复合材料已然蓄势待发。复合材料在各领域的应用日渐普遍。一度应用于水上运动领域的复合材料现在已经拓展应用到了航空、汽车、风电和运动设备中。复合材料的优势是什么?将两种本无法融合的材料组合在一起,形成轻质、坚固的性能,且无论单独使用哪一种,都无法实现相同的性能。
这种复合材料含有增强体部分(如碳纤维或玻璃纤维),能够保证复合材料的机械强度,而基质可以为金属、矿物(陶瓷)或有机物—即热塑或热固性聚合树脂基塑料。目前工业上使用规模**是碳纤维或玻璃纤维加强的有机复合材料(OMC)。
Composite material is a new material that people use advanced material preparation technology to optimize the composition of different materials. The general definition of composite materials should meet the following conditions:
(i) Composite materials must be man-made and designed and manufactured according to people's needs;
(II) the composite material must be composed of two or more material components with different chemical and physical properties in the designed form, proportion and distribution, with obvious interface between the components;
(III) it is structurally designable and can be used for composite structural design;
(IV) composite materials not only maintain the advantages of the properties of each component, but also obtain the comprehensive properties that can not be achieved by a single component through the complementary and correlation of the properties of each component[ 1]
The matrix materials of composites can be divided into metal and non-metal. Aluminum, magnesium, copper, titanium and their alloys are commonly used in metal matrix. Nonmetallic matrix mainly includes synthetic resin, rubber, ceramics, graphite, carbon, etc. The reinforcing materials mainly include glass fiber, carbon fiber, boron fiber, aramid fiber, silicon carbide fiber, asbestos fiber, whisker and metal.
Characteristics of various materials draw on each other's strong points and complement each other's weak points in performance, and they are classified into two categories: metal and non-metal
catalogue
1 History
2 classification
3 performance
4 molding method
5 Application
▪ application area
▪ Development and Application
▪ Reinforcing material
▪ glass fibre
▪ carbon fibre
▪ Aramid fiber
▪ Composite material innovation
▪ Composite market
▪ Infrastructure applications
▪ Treatment and regeneration
▪ Automotive Applications
Historical phonetics
The history of composite materials can be traced back to ancient times. Rice straw or wheat straw reinforced clay used since ancient times and reinforced concrete used for hundreds of years are composed of two kinds of materials. In the 1940s, due to the needs of aviation industry, glass fiber reinforced plastics (commonly known as glass fiber reinforced plastics) were developed. Since then, the name of composite material appeared. After 1950s, carbon fiber, graphite fiber and boron fiber with high strength and high modulus have been developed. Aramid fiber and silicon carbide fiber appeared in 1970s. These high strength and high modulus fibers can be compounded with synthetic resin, carbon, graphite, ceramics, rubber and other non-metal matrix or aluminum, magnesium, titanium and other metal matrix to form unique composite materials.
The development of modern high technology is inseparable from composite materials. Composite materials play a very important role in the development of modern science and technology. The research depth and application scope of composite materials, as well as the speed and scale of production and development, have become one of the important symbols to measure the advanced level of science and technology of a country. Since the beginning of the 21st century, the global composite market has grown rapidly, especially in Asia and China. From 2003 to 2008, China's average annual growth rate was 15%, India's was 9.5%, while Europe and North America's average annual growth rate was only 4%.
Composite materials for the fifth generation fighter
Composite materials for the fifth generation fighter
In the 1960s, in order to meet the needs of materials used in aerospace and other cutting-edge technologies, composites reinforced with high-performance fibers (such as carbon fiber, boron fiber, aramid fiber, silicon carbide fiber, etc.) were developed and produced successively, with the specific strength greater than 4 × 10 cm, and the specific modulus is greater than 4 × 10cm。 In order to distinguish from the first generation of glass fiber reinforced resin composites, this kind of composites is called advanced composites. According to different matrix materials, advanced composites can be divided into resin matrix, metal matrix and ceramic matrix composites. The service temperature of the system is 250-350 ℃, 350-1200 ℃ and above 1200 ℃. In addition to being used as structural materials, advanced composite materials can also be used as functional materials, such as gradient composite materials (functional composite materials whose chemical and crystallographic composition, structure and voids of materials continuously change in space), smart composite materials (functional composite materials with sensing, processing and executive functions and can adapt to environmental changes), bionic composite materials, stealthy composite materials, etc.
