Aramid

Aramid fibers, short for aromatic polyamide, 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 marine cordage, marine hull reinforcement, as an asbestos substitute,^[1] and in various lightweight consumer items ranging from phone cases to tennis rackets.

The chain molecules in the fibers are highly oriented along the fiber axis. As a result, a higher proportion of the chemical bond contributes more to fiber strength than in many other synthetic fibres in the world. Aramids have a very high melting point (>500 °C (932 °F)).

Common aramid brand names include Kevlar, Nomex, and Twaron.

Terminology and chemical structure

Structure of Twaron and Kevlar. The aromatic rings appear as hexagons. The rings are attached alternately to either two NH groups or two CO groups. The attachment points on each ring are diametrically opposite each other, a characteristic of the structure called para-aramid.

The term aramid is shortened from aromatic polyamide. It was introduced in 1972,^[2] accepted in 1974 by the Federal Trade Commission of the USA as the name of a generic category of fiber distinct from nylon,^[3]^[4] and adopted by the International Standards Organisation in 1977.^{[citation needed]}

Aromatic in the longer name refers to the presence of aromatic rings of six carbon atoms. In aramids these rings are connected via amide linkages each comprising a CO group attached to an NH group.

In order to meet the FTC definition of an aramid,^[4] at least 85% of these linkages must be attached to two aromatic rings.^[5] Below 85%, the material is instead classed as nylon.^[4]

Para-aramids and meta-aramids

Aramids are divided into two main types according to where the linkages attach to the rings. Numbering the carbon atoms sequentially around a ring, para-aramids have the linkages attached at positions 1 and 4, while meta-aramids have them at positions 1 and 3.^[6] That is, the attachment points are diametrically opposite each other in para-aramids, and two atoms apart in meta-aramids. The illustration thus shows a para-aramid.

History

Kevlar brand aramid rope

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.^[7] 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-aramids are also produced in the Netherlands and Japan by Teijin Aramid under the trade name Teijinconex,^[7] and by Toray under the trade name Arawin, in China by Yantai Tayho under the trade name New Star and by SRO Group 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 and 1970s by DuPont and AkzoNobel, both profiting from their knowledge of rayon, polyester and nylon processing. In 1973, DuPont was the first company to introduce a para-aramid fiber, calling it Kevlar; this remains one of the best-known^{[citation needed]} para-aramids and/or aramids.

In 1978, Akzo introduced a similar fiber with roughly the same chemical structure calling it Twaron. Due to earlier patents on the production process, Akzo and DuPont engaged in a patent dispute in the 1980s. Twaron subsequently came under the ownership of the Teijin Aramid Company. In 2011, Yantai Tayho introduced similar fiber which is called Taparan in China (see Production).

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

Both meta-aramid and para-aramid fiber can be used to make aramid paper. Aramid paper is used as electrical insulation materials and construction materials to make honeycomb core. Dupont made aramid paper during the 1960s, calling it Nomex paper. Yantai Metastar Special Paper introduced an aramid paper in 2007, which is called metastar paper. Both Dupont and Yantai Metastar make meta-aramid and para-aramid paper.^{[citation needed]}

Health

Carbon and Aramid, carbon yarn and textile, composite material, aramid glove (Twaron), cable (braided glass fibre, aramid core), aramid yarn, braided textile (aramid and carbon). Tray and samples of the textile cabinet in the Textielmuseum in Tilburg.

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.^[8] However, in 2009, it was shown that inhaled aramid fibrils are shortened and quickly cleared from the body and pose little risk.^[9] A declaration of interest correction was later provided by the author of the study stating that "This review was commissioned and funded by DuPont and Teijin Aramid, but the author alone was responsible for the content and writing of the paper."^[10]

Production

Aramid process diagram

World capacity of para-aramid production was estimated at 41,000 t (40,000 long tons; 45,000 short tons) per year in 2002 and increases each year by 5–10%.^[11] In 2007 this means a total production capacity of around 55,000 tonnes per year.^{[citation needed]}

Polymer preparation

Aramids are generally prepared by the reaction between an amine group and a carboxylic acid halide group. Simple AB homopolymers have the connectivity −(NH−C₆H₄−CO)_n−.

Well-known aramid polymers such as Kevlar, Twaron, Nomex, New Star, and Teijinconex) are prepared from diamine and diacid (or equivalent) precursors. These polymers can be further classified according to the linkages on the aromatic subunits. Nomex, Teijinconex, and New Star contain predominantly the meta-linkage. They are called poly-metaphenylene isophthalamides (MPIAs). By contrast, Kevlar and Twaron both feature para-linkages. They are called p-phenylene terephthalamides (PPTAs). 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 at Akzo. Apart from the carcinogenic 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

Fiber
Chopped fiber
Powder
Pulp

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).^[12] This relatively simple process uses only one amide solvent, and therefore spinning can be done directly after the polymer production.

