Overview of domestic and international development of composite materials

Source:http://www.siegrid.com Author:Shirui Time:2016/12/01 13:09
Since high performance composites are included in the whole composite material and high performance is relatively range, it is better to discuss the whole composite material to describe the domestic and international development overview. Composites can be divided into resin matrix composites, metal matrix composites, ceramic matrix composites, cement matrix composites, etc. according to the type of matrix.

(A) Overview of the development of resin-based composites domestic and abroad

Resin matrix composites are the first to be developed and promoted industrially, so they have the widest application and the highest industrialization degree. According to the thermal behavior of the matrix, it can be divided into thermoplastic composites and thermosetting composites.

1. Thermosetting resin matrix composites

Thermosetting resin-based composites are composites made of thermosetting resin such as unsaturated polyester resin, epoxy resin, phenolic resin, vinylester resin etc, reinforced with fiberglass, carbon fiber, aramid fiber, ultra-high molecular weight polyethylene fiber, etc.

Resin matrix composites have been developed for nearly 70 years since its birth in the United States in 1932. From 1940 to 1945, the United States used hand laminated glassfiber reinforced polyester (GRP) resin for the first time to manufacture military radome and aircraft fuel tank, which opened the way for the application of resin matrix composites in military industry.
In 1944, the United States Air Force used resin matrix composite laminated structure the first time to manufacture the wings and aircraft fuselage; in 1946, fiber winding molding was patented in the United States; in 1950, the vacuum bag and pressure bag molding process was successfully developed and the propeller of helicopter was successfully manufactured on a trial basis; in 1949, fiberglass premix was developed successfully, and the resin-based composite parts with a smooth surface were pressed using the traditional pair of molding;
In the 1960s, the U.S. used fiber winding technology successfully developed "In the 1960s, the U.S. developed the Polaris A missile engine housing by fiber winding. In order to improve the productivity of the hand laminated molding process, the injection molding process was developed and applied during this period, which increased the production efficiency by 2-4 times.

1961 Germany successfully developed sheet molding compound (SMC), so that the molding process reached a new level (medium pressure, medium temperature, large table surface products).

In 1963, the industrial production of resin-based composite materials began, the United States, France and Japan have built continuous production lines with high output and large widths, and successfully developed transparent composite materials and their laminated structural sheets.

In 1965, the United States and Japan used SMC to press automobile parts, bath tubs, ship components, etc.; pultrusion molding process began in the 1950s, in the mid-1960s to achieve continuous production, in addition to bars(rods), also the production of thin tubes, square, I beam, channel profiles, etc., until in the 1970s, there was a major breakthrough in pultrusion technology, and the present most advanced pultrusion equipment unit is currently produced in the United States, with a product section of 76×20cm2 and designed with a ring winding mechanism; in the 1970s, resin reaction injection molding (RRIM) was successfully researched, which improved the hand-laminating process and led the product smooth on both sides, has been used in the production of sanitary ware and auto parts. Thermoplastic composites were developed in the early 1970s, and the production process was mainly injection molding and extrusion, which were only used to produce short fiber reinforced plastics.

In 1972, PPG successfully developed glass fiber mat reinforced thermoplastic sheet molding compound (GMT) and put it into production in 1975, the most important feature is that the molding cycle is short and the waste can be recycled. France successfully developed wet production of thermoplastic sheet molding compound (GMT) in the 1980s and had been used in the automotive industry very well. Centrifugal casting molding process began in Switzerland in the 1960s, was developed in the 1980s. 10m long composite wire poles were produced in the UK with this technology, while large diameter pressure pipes were produced by centrifugal method for urban water supply projects with remarkable technical and economic effects. So far, there are nearly 20 kinds of production processes of resin-based composites, and new production processes are still emerging.

Regarding the development and application of resin-based composites, the development paths of each country are different. The U.S. first applied in military industry, and gradually turned to civilian application after World War II. In Western European countries, the development of civil applications (such as waveform plates, anti-corrosion materials, sanitary ware, etc.) started directly, covered the military industry same time. As far as the global world is concerned, a more complete industrial system has been formed from raw materials, molding process, mechanical equipment, product types and performance testing, etc. Compared with other industries, the development speed is very fast.