In 2007, China (mainland) produced 1.6 million tons of composite glass fiber, of which 1.155 million tons were used in FRP industry; The output of unsaturated polyester resin (UPR) is 1.35 million tons, of which 688000 tons are used in the field of FRP, accounting for 51%; The output of vinyl resin is 12640 tons and gel coat resin is 15870 tons.
In 2008, the economy of China's composite industry was stable, and the output increased by about 12%. The annual industrial added value of Enterprises above Designated Size in the industry was 8.67 billion yuan, the total industrial output value was 25.8 billion yuan, the output value of new products was 1.16 billion yuan, and the sales output value was 25.3 billion yuan.
At present, China's FRP and composite industry is facing a new period of great development, such as large-scale municipal construction in the process of urbanization, utilization and large-scale development of new energy, introduction of environmental protection policies, development of automobile industry, large-scale railway construction, large aircraft projects, etc. Under the huge market demand, the development of composite material industry will have a very broad development space.
Since the beginning of 2010, the national development and Reform Commission, the Ministry of science and technology, the Ministry of Finance and the Ministry of industry and information technology have jointly formulated and issued the draft of the decision on accelerating the cultivation of strategic emerging industries. After six months of consultation, the main fields have expanded from seven to nine, including two items of special function and high-performance composite materials.
After the "ten major industries revitalization plan", the "strategic emerging industries" has been regarded as another major measure to revitalize the economy. Since then, large-scale government investment has also been widely expected by the market. Therefore, it is also regarded as another large-scale industrial investment plan after the national "4 trillion" investment plan[ 4]
Classified speech
Composite [5] is a mixture. In many areas have played a great role, instead of a lot of traditional materials. According to its composition, composites can be divided into metal to metal composites, nonmetal to metal composites, nonmetal to nonmetal composites. According to its structural characteristics, it can be divided into: 1) fiber reinforced composites. All kinds of fiber reinforcements are compounded in the matrix material. Such as fiber reinforced plastics, fiber reinforced metals, etc. ② Sandwich composites. It is composed of different surface materials and core materials. Generally, the surface material is high strength and thin; The core material is light, low strength, but has a certain stiffness and thickness. It can be divided into solid sandwich and honeycomb sandwich. ③ Fine grained composites. The hard particles are uniformly distributed in the matrix, such as dispersion strengthened alloy, cermet and so on. ④ Hybrid composites. It is composed of two or more kinds of reinforcing materials mixed in one matrix material. The impact strength, fatigue strength and fracture toughness of the composites are significantly higher than those of the ordinary single reinforced composites, and the composites have special thermal expansion properties. It can be divided into interlaminar hybrid, interlaminar hybrid, sandwich hybrid, interlaminar / interlaminar hybrid and super hybrid composites.
Composites can be divided into structural composites and functional composites.
Structural composite is a kind of material used as load-bearing structure, which is basically composed of reinforcement component that can bear load and matrix component that can connect reinforcement to form a whole material and transfer force at the same time. Reinforcements include various glass, ceramics, carbon, polymers, metals, natural fibers, fabrics, whiskers, sheets and particles, while the matrix includes polymers (resins), metals, ceramics, glass, carbon and cement. A variety of structural composites can be made up of different reinforcements and different matrix, and named after the matrix used, such as polymer (resin) matrix composites. The characteristic of structural composite material is that it can select materials according to the requirements of the material in use. More importantly, it can also carry out the composite structure design, that is, the reinforcement arrangement design, which can reasonably meet the needs and save materials.
Functional composites are generally composed of functional components and matrix components. The matrix not only plays the role of forming a whole, but also has the role of synergy or strengthening function. Functional composites refer to the composites that provide other physical properties besides mechanical properties. Such as: conductive, superconducting, semiconductive, magnetic, piezoelectric, damping, wave absorption, wave transmission, friction, shielding, flame retardant, heat proof, sound absorption, heat insulation, highlight a function. They are called functional composites. Functional composites are mainly composed of functional body, reinforcement and matrix. The functional body can be composed of one or more functional materials. The composite material of multi-functional body can have many functions. At the same time, there may be new functions due to the compound effect. Multifunctional composites are the development direction of functional composites.
