Aramid fiber is a new high-tech synthetic fiber, which was successfully developed by DuPont in the United States in the 1960s and took the lead in industrialized fiber products. The advent of aramid fiber is considered an important milestone in the development of the materials industry. Because of its excellent performance, aramid fiber has been widely used in aerospace, sports materials, tires, high-strength ropes and other materials, so it has been widely concerned. This paper introduces the structure, properties, applications and production methods of aramid fiber, analyzes the current development situation of aramid fiber at home and abroad, and puts forward some suggestions for the development of high performance aramid fiber in our country.
Aramid fiber is mainly divided into para-aramid fiber (aramid 1414) and meta-aramid fiber (Aramid 1313). Aramid fiber is a kind of high-performance synthetic fiber, with ultra-high strength, high modulus and high temperature resistance, acid and alkali resistance, light weight and other excellent properties, its strength is 5 to 6 times of steel wire, modulus is 2 to 3 times of steel wire or glass fiber, toughness is 2 times of steel wire, and the weight is only 0.2 times of steel wire. In addition, aramid fiber also has good insulation and anti-aging properties, and its application fields are very wide. Para-aramid fiber is mainly used in rubber reinforced products, bulletproof fabrics, composite structural materials, cable materials, heat insulation, radiation insulation structure board and so on. The intermediate arylon fiber is mainly used for electrical insulation paper, flame retardant fabric, heat insulation, radiation protection structure board, aircraft bearing structural materials, dust filter bag and so on.
The full name of aramid fiber is aromatic polyamide fiber, which is a kind of organic synthetic fiber with high strength, high modulus, low density and high wear resistance. Aramid fiber is divided into para-aramid fiber (PPTA) and para-aramid fiber (PMIA). Poly (p-benzoyl-p-phenylenediamine) fiber is the most representative of PPTA, and the English full name is AramidFiber.
As for the microstructure of aramong fibers, the most representative structure model is the skin and core layer. Morgan et al. believe that each single fiber has distinguishable skin and core characteristics, and the skin and core layer have different structures and properties. The thickness of the layer is 0.1-lum, and the structure of the layer is similar to that of mica sheet, and the structure is consistent in the length direction, while the core layer has no such structure. In 1973, Akzo Nobel scientists van A artser and Nort holt published the results of their fundamental research on the crystalline structure of their company’s Twaron fiber. The main reason for the rod-like morphology of PPTA chain molecules is the steric hindrance between benzene ring and the axial parallel orientation of molecule and warp dimension. The subcrystalline structure is a single-phase crystal structure in which the local crystallization is nearly complete, but there are some crystal defects in a longer distance. Twaron is strong in the axial direction of the fiber (strong covalent bond) and weak in the transverse direction. The model shows that the molecular chains are held together in one direction by relatively weak hydrogen bonds, while the molecular chains are held together in the other direction by even weaker van der Waals forces. The tendency of fiber fibrination due to abrasion is caused by the lack of strong transverse bonding force.
The rigidity of the aromatic amide molecular chain increases, so the glass transition temperature, heat resistance and modulus of the fiber are higher. Because of the different molecular chain structure of arylamide, it can be divided into different kinds of aramid fiber products, and the performance, processing methods and uses of these products are very different.