The resin matrix of nowadays composite materials is still mainly thermosetting resin. According to the statistics in 2000, there are more than 40,000 kinds of resin-based composite products in the world, and the total output reaches 6 million tons, among which the output of high-performance resin-based composite materials is more than 3 million tons, the production of high-performance thermoplastic composite materials is more than 1.2 million tons.

Resin matrix composites have a wide range of applications, Table 1 shows the proportion of resin-based composite materials used in the industries of automobile, construction and shipbuilding in several major countries such as the United States, Western Europe and Japan.

China's resin-based composite materials began in 1958, the resin-based composite fishing boats were developed by hand-laminated process at that time, and resin-based composite plates, tubes and rocket barrels were successfully developed by lamination and rolling process, etc. In 1961, the ablation-resistant ends were developed, in 1962, unsaturated polyester resin and honeycomb molding machine and injection molding machine were introduced to develop aircraft propellers and fan blades.

In 1962, the research succeeded in the winding process and produced a batch of oxygen cylinders and other pressure vessels.In 1970, a large radome of resin matrix composite material with diameter of 44 meters was manufactured by hand-laminated structural plate. Before 1971, China's resin-based composite industry was mainly for military products, and after the 1970s, it began to turn to civilian use. 1987, a large number of foreign advanced technologies such as pool kiln drawing, short-cut felt, surface felt production lines and various grades of polyester resin (U.S., Germany, Netherlands, UK, Italy, Japan) and epoxy resin (Japan, Germany) were introduced to China; In terms of molding technology, we have been introduced winding pipe and tank production line, pultrusion process production line, SMC production line, continuous plate making unit, resin transfer molding machine (RTM), injection molding technology, resin injection molding technology and fishing rod production line, etc. We have formed a complete industrial system from research, design, production and raw material matching. By the end of 2000, China's resin-based composite materials production enterprises reached more than 3,000. ISO9000 quality system certified company number of 51, more than 3,000 kinds of products, the total output of 730,000 tons / year, ranking second in the world. Products are mainly used in construction, anti-corrosion, light industry, transportation, shipbuilding and other industrial fields. In recent years, carbon fiber sheet reinforced building structures, pultruded composite doors and windows, SMC or BMC molded meter boxes, RTM products, etc. have emerged rapidly.

In construction industry, resin-based composites have been widely used in interior and exterior wall panels, transparent tiles, cooling towers, air conditioning covers, fans, FRP water tanks, sanitary ware, purification tanks, etc.

In petrochemical industry, it is mainly used in pipelines and storage tanks. Among them, FRP pipes are fixed-length pipes, centrifugal casting pipes and continuous pipes. According to the pressure level, it is divided into low and medium pressure pipes and high pressure pipes. China's "Eighth Five-Year Plan", "Ninth Five-Year Plan" during the introduction of 40 pipe and tank production lines, on-site winding of large storage tanks up to 12 meters in diameter, the maximum volume of storage tanks 10,000 cubic meters. Domestic development and production of glass fiber reinforced plastic pipe and tank production equipment, some technical indicators have exceeded the technical level of similar foreign equipment.


In transportation, in order to make transportation tools lighter, save fuel consumption, improve the service life and safety factor, currently in the transport has been used a large number of composite materials. In cars, there are mainly body, hood, bumpers and other accessories; in trains, there are carriage panels, doors and windows, seats, etc.; in boats, there are mainly hovercraft, lifeboats, reconnaissance boats, fishing boats, etc. At present, the longest FRP fishing boat made in China is 33 meters. In the field of machinery and electrical appliances such as roof fans, axial fans, cable trays, insulation rods, integrated circuit boards and other products have a considerable scale.


In the aerospace and military fields, such as light aircraft, tail fins, satellite antennas, rocket nozzles, bulletproof plates, bulletproof vests, torpedoes, etc. have made significant breakthroughs and contributed significantly to the national defense of China.

The main matrixes used in high performance thermosetting resin-based composites are epoxy resins, phenolic resins, vinylester resins, etc.

(1) Epoxy resin

Epoxy resin is characterized by excellent chemical stability, electrical insulation, corrosion resistance. They are widely used in various fields such as chemical industry, light industry, machinery, electronics, water conservancy, transportation, automobiles, home appliances and aerospace, etc as per good adhesive properties and high mechanical strength.


