Aramid

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Para-aramid structure

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[edit]

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 under the trade name Conex,[2] 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, a fiber – para-aramid – 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).

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[edit]

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] In 2009, it has been shown that inhaled Aramid fibrils are shortened and quickly cleared from the body and pose little risk.[4]

Production[edit]

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

Polymer preparation[edit]

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

nNH2-Ar-COCl → -(NH-Ar-CO)n- + nHCl

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. Prior to the invention of this process by Leo Vollbracht, who worked at the Dutch chemical firm Akzo, no practical means of dissolving the polymer was known. The use of this system led to an extended patent dispute between Akzo and DuPont.

Spinning[edit]

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[edit]

Other types of aramids[edit]

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[edit]

Aramids share a high degree of orientation with other fibers such as ultra high molecular weight polyethylene, a characteristic that dominates their properties.

General[edit]

  • good resistance to abrasion
  • good resistance to organic solvents
  • nonconductive
  • no melting point, degradation starts from 500°C
  • low flammability
  • good fabric integrity at elevated temperatures
  • sensitive to acids and salts
  • sensitive to ultraviolet radiation
  • prone to static build-up unless finished[7]

Para-aramids[edit]

  • 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 [7]

Major industrial uses[edit]

See also[edit]

Para-aramid

Meta-aramid

Others

Notes and references[edit]

  1. ^ Karlheinz Hillermeier, ed. (1984). Prospects of Aramid as a Substitute for Asbestos. Textile Research Journal. pp. 575–580. ISSN 0040-5175. 
  2. ^ a b 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. 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. 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. ^ a b 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[edit]

  • 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. 
  • Karlheinz Hillermeier (1984). "Prospects of Aramid as a Substitute for Asbestos". Research Journal, Vol. 54, No. 9 (pages 575-580). 
  • 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 and H.G. Weijland (1977). "An aramid yarn for reinforcing plastics". Plastica (11): 374–380. 
  • DuPont and Teijin to expand aramid production - September 2004