a solid fiber from a liquid chemical blend. Polymer solvent for spinning PPTA is generally 100% anhydrous sulfuric acid (H2SO4).
Other types of aramids
Besides meta-aramids like Nomex, other variations belong to the aramid fiber range. These are mainly of the copolyamide type, best known under the brand name Technora, as developed by Teijin and introduced in 1976. The manufacturing process of Technora reacts PPD and 3,4'-diaminodiphenylether (3,4'-ODA) with terephthaloyl chloride (TCl). This relatively simple process uses only one amide solvent, and therefore spinning can be done directly after the polymer production.
In Europe, there is a POD (poly-oxadiazole polymer) known under the brand name Arselon, which was developed in the beginning of 70s at Research and Production Association "Khimvolokno" (Moscow region).
Since 1975 Arselon based on polyphenylene-1,3,4-oxadiazole is produced at OJSC "SvetlogorskKhimvolokno" (Svetlogorsk, Belarus).
This fiber made from terephthalic acid (PTA), hydrazine-sulphate and oleum.
Arselon fiber can resist 250 °C and withstands short-term heat shock at 400 °C with no shrinkage or melting. LOI of Arselon - 30%.
Range of products based on Arselon:
- filament yarns;
- staple fiber;
- milled fiber;
- spun yarns;
- non-woven felt Filars;
- FR fabrics and ready made PPE;
- bag filters for hot gas filtration
Aramid fiber characteristics
Aramids share a high degree of orientation with other fibers such as ultra-high-molecular-weight polyethylene, a characteristic that dominates their properties.
- good resistance to abrasion
- good resistance to organic solvents
- no melting point
- low flammability
- good fabric integrity at elevated temperatures
- sensitive to acids and salts
- sensitive to ultraviolet radiation
- prone to electrostatic charge build-up unless finished
- para-aramid fibers, such as Kevlar and Twaron, provide outstanding strength-to-weight properties
- high Young's modulus
- high tenacity
- low creep
- low elongation at break (~3.5%)
- difficult to dye – usually solution-dyed
- flame-resistant clothing (for example, military MIL-G-181188B suits).
- heat-protective clothing and helmets
- body armor, competing with PE-based fiber products such as Dyneema and Spectra
- composite materials
- asbestos replacement (e.g. brake linings)
- hot air filtration fabrics
- tires, newly as Sulfron (sulfur-modified Twaron)
- mechanical rubber goods reinforcement
- ropes and cables
- wicks for fire dancing
- optical fiber cable systems
- sail cloth (not necessarily racing boat sails)
- sporting goods
- wind instrument reeds, such as the Fibracell brand
- loudspeaker diaphragms
- boathull material
- fiber-reinforced concrete
- reinforced thermoplastic pipes
- tennis strings (e.g. by Ashaway and Prince tennis companies)
- hockey sticks (normally in composition with such materials as wood and carbon)
- jet engine enclosures
Notes and references
- Hillermeier, Karlheinz (1984). "Prospects of Aramid as a Substitute for Asbestos". Textile Research Journal. 54 (9): 575–580. doi:10.1177/004051758405400903.
- James A. Kent, ed. (2006). Handbook of Industrial Chemistry and Biotechnology. Springer. p. 483. ISBN 0-387-27842-7.
- Marsh, J. P.; Mossman, B. T.; Driscoll, K. E.; Schins, R. F.; Borm, P. J. A. (1 January 1994). "Effects of Aramid, a high Strength Synthetic Fiber, on Respiratory Cells in Vitro". Drug and Chemical Toxicology. Informa Healthcare. 17 (2): 75–92. doi:10.3109/01480549409014303. PMID 8062644. Retrieved 15 August 2011.
- Donaldson, K. (1 July 2009). "The inhalation toxicology of p-aramid fibrils". Critical Reviews in Toxicology. Informa Healthcare. 39 (6): 487–500. doi:10.1080/10408440902911861. PMID 19545198. Retrieved 1 October 2012.
- Committee on High-Performance Structural Fibers for Advanced Polymer Matrix Composites, National Research Council (2005). High-Performance Structural Fibers for Advanced Polymer Matrix Composites. The National Academies Press. p. 34. ISBN 0-309-09614-6.
- Ozawa S (1987). "A New Approach to High Modulus, High Tenacity Fibers". Polym. J. Japan. 19: 199. doi:10.1295/polymj.19.119.
- Kadolph, Sara J. Anna L. Langford (2002). Textiles. Pearson Education, Inc. Upper Saddle River, NJ.
- Reisch, Marc S (2005). "High-performance fiber makers respond to demand from military and security users". Chemical and Engineering News. 83 (31): 18–22. doi:10.1021/cen-v083n050.p018.
|Wikimedia Commons has media related to Aramids.|
- J M Garcia; F C Garcia; F Serna; J L de la Peña (2010). "High-performance aromatic polyamides". Progress in Polymer Science. 35 (5): 623–686. doi:10.1016/j.progpolymsci.2009.09.002.
- JWS Hearle (2000). "High-performance fibers". Woodhead Publishing Ltd., Abington, UK – the Textile Institute. ISBN 1-85573-539-3.
- Doetze J. Sikkema (2002). "Manmade fibers one hundred years: Polymers and polymer design". J Appl Polym Sci. John Wiley & Sons, Inc. (83): 484–488.
- Kh. Hillermeier & H.G. Weijland (1977). "An aramid yarn for reinforcing plastics". Plastica (11): 374–380.
- DuPont and Teijin to expand aramid production – September 2004