The world epoxy resin production capacity was 1.3 million tons in 1993, increased to 1.43 million tons in 1996, 1.48 million tons in 1997, 1.5 million tons in 1999, and is expected to reach 1.6 million tons in 2003.


China started to research epoxy resin in 1975. According to incomplete statistics, there are more than 170 epoxy resin manufacturers in China, with a total production capacity of more than 150,000 tons and an equipment utilization rate of about 50%.

(2) Phenolic resin

Phenolic resin has the characteristics of heat resistance, abrasion resistance, high mechanical strength, excellent electrical insulation, low smoke generation and excellent acid resistance, etc., so it is widely used in various fields of the composite material industry. In recent years, they have been used in certain high-technology fields such as electronics industry, automotive industry, and aerospace industry.


In 1997, the global production of phenolic resin was 3 million tons, including 1.64 million tons in the United States. China's production was 180,000 tons and imported 40,000 tons. The applications of phenolic resin include automotive brake pads, phenolic capacitor encapsulation material, deep filtration materials, aerospace and other industries.

(3) Vinylester resin

Vinylester resin is a new type of thermosetting resin developed in the 1960s, characterized by good corrosion resistance, good solvent resistance, high mechanical strength, high elongation, good bonding performance with metal, plastic, concrete and other materials, good fatigue resistance, good electrical properties, heat aging, low curing shrinkage, can be cured at room temperature or heated.


Nanjing Jinling DSM Resin Co., Ltd. has introduced advanced technology from Holland to produce Atlac series of strong corrosion resistant vinylester resin, which has been widely used in storage tanks, containers, pipes, etc. Some varieties can also be used for waterproofing and hot press molding. Ltd., Shanghai Xinhua Resin Factory, Nantong Mingjia Polymer Co., Ltd. and other manufacturers also produce vinylester resin.

2. Thermoplastic resin matrix composites

Thermoplastic resin-based composites were developed in the 1980s, the proportion in the total number of composites is increasing year by year because they can be recycled. The main varieties are long fiber reinforced pellets (LFP), continuous fiber reinforced prepreg tape (MITT) and fiber thermoplastic sheet tree (GMT). According to the different requirements of use, the resin matrix mainly includes PP, PE, PA, PBT, PEI, PC, PEI, PES, PEEK, PI, PAI and other thermoplastic engineering plastics, and the fiber types include all possible fiber varieties such as glass fiber, carbon fiber, aramid fiber and boron fiber.


Thermoplastic resin-based composites account for more than 3O% of the total resin-based composites in developed countries in Europe and the U.S. In 2000, the output of thermosetting resin-based composites in Western Europe was 1.06 million tons, and that of thermoplastic composites was 540,000 tons, accounting for 34% of total resin-based composites.

High-performance thermoplastic resin-based composites are mostly injection parts, and the matrix is mainly PP and PA. Products include pipe fittings (elbows, tees, flanges), valves, impellers, bearings, electrical and automotive parts, extruded pipes, GMT (thermoplastic sheet molding plastic) molded products such as jeep seat brackets, car pedals, seats, etc. Applications of glass fiber reinforced polypropylene in automobiles include ventilation and heating systems, air filter housings, transmission covers, seat frames, fender gaskets, drive belt protectors, etc.


Talc-filled PP has high rigidity, high strength, excellent heat and aging resistance and cold resistance. Talc-reinforced PP has important applications in vehicle interior decoration, such as used as ventilation system parts. Instrument panel and automatic brake control bar, etc. Automotive parts are mostly used for ordinary PP and composite PP with inorganic filler materials such as talcum powder. The United States HPM company with 20% talc-filled PP made of 168m2, 5kg honeycomb structure of the acoustic ceiling and the car's roll-up window lifter rope tube shell.

Mica composite material has high rigidity, high heat deflection temperature, low shrinkage, low flexural matter, dimensional stability and low density and low price compared with metal, etc. Using mica/pp composite material, we can make automobile dashboard, headlight protection ring, fender cover, door guard, lively shell, motor fan, shutter and other parts, using the damping property of the material, we can make audio parts, using its shielding property, we can make Battery box, etc.


At present, Toyota Motor Corporation and Mitsubishi Chemical Corporation jointly developed PP/EPR/talc nanocomposite materials for front and rear bumpers, which were commercialized in 1991, thus reducing the thickness of bumpers on Toyota vehicles from 4mm to 3mm and reducing their mass by about 1/3. In 1994, Toyota developed nanocomposites such as TSOP-2 and TSOP-3 for automotive interior decoration.