Structural properties of arylamide fibers | ||||
Para | Trade name | Fibre variety | Main raw material (monomer) | Performance characteristics |
Kevlar®49(USA) | Polyp-benzamide fibre | p-aminobenzamide | Ultra high, modulus | |
Kevlar®(USA) | Polyterephthalyl | P-benzoyl chloride | High strength, high mold | |
Technor@ (Japan) | Poly3, 4-diphenylene p-benzoyl P-phenylenediamine fiber | P-phenylenediamine P-benzoyl chloride | Heat resistant, high strength | |
Terlon (Russia) | Polyterephthalyl P-phenylenediamine fiber | P-benzoyl chloride p-phenylenediamine | High strength, high mold | |
SVM®(Russia) | Polypara-aromatic heterocyclic ring Polyimide fiber | Para aromatic miscella Cyclic polyimide | High mode | |
Armos® | Polypara-aromatic Heterocyclic copolyamide fiber | Para aromatics Heterocyclic copolyamide | High mold, high strength | |
Meta | Nomex@(United States) Aramid 1313(China) | polyresorcin | Isophthalyl chloride M-phenylenediamine | High temperature resistance |
Conex®(USA) Fennelon(Russia) | polyresorcin | Isophthalyl chloride m-phenylenediamine | High temperature resistance | |
Aramid 1414 fiber is a kind of para-arranged rigid polymer material, and the macromolecules on its main chain structure are usually arranged in a high degree of regularity. In its rigid linear molecular chain, due to the existence of strong covalent bonds and weak hydrogen bonds and in the amide group, the electrons of oxygen and nitrogen atoms will produce conjugation effects, so aramidon 1414 fiber usually has excellent mechanical strength, fire resistance, high temperature resistance, chemical corrosion resistance, fatigue resistance and other properties. Its strength, modulus and decomposition temperature are significantly higher than those of aramid 1313 fiber. In addition, aramid 1414 fiber also has good chemical corrosion resistance, hydrolysis resistance and mechanical properties, in organic solvents, aramid 1414 fiber is insoluble, only soluble in a few strong acid solvents. Its strength is more than 3 times higher than the general organic fiber, the initial modulus is lo times of nylon, 9 times of polyester; Its relative strength is equivalent to 6 to 7 times that of steel, the modulus is about 2 to 3 times that of steel wire and glass fiber, and the specific gravity is only about 1/5 of steel wire. Aramid 1414 fiber also has good impact resistance, fatigue resistance, and rubber has good adhesion; And the bending resistance and processing performance is good, so it can be woven and woven by ordinary loom, the strength of the fabric is generally not less than 90% of the strength of the fiber, so it is an ideal cord fabric raw material.
Aramid fiber has excellent chemical stability, thermal stability and high strength, high characteristics, so as a special fiber with superior performance, IT has been widely used in many fields such as industry, national defense, military, aerospace, electronic information (IT), transportation, engineering and construction.
Aramid 1414 is more widely used because of its better performance. Aramid 1414 was first used in cutting-edge fields such as national defense and military industry. In order to meet the needs of modern war and anti-terrorism, the United States, Russia, Britain, Germany, France, Israel, Italy and many other countries of the military police body armor, bulletproof helmet, stab and cut clothing, explosive suit, high-strength parachute, bulletproof body, armor plate, etc., are a large number of arylon 1414. Now, in addition to the military field, aramid 1414 has been widely used as a high-tech fiber material in aerospace, electrical and mechanical, construction, automobiles, Marine fisheries, sporting goods and other aspects of the national economy. In aerospace, aramid fiber resin-based reinforced composites are used as structural materials for aerospace, rockets and aircraft, which can reduce weight, increase payload and save a lot of power fuel. For example, the shell, interior trim and seat of Boeing aircraft have been reduced by 30% due to the successful application of aramid 1414 material. Because aramid 1414 has low specific gravity, high strength and good heat resistance, and has good adhesion to rubber, it becomes the most ideal cord fiber. In addition, arnylon 1414 can also be used as a skeleton material in inflatable rubber products (such as inflatable life rafts, inflatable boat Bridges, etc.), corrosion resistant containers, light oil tanks and large-caliber crude oil drainage pipettes; Used for making high temperature and cutting resistant protective gloves; Using its self-lubricity, heat resistance and toughness, it can replace the carcinogenic asbestos to make heat insulation protective screen, protective clothing and sealing materials; It can also replace asbestos and glass fiber to strengthen resins and be used as friction-resistant, adiabatic and electrical insulating materials; Production of ship cables, submarine cables, radar buoy systems and fiber-optic reinforced cables; Manufactures high-strength, low-weight sports equipment such as skis, rowboats and kayaks. In short, in the application fields requiring materials with high strength, tensile resistance, tear resistance, puncture resistance and high temperature resistance, aramid 1414 has irreplaceable advantages.