Composite materials can also be divided into common and advanced types.
Common composite materials, such as glass fiber reinforced plastics, are composed of low performance reinforcements such as glass fiber and common polymers (resins). Because of its low price, it has been widely used in ships, vehicles, chemical pipelines and tanks, building structures, sporting goods and so on.
Fiber reinforced materials are the most widely used and used in composites. It is characterized by small specific gravity, high specific strength and specific modulus. For example, the specific strength and specific modulus of carbon fiber / epoxy resin composites are several times higher than those of steel and aluminum alloy. They also have excellent chemical stability, friction and wear resistance, self lubrication, heat resistance, fatigue resistance, creep resistance, noise elimination, electrical insulation and other properties. The composite of graphite fiber and resin can obtain the material with the coefficient of thermal expansion almost equal to zero. Another characteristic of fiber reinforced materials is anisotropy, so the arrangement of fibers can be designed according to the strength requirements of different parts of the parts. The aluminum matrix composites reinforced with carbon fiber and silicon carbide fiber can maintain enough strength and modulus at 500 ℃. Silicon carbide fiber and titanium composite, not only improve the heat resistance of titanium, and wear resistance, can be used as engine fan blade. The composite of SiC fiber and ceramic can be used at 1500 ℃, which is much higher than that of super alloy turbine blade (1100 ℃). Carbon fiber reinforced carbon, graphite fiber reinforced carbon or graphite fiber reinforced graphite constitute ablation resistant materials, which have been used in spacecraft, rocket missiles and nuclear reactors. Because of its low density, nonmetal matrix composites can reduce weight, improve speed and save energy when used in automobiles and airplanes. The composite leaf spring made of carbon fiber and glass fiber has the same stiffness and bearing capacity as the steel leaf spring which is more than five times of its weight.
Molding method
The forming methods of composite materials are different according to different matrix materials. There are many molding methods of resin matrix composites, including hand lay up molding, spray molding, filament winding molding, molding, pultrusion molding, RTM molding, autoclave molding, diaphragm molding, migration molding, reaction injection molding, soft film expansion molding, stamping molding, etc. The forming methods of metal matrix composites can be divided into solid forming method and liquid forming method. The former is formed by applying pressure at a temperature lower than the melting point of the substrate, including diffusion welding, powder metallurgy, hot rolling, hot drawing, hot isostatic pressing and explosive welding. The latter is to melt the matrix and fill it into the reinforcement materials, including traditional casting, vacuum suction casting, vacuum back pressure casting, squeeze casting and spray casting, etc.
Application
The main application fields of composite materials are: (1) aerospace field. Due to its good thermal stability, high specific strength and stiffness, the composite can be used to manufacture aircraft wings and forebodies, satellite antennas and their supporting structures, solar cell wings and shells, large launch vehicle shells, engine shells, space shuttle structural parts, etc. ② Automobile industry. Because of the special vibration damping characteristics, the composite material can reduce vibration and noise, has good anti fatigue performance, is easy to repair after damage, and is convenient for integral forming, so it can be used to manufacture automobile body, stressed components, transmission shaft, engine frame and its internal components. ③ Chemical industry, textile and machinery manufacturing. Carbon fiber with good corrosion resistance is compounded with resin matrix, which can be used to manufacture chemical equipment, textile machine, paper machine, copier, high-speed machine tool, precision instrument, etc. ④ Medical field. Carbon fiber composite has excellent mechanical properties and non absorption of X-ray, which can be used to manufacture medical X-ray machine and orthopedic bracket. Carbon fiber composite materials also have biocompatibility and blood compatibility, good stability in biological environment, and can also be used as biomedical materials. In addition, the composite materials are also used in the manufacture of sports devices and building materials.
Development and Application
Composite material is a material composed of two or more different materials in different ways. It can give full play to the advantages of various materials, overcome the defects of a single material and expand the application scope of materials. Due to the characteristics of light weight, high strength, convenient processing, excellent elasticity, chemical corrosion resistance and good weather resistance, composite materials have gradually replaced wood and metal alloys, and are widely used in aerospace, automobile, electronic and electrical, construction, fitness equipment and other fields, and have been developed rapidly in recent years.
