Aramid

Structure of Kevlar, a para-aramid

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.[1] 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.

History

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.[2] 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 Aramid under the trade name Teijinconex,[2] 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.

In 1973 DuPont was the first company to introduce a para-aramid fiber called Kevlar to the market. 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).

Para-aramids are used in many high-tech applications, such as aerospace and military applications, for "bullet-proof" body armor fabric.

The Federal Trade Commission definition for aramid fiber is:

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.

Health

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.[3] However, in 2009, it was shown that inhaled aramid fibrils are shortened and quickly cleared from the body and pose little risk.[4]

Production

World capacity of para-aramid production was estimated at about 41,000 tonnes per year in 2002 and increases each year by 5–10%.[5] In 2007 this means a total production capacity of around 55,000 tonnes per year.

Polymer preparation

Aramids are generally prepared by the reaction between an amine group and a carboxylic acid halide group. Simple AB homopolymers may look like

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.

Spinning

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).

Appearances

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).[6] This relatively simple process uses only one amide solvent, and therefore spinning can be done directly after the polymer production.

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.

General

Para-aramids

Uses

See also

Para-aramid

Meta-aramid

Others

Notes and references

  1. ↑ Hillermeier, Karlheinz (1984). "Prospects of Aramid as a Substitute for Asbestos". Textile Research Journal. 54 (9): 575–580. doi:10.1177/004051758405400903.
  2. 1 2 James A. Kent, ed. (2006). Handbook of Industrial Chemistry and Biotechnology. Springer. p. 483. ISBN 0-387-27842-7.
  3. ↑ 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. PMID 8062644. doi:10.3109/01480549409014303. Retrieved 15 August 2011.
  4. ↑ Donaldson, K. (1 July 2009). "The inhalation toxicology of p-aramid fibrils". Critical Reviews in Toxicology. Informa Healthcare. 39 (6): 487–500. PMID 19545198. doi:10.1080/10408440902911861. Retrieved 1 October 2012.
  5. ↑ 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.
  6. ↑ Ozawa S (1987). "A New Approach to High Modulus, High Tenacity Fibers". Polym. J. Japan. 19: 199. doi:10.1295/polymj.19.119.
  7. 1 2 Kadolph, Sara J. Anna L. Langford (2002). Textiles. Pearson Education, Inc. Upper Saddle River, NJ.
  8. ↑ 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.

Further reading

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