In 1962, DuPont took the lead in developing the aramid 1313 fiber named “Nomex”, and began industrial production in 1967. In 1966, the company developed the aramid 1414 fiber under the trade name “Kevlar” and began industrial production in 1971. Because aramid fiber has high strength, high quantity, high temperature resistance, has a very wide range of application fields and development prospects, so it has been widely concerned by countries around the world, such as the Dutch Akzo company, the Japanese Teijin and Unijica Company, the Russian synthetic fiber Institute and heat-resistant textile company, Germany Hearst Company and so on have joined the development of aramid fiber. And has launched a number of excellent performance of aramid fiber products.
The world’s main manufacturer of arylamide fiber | ||||
Company/Factory address | Trade name | Output /(t/a) | remark | |
Para | Dupont/ United States | Kevlar | 20000 | About 54.4% of the world’s total para-aramid output |
Dupont/ United Kingdom | Kevlar | 5000 | ||
Toray/Japan | Kevlar | 2500 | ||
AKZO/ Netherlands | Twaron | 18500 | About 40% of the world’s para-aramid production (now acquired by Teijin Corporation, renamed Tejin lwaron Corporation) | |
Technora | 2000 | |||
Terlon | 100 | |||
SVM | 1000 | |||
Armos | 500 | |||
Rusar | 500 | |||
Pycap® | 100 | |||
Meta | Toray -Dupont/ Japan | Nommex | 19000 | It accounts for about 70% of the world’s total output of meso-aramid |
All-russian Synthetic Fiber Institute/Russia | Phenylon | 4500 | It accounts for about 16.6% of the world’s total output of meso-aramid | |
Teijin/Japan | Conex | 2650 | It accounts for about 9.8% of the world’s total output of meso-aramid | |
Unijica/ Japan | Apeil | 1000 | It accounts for about 3.7% of the world’s total output of meso-aramid | |
At present, the world’s manufacturers engaged in the production of aramid 1414 fiber are mainly: DuPont (Kevlar), the Netherlands Aczo company (Tw arOn), Japan’s Emperor company (Technora), Russia’s Heat resistant company (Pycap) and so on. Among them, DuPont ranks first in the world in production, Teijin ranks second, and the two companies account for 55% and 40% of the world’s total aramid output respectively. In addition, Germany’s Hearst company and Russia’s all-Russian synthetic fiber Institute and heat-resistant company also have a small amount of production It is worth mentioning that in recent years, Japan’s Emperor actively expand the production of para-aramid fiber, the company’s recent development strategy is to catch up with DuPont, as soon as possible to become the world’s largest and strongest aramid fiber manufacturing enterprises. To this end, Teijin acquired the Tsi arOn plant of Akzo in the Netherlands in late 2000 and invested US $180 million in the acquisition company in 2003 to expand its production capacity; It also acquired Aramid, a joint venture between Aco Foundation and UInitomo.
At present, the main manufacturers of aramid 1313 fiber in the world are DuPont Company, Teijin Company, Russia’s all-Russian composite fiber Institute and heat-resistant textile Company, and Japan Unijica Company. Dupont ranks first in the world in production, Teijin ranks second, and other companies also have a small amount of production. In recent years, some foreign manufacturers are very optimistic about Asia, especially the Chinese market, DuPont took the lead in establishing an office in Shanghai, as an important window to carry out Kevlar fiber sales in China; Dupont established Kevlar Fiber production Company (Toray DuPont) in cooperation with Toray Japan; Dupont has also partnered with Teijin to establish DuPont ITeijin Advanced Fibers (Hong Kong) to jointly develop the “Kevlar” and “Nomex” fiber markets in Asia, and the company has recently launched arylon 1414 fiber products with excellent physical and mechanical properties for general clothing to industrial products. The research and development of China’s aramid fiber began in the 1970s of last century. Chinese Academy of Sciences, Tsinghua University, China Textile University, Shanghai Textile Research Institute, Sinopec Yanshan Petrochemical Company, Jinan Qilu Chemical Fiber Group and other units have carried out research and pilot production of aramid fiber. Among them, the Chinese Academy of Sciences and Tsinghua University have carried out theoretical research on aramid fiber, Shanghai Textile Research Institute, Sichuan Chenguang Research Institute, as well as Shanghai Synthetic fiber Research Institute and China Textile Research Institute have carried out trial production of aramid fiber.