With the development of science and technology, the technology of resin and glass fiber is constantly improved, and the manufacturing capacity of manufacturers is generally improved. The price and cost of glass fiber reinforced composites have been accepted by many industries, but the strength of glass fiber reinforced composites is not enough to compete with metal. Therefore, carbon fiber, boron fiber and other reinforced composites have come out one after another, which makes the polymer composite family more complete and has become a necessary material for many industries. At present, the annual output of composite materials in the world has reached more than 5.5 million tons, with an annual value of more than 130 billion US dollars.If the high-value products of European and American military aerospace are included, the output value will be even more amazing. Globally, the production of composite materials in the world is mainly concentrated in Europe, America and East Asia. In recent years, the production and demand of composite materials in Europe and America continue to grow, while Japan in Asia develops slowly due to the economic downturn. However, the market in China, especially in the mainland of China, develops rapidly. According to the statistics of PPG, the world's leading composite material manufacturer, the global share of composite materials in Europe was about 32% in 2000, with an annual output of about 2 million tons. At the same time, the average annual growth rate of composite materials in the U.S. in the 1990s was about twice that of the U.S. GDP, reaching 4% ~ 6%. In 2000, the annual output of composite materials in the United States reached about 1.7 million tons. In particular, the rapid increase of composite materials for automobile makes American automobile rise again in the global market.
The development of composite materials in Asia in recent years is closely related to the overall changes of politics and economy, and the share of each country has changed greatly. Overall, Asia's composite materials will continue to grow, with a total output of 1.45 million tons in 2000 and 1.8 million tons in 2005.In terms of application, composite materials are mainly used in aerospace, automobile and other industries in the United States and Europe. In 2000, the consumption of composite materials for automobile parts in the United States reached 148000 tons, while that in Europe is estimated to reach 105000 tons by 2003. In Japan, composite materials are mainly used in residential construction, such as bathroom equipment, etc. the consumption of such products reached 75000 tons in 2000, and the consumption of automobile and other fields was only 24000 tons. However, from a global perspective, the automotive industry is the largest user of composite materials, and its future development potential is still very huge.
At present, many new technologies are still under development. For example, in order to reduce engine noise and increase car comfort, efforts are being made to develop damping steel plates with thermoplastic resin adhered between two layers of cold rolled plates; In order to meet the requirements of high-speed, supercharging and high load development of engine, metal matrix composites have been used in piston, connecting rod and bearing bush of engine. In order to meet the requirements of automobile lightweight, more and more new composite materials will be applied to automobile manufacturing industry. At the same time, with the increasing attention to environmental protection in recent years, the application of polymer composites to replace wood has been further promoted. For example, composite materials made from plant fibers and waste plastics have been widely used as pallets and packing boxes in North America to replace wooden products; And degradable composites have become the focus of research and development at home and abroad.
In addition, nanotechnology has gradually attracted people's attention, and the research and development of nanocomposites has become a new hot spot. By modifying plastics with nano particles, the aggregation state and crystalline form of plastics can be changed, so that they have new properties. The contradiction between rigidity and toughness of traditional materials is overcome, and the comprehensive properties of materials are greatly improved.
Reinforcing material
The reinforced materials used in resin matrix composites mainly include glass fiber, carbon fiber, aramid fiber, UHMWPE fiber, etc.
glass fibre
At present, the glass fibers used in high-performance composites mainly include high-strength glass fiber, quartz glass fiber and high silica glass fiber. Due to the high cost performance of high-strength glass fiber, the growth rate is relatively fast, with an annual growth rate of more than 10%. High strength glass fiber composites are not only used in military, but also widely used in civil products in recent years, such as bulletproof helmets, bulletproof suits, helicopter wings, early warning aircraft radome, various high-pressure pressure vessels, civil aircraft straight board, sporting goods, various high-temperature products and recently reported tire cord with excellent performance. Quartz glass fiber and high silica glass fiber are high temperature resistant glass fibers, which are ideal heat-resistant and fireproof materials. Phenolic resin reinforced with quartz glass fiber can be used to make high temperature resistant and ablation resistant composite parts with various structures, which are widely used in heat-resistant materials of rockets and missiles. So far, only high strength glass fiber has reached the international advanced level, and has independent intellectual property rights, forming a small-scale industry. At present, the annual output can reach 500 tons.