For thermoplastic composites such as PA, PP and other general matrices, they have not been popularly used due to their poor heat resistance. In recent years, the modification of existing thermoplastic resins on the one hand and the development of high-performance thermoplastic resins such as PPO, PEEK, PEI, PPS, PSF, etc. on the other hand have led to the increasing application of thermoplastic composites.


The thermoplastic resin-based composites in China started in the late 1980s and have made rapid development in the past decade (see Table 3), with the output reaching 120,000 tons in 2000, accounting for about 17% of the total output of resin-based composites, which is still far from the developed countries. The matrix materials used are still mainly PP and PA, and the reinforcing materials are mainly glass fiber, a small amount of carbon fiber, which failed to make a major breakthrough in thermoplastic composites. China's nanotechnology provides good opportunities for polymer modification and application, such as nano-modified PA, but there is still a single composite system, industrialization is not high, most of them are only in the laboratory research stage, not fully promote the practical, polymer nanocomposites have the characteristics and potential, in the future for a long time to rely on nanotechnology to create a precedent and improve.


The reinforcing materials used in resin-based composites are mainly glass fiber, carbon fiber, aramid fiber, ultra-high molecular weight polyethylene fiber, etc.

(1) Glass fiber

Currently used in high-performance composite materials, glass fibers are mainly high-strength glass fibers, quartz glass fibers and high-silica oxygen glass fibers.


The late 1950s, the United States first research and development of high-strength glass fiber (S-994), so far, the world only the United States, France, Japan, Russia, Canada and China's six countries can produce high-strength glass fiber. Due to the high strength glass fiber performance and price is relatively good, with an annual growth rate of more than 10%. 1991 the total production of Western countries has reached 480 tons, is now estimated to have been in more than 5000 tons. High-strength glass fiber composites are not only used in military applications, in recent years, civilian products are also widely used, such as bulletproof helmets, bulletproof clothing, helicopter wings, early warning aircraft radome, a variety of high-pressure pressure vessels, civilian aircraft straight plate, sporting goods, all kinds of high-temperature products and recently reported excellent performance of the tire cord and so on.


Quartz glass fiber and high silica oxygen glass fiber belongs to the high temperature resistant glass fiber, is more ideal for heat and fire resistant materials, with its reinforced phenolic resin can be made into a variety of structures of high temperature resistant, ablation resistant composite parts, a large number of applications in rockets, missiles, heat-resistant materials.


So far, China has been practical high-performance resin-based composite materials with carbon fiber, aramid fiber, high-strength glass fiber three reinforcing fibers, only high-strength glass fiber has reached the international advanced level, and has independent intellectual property rights, the formation of a small-scale industry, the current stage of annual output of up to 500 tons.

(2) carbon fiber

Carbon fiber has high strength, high modulus, high temperature resistance, electrical conductivity and a series of properties, first in the aerospace field is widely used, and in recent years in sports equipment and sports goods are also widely used. It is predicted that carbon fiber composite materials will be expanded in recent years to open up new applications, civil engineering, transportation, automotive, energy and other fields will be large-scale use of industrial carbon fiber. 1997 to 2000, the annual growth rate of carbon fiber for aerospace is estimated at 31%, while the annual growth rate of industrial carbon fiber is estimated to reach 130%.


The overall level of carbon fiber in China is still relatively low, equivalent to the level of foreign countries in the middle and end of the seventies, and the gap between foreign countries is about 20 years. The main problems of domestic carbon fiber are less stable performance and large dispersion coefficient, no high-performance carbon fiber, single species, incomplete specifications, continuous length is not enough, no surface treatment, high prices, etc.

(3) Aramid fiber

In 1972, the United States DuPont company research and development of successful all-para aromatic polyamide named Kevlar goods officially used in high-performance summer materials. 1972 production of only 45 tons, to 1977 increased to 4200 tons, rose to 21000 tons in 1982, the annual growth rate of 20%. 20 century since the 1980s, the Netherlands, Japan, the former Soviet Union has also carried out Aramid fiber research and development work. The "Twaron" series of fibers of Enka, a subsidiary of AKZO in the Netherlands, had an annual production capacity of 1,000 to 2,000 tons in 1986 and is expected to reach 15,000 tons in 2000. Aramid fibers from Teijin, Japan and Russia have been put on the market, and the annual growth rate has reached about 20%.