Since entering the 1990s, the domestic research and development of aramid fiber has made great progress, the former Ministry of Chemical industry built a 30t/a aramid 1313 production plant in Nantong; The drawing test of aramid fiber was carried out by Shanghai Composite Fiber Institute. At the same time, China National Textile University has also developed batch polymerization spinning technology. In 1998, Yantai Textile Corporation began to invest 200 to 300 million yuan, the introduction of complete sets of Russian aramid production technology and equipment, the construction of 500t/a aramid 1313 production line. For a long time, the localization and large-scale production technology of aramid fiber has been the concern of many domestic chemical fiber enterprises. The relevant state departments have successively included the development of aramid 1414 fiber complete set of production technology in the national “ninth Five-Year Plan” and “fifteen key development projects.” At present, the development of complete PPTA production technology has been completed, and the pilot production of fiber has been realized. Some scientific research institutions have gradually formed independent intellectual property rights through research. Through the unremitting efforts of scientific researchers, our country has achieved large-scale production of aramid 1313 fibers, and the development of complete sets of technology of aramid 1414 has also made a breakthrough, so as to lay a solid foundation for the early realization of large-scale production of aramid 1414 fibers in our country.
Aramid fiber, as a kind of high performance synthetic fiber, its international development prospect is showing vigorous vitality. According to market research data, the global aramid market size has reached $3.9 billion in 2021, and is expected to continue to expand at a compound annual growth rate (CAGR) of 9.7%, and is expected to grow to $5.3 billion by 2025. This significant growth is indicative of the rising demand for aramid fibers worldwide.
In China, the demand for aramid fiber is also remarkable. In 2022, China’s demand for aramid was 23,000 tons, and by 2023, this figure has grown to about 41,500 tons, of which para-aramid 23,300 tons and para-aramid 18,200 tons. It is expected that by 2025, China’s aramid demand will further increase to 29,000 tons, and may even reach a higher level. This continuous growth in demand for China’s aramid fiber industry provides a broad space for development.
Technological progress and capacity improvement are key factors to promote the development of the aramid fiber industry. In the world, the production technology of aramid fiber continues to improve, the production cost is gradually reduced, and the production efficiency is significantly improved. This technological advance makes possible the application of aramid fibers in a wider range of fields. At the same time, Chinese companies such as Taihe New Materials are also actively expanding production capacity to meet market demand. The production capacity of these enterprises has reached the 10,000-ton class and is still growing.
In the international market, the competitive landscape of aramid fiber is changing. Although the global aramid fiber market is currently dominated by a few international giants such as DuPont in the United States and Toray in Japan, this pattern is being broken with the rapid rise of Chinese enterprises. Chinese enterprises have made remarkable progress in technological innovation, capacity expansion and market exploration, gradually taking a place in the international market.
In addition, the application field of aramid fiber is also expanding. In addition to traditional fields such as aerospace, national defense, automobile manufacturing, electrical communications, etc., the demand for aramid fibers in emerging fields such as new energy vehicles, wind power generation, civil construction, and ship cables is also increasing. Especially in the field of new energy vehicles, aramid fiber as an important choice of lightweight materials, its market demand will usher in explosive growth.
To sum up, aramid fiber with its excellent performance and a wide range of application fields, in the international market has shown broad prospects for development. With the continuous growth of demand in China and the global market, the promotion of technological progress and capacity improvement, as well as the continuous expansion of emerging fields, the aramid fiber industry will usher in a more brilliant development period in the future.
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