carbon fibre
Carbon fiber has a series of properties, such as high strength, high modulus, high temperature resistance, electrical conductivity and so on. First of all, it has been widely used in the field of aerospace. In recent years, it has also been widely used in sports equipment and sporting goods. It is predicted that industrial carbon fiber will be widely used in civil construction, transportation, automobile, energy and other fields. From 1997 to 2000, the annual growth rate of aerospace carbon fiber is estimated to be 31%, while the annual growth rate of industrial carbon fiber is estimated to be 130%. The overall level of carbon fiber in China is still relatively low, which is equivalent to the level of foreign countries in the mid and late 1970s, and the gap with foreign countries is about 20 years. The main problems of domestic carbon fiber are unstable performance, large dispersion coefficient, no high performance carbon fiber, single variety, incomplete specification, insufficient continuous length, no surface treatment and high price.
Aramid fiber
Since the 1980s, the Netherlands, Japan and the former Soviet Union have also carried out the research and development of aramid fiber. Aramid fibers from Japan and Russia have been put into the market with an annual growth rate of about 20%. Aramid fiber has high specific strength and modulus, so it is widely used in high-performance composite parts (such as rocket engine shell, 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, etc.) High pressure cylinder, etc.) and heat-resistant transport belt, sports equipment, etc.
UHMWPE fiber
The strength of UHMWPE fiber is the highest among all kinds of fibers, especially its chemical resistance and corrosion resistance. It also has excellent high-frequency sonar permeability and seawater corrosion resistance. Many countries have used it to manufacture high-frequency sonar deflector of warships, which greatly improves the capability of mine detection and mine sweeping of warships. In addition to the military field, UHMWPE fiber also has broad application prospects in automobile manufacturing, shipbuilding, medical equipment, sports equipment and other fields. As soon as the fiber came out, it attracted great interest and attention of developed countries in the world.
Thermosetting resin matrix composites
Thermosetting resin matrix composites refer to the composites made of thermosetting resins such as unsaturated polyester resin, epoxy resin, phenolic resin, vinyl ester resin, glass fiber, carbon fiber, aramid fiber, ultra-high molecular weight polyethylene fiber, etc. Epoxy resin is characterized by excellent chemical stability, electrical insulation, corrosion resistance, good adhesion and high mechanical strength. It is widely used in chemical industry, light industry, machinery, electronics, water conservancy, transportation, automobile, household appliances, aerospace and other fields. The production capacity of epoxy resin in the world 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 about 1.8 million tons in 2003. China began to study epoxy resin in 1975. According to incomplete statistics, there are about 170 epoxy resin manufacturers in China, with a total production capacity of more than 500000 tons and an equipment utilization rate of about 80%. Phenolic resin is widely used in various fields of composite material industry because of its excellent heat resistance, abrasion resistance, high mechanical strength, excellent electrical insulation, low smoke and acid resistance. In 1997, the global output of phenolic resin was 3 million tons, including 1.64 million tons in the United States. China's output is 180000 tons and imports 40000 tons. Vinyl ester resin is a new type of thermosetting resin developed in the 1960s. It is characterized by good corrosion resistance, solvent resistance, high mechanical strength, high elongation, good bonding performance with metal, plastic, concrete and other materials, good fatigue resistance, good electrical performance, heat aging, low curing shrinkage, and can be cured at room temperature or by heating. Nanjing Jinling DSM resin Co., Ltd. has imported Atlac series strong corrosion resistant vinyl ester resin from Holland, which has been widely used in storage tanks, containers, pipes, etc., and some varieties can also be used for waterproof and hot pressing. Nanjing Julong composite material Co., Ltd., Shanghai Xinhua resin factory and Nantong Mingjia polymer Co., Ltd. also produce vinyl ester resin.