Aramid fiber has high specific strength and modulus, so it is widely used in high performance composite parts in the aerospace field (such as rocket engine housing, aircraft engine compartment, fairing, rudder, etc.), ships (such as aircraft carriers, nuclear submarines, yachts, lifeboats, etc.), automobiles (such as tire cord, high-pressure hose, friction materials, high-pressure gas cylinders, etc.) and heat-resistant transportation belts, sports equipment, etc.

(4) Ultra-high molecular weight polyethylene fiber

At present, the main products on the market are Ailled Spectra900 and 1000, DSM (Netherlands)-Toyoba (Japan) joint production of DyneemaSK60 and Mitsui (Japan) company's TekmilonI, etc.. The specific strength of UHMWPE fiber is the first among all kinds of fibers, especially it has excellent resistance to chemical reagent erosion and aging. It also has excellent high-frequency sonar permeability and seawater corrosion resistance, and many countries have used it to manufacture high-frequency sonar deflector shields for ships, which greatly improves the mine detection and mine sweeping capabilities of ships. In the offshore oil field applications of high-performance lightweight composite


In addition to playing a pivotal role in military applications, it also has broad application prospects in automobile manufacturing, shipbuilding, medical equipment, sports equipment and other fields. The fiber has attracted great interest and attention from developed countries around the world since its introduction, and the growth rate of the United States in 1989 was 26%, much higher than other high-performance fibers. Aramid fiber and high molecular weight polyethylene fiber have not been commercialized in China so far. Although in 1972 China began to research aramid fiber, in February 1981 and the end of 1985, respectively, aramid worker, aramid for technical identification, its high-purity material block in Nantong Synthetic Resin Factory trial, drawn into fiber by the Shanghai Synthetic Fiber Research Institute, due to the uniformity of monofilament diameter, there are some problems in the set, to the early 1990s, the output is only a few tons, and foreign The gap with foreign countries is very big.


High-performance resin matrix composite technology in the 21st century is an intelligent material that gives composite materials self-healing, self-decomposition, self-diagnosis and self-made functions. To develop high stiffness and high strength. Focus on composite materials used in high humidity and heat environments, and construct material systems that integrate materials, molding and processing, design, and inspection. The organizational system will be alliance (such as the American Automobile Alliance) and grouping. This will make fuller use of the resources (technical resources, material resources) of all parties and closely link the advantages of all parties in order to promote the further development of the composite material industry.

(II) Metal matrix composites

Metal matrix composites mainly emerged with the requirements of high strength and low density in the aerospace industry, so the metal matrix composites that are widely researched and applied are those with Al, Mg and other light metals as the matrix. 1960s, metal matrix composites continuously reinforced with crane and boron fibers sprang up. Due to the high price of continuous fiber-reinforced composites and the complexity of the manufacturing process, research on this material slipped in the 1970s. The increasing demand for high temperature resistant materials for high temperature components in turbine engines triggered a revival of research on metal matrix composites, especially titanium matrix materials.


Discontinuous reinforced composites developed rapidly in the 1980s, with research focusing on aluminum-based composites reinforced with silicon carbide or alumina particles and short fibers. These materials, regardless of the ratio of the matrix and reinforcement to the load, are between the two extremes of dispersion and continuous fiber reinforcement, which has excellent transverse properties, low consumption and excellent processability, compared with unreinforced alloys, performance has also been substantially improved. All these factors have made these materials the most commercially attractive materials in many applications.


Metal matrix composites in aerospace and astronautics applications include primarily the replacement of light but toxic beryllium. For example, SiCp/Al composites were used to replace beryllium in U.S. Trident missiles, and silicon carbide particle/aluminum matrix composites are also used to replace carbon/epoxy in aircraft electronics. In non-aerospace and aerospace applications, short fiber reinforced metal matrix composites are gaining general interest in automotive applications. Examples include partially reinforced internal combustion engine pistons, which are topped by alumina short fibers or mixed alumina and silica short fiber reinforced aluminum matrix composites. Conventional internal combustion engine pistons are manufactured from Al-Si casting alloys, and some use high nickel cast iron rings inlaid in the first ring groove.