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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.
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%.
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 Ⅱ 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.
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