Before 1971, China's thermosetting resin matrix composites industry was mainly military products, but after 1970s, it began to turn to civilian. Since 1987, a large number of foreign advanced technologies have been introduced, such as tank furnace drawing, chopped strand mat, surface mat production line, polyester resin (US, Germany, Netherlands, UK, Italy, Japan) and epoxy resin (Japan, Germany) production technologies of various brands; In terms of molding process, we have introduced winding pipe, can production line, pultrusion process production line, SMC production line, continuous plate making unit, resin transfer molding (RTM) molding machine, spray molding technology, resin injection molding technology and fishing rod production line, etc., forming a complete industrial system from research, design, production and raw material matching, There are more than 3000 manufacturers of thermosetting resin matrix composites in China, and 51 of them have passed the ISO9000 quality system certification. There are more than 3000 varieties of products, with a total output of 730000 tons / year, ranking second in the world. The products are mainly used in construction, anticorrosion, light industry, transportation, shipbuilding and other industrial fields. In architecture, there are internal and external wall panels, transparent tiles, cooling tower, air conditioning cover, fan, FRP water tank, sanitary ware, purification tank, etc; In petrochemical industry, it is mainly used for pipeline and storage tank; In terms of transportation, there are mainly car body, hood, bumper and other accessories on the car, carriage plate, doors and windows, seats on the train, and hovercraft, lifeboat, reconnaissance boat, fishing boat and so on on on the boat; In the field of machinery and electrical appliances, such as roof fan, axial fan, cable tray, insulating rod, integrated circuit board and other products have considerable scale; In the aerospace and military fields, major breakthroughs have been made in light aircraft, tail, satellite antenna, rocket nozzle, bulletproof plate, bulletproof vest and torpedo.
Thermoplastic resin matrix composites
Thermoplastic resin matrix composites were developed in 1980s, mainly including long fiber reinforced granular (LFP), continuous fiber reinforced prepreg (mitt) and glass fiber mat reinforced thermoplastic composites (GMT). According to different application requirements, the resin matrix mainly includes PP, PE, PA, PBT, Pei, PC, PES, peek, PI, Pai and other thermoplastic engineering plastics. The fiber types include glass fiber, carbon fiber, aramid fiber, boron fiber and other possible fiber varieties. With the continuous maturity of thermoplastic resin matrix composite technology and the advantages of recycling, the development of this kind of composite material is fast, and the thermoplastic resin matrix composites in developed countries in Europe and America have accounted for more than 30% of the total amount of resin matrix composites.
Most of the high performance thermoplastic resin matrix composites are injection parts, and the matrix is PP and PA. The products include pipe fittings (elbow, tee, flange), valves, impellers, bearings, electrical and automotive parts, extruded pipes, GMT molded products (such as jeep seat bracket), car pedals, seats, etc. The application of glass fiber reinforced polypropylene in automobile includes ventilation and heating system, air filter shell, gearbox cover, seat frame, fender gasket, drive belt cover, etc.
Talc Filled PP has high rigidity, high strength, excellent heat aging resistance and cold resistance. Talc reinforced PP has important applications in interior decoration, such as parts of ventilation system, instrument panel and automatic brake control lever, etc. for example, the sound-absorbing ceiling with honeycomb structure made of 20% talc Filled PP by HPM company of the United States and the rope barrel shell of car window lifter.
Mica / polypropylene composite has the characteristics of high rigidity, high thermal deformation temperature, low shrinkage, low flexibility, stable size, low density and low price. It can be used to make automobile instrument panel, headlamp protection ring, baffle cover, door guardrail, motor fan, shutter and other parts. The damping property of the material can be used to make audio parts, The battery box can be made by using its shielding property.
The research of thermoplastic resin matrix composites in China began in the late 1980s, and has achieved rapid development in the past decade. In 2000, the output reached 120000 tons, accounting for 17% of the total output of resin matrix composites. The matrix materials used are still mainly PP and PA, the reinforcement materials are mainly glass fiber, and a small amount of carbon fiber. There is no significant breakthrough in thermoplastic composites, There is still a gap with developed countries.
Composite material innovation
The innovation of composite materials includes the development of composite materials technology, composite materials technology, composite materials products and composite materials application. Specifically, we should grasp the innovation of resin matrix development, reinforced materials development, production technology development and product application