Aramid fiber characteristics

Aramid anchor rope used on board the MV Bornholm in the port of Delfzijl, June 2006

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

General

good resistance to abrasion
good resistance to organic solvents
nonconductive ^[ambiguous]
very high melting point (>500 °C (932 °F))
low flammability
good fabric integrity at elevated temperatures
sensitive to acids and salts ^[how?]
sensitive to ultraviolet radiation ^[how?]
prone to electrostatic charge build-up unless finished^[13]

Para-aramids

para-aramid fibers, such as Kevlar and Twaron, provide outstanding strength-to-weight properties
high chord modulus
high tenacity
low creep
low elongation at break (~3.5%)
difficult to dye – usually solution-dyed^[13]

Uses

flame-resistant clothing
heat-protective clothing and helmets
body armor,^[14] competing with polyethylene-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^[15]
V-belts (automotive, machinery, equipment, and more)
wicks for fire dancing
optical fiber cable systems
sail cloth (not necessarily racing boat sails)
sporting goods
drumheads
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)
snowboards
jet engine enclosures
fishing reel drag systems
asphalt reinforcement
Prusiks for rock climbers (which slide along the main rope and can otherwise melt due to friction).
Snowboards core reinforcement

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. S2CID 136433442.575-580&rft.date=1984&rft_id=info:doi/10.1177/004051758405400903&rft_id=https://api.semanticscholar.org/CorpusID:136433442#id-name=S2CID&rft.au=Hillermeier, Karlheinz&rfr_id=info:sid/en.wikipedia.org:Aramid" class="Z3988">
^ Gooch, J W, ed. (2006). "Aramid". Encyclopedic Dictionary of Polymers. New York: Springer. pp. 64–65. doi:10.1007/978-0-387-30160-0_760. ISBN 978-0-387-31021-3. Retrieved 16 September 2021.64-65&rft.pub=Springer&rft.date=2006&rft_id=info:doi/10.1007/978-0-387-30160-0_760&rft.isbn=978-0-387-31021-3&rft_id=https://link.springer.com/referenceworkentry/10.1007/978-0-387-30160-0_760&rfr_id=info:sid/en.wikipedia.org:Aramid" class="Z3988">
^ Wingate, Isabel Barnum (1979). Fairchild's dictionary of textiles. Internet Archive. New York : Fairchild Publications. p. 25. ISBN 978-0-87005-198-2.
^ ^a ^b ^c Commercial Practices, Part 303, §303.7 Generic names and definitions for manufactured fibers.
^ The full definition of aramid fibre 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, ( ) are attached directly to two aromatic rings", with a diagram between the parentheses which shows a vertically oriented CO group attached horizontally to an NH group. There is an incoming bond to the C atom and an outgoing one from the NH group.
^ Position 1 is simply chosen as the point where one of the chains is attached. We then count around the ring in the shortest direction until we reach the other one.
^ ^a ^b James A. Kent, ed. (2006). Handbook of Industrial Chemistry and Biotechnology. Springer. p. 483. ISBN 978-0-387-27842-1.
^ 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. 17 (2): 75–92. doi:10.3109/01480549409014303. PMID 8062644.75-92&rft.date=1994-01-01&rft_id=info:doi/10.3109/01480549409014303&rft_id=info:pmid/8062644&rft.aulast=Marsh&rft.aufirst=J. P.&rft.au=Mossman, B. T.&rft.au=Driscoll, K. E.&rft.au=Schins, R. F.&rft.au=Borm, P. J. A.&rfr_id=info:sid/en.wikipedia.org:Aramid" class="Z3988">
^ Donaldson, K. (1 July 2009). "The inhalation toxicology of p-aramid fibrils". Critical Reviews in Toxicology. 39 (6): 487–500. CiteSeerX 10.1.1.468.7557. doi:10.1080/10408440902911861. PMID 19545198. S2CID 6508943.487-500&rft.date=2009-07-01&rft_id=https://citeseerx.ist.psu.edu/viewdoc/summary?doi=10.1.1.468.7557#id-name=CiteSeerX&rft_id=https://api.semanticscholar.org/CorpusID:6508943#id-name=S2CID&rft_id=info:pmid/19545198&rft_id=info:doi/10.1080/10408440902911861&rft.aulast=Donaldson&rft.aufirst=K.&rfr_id=info:sid/en.wikipedia.org:Aramid" class="Z3988">
^ Donaldson, Ken (22 July 2009). "Corrigendum: The inhalation toxicology of - aramid fibrils". Critical Reviews in Toxicology. 39 (6): 540. doi:10.1080/10408440903083066. S2CID 218987849.
^ 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 978-0-309-09614-0.
^ Ozawa S (1987). "A New Approach to High Modulus, High Tenacity Fibers". Polymer Journal. 19: 199. doi:10.1295/polymj.19.119.
^ ^a ^b 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.p018.18-22&rft.date=2005&rft_id=info:doi/10.1021/cen-v083n050.p018&rft.au=Reisch, Marc S&rft_id=http://pubs.acs.org/email/cen/html080205142022.html&rfr_id=info:sid/en.wikipedia.org:Aramid" class="Z3988">
^ "Aramid Cables". FibreMax. Archived from the original on 2021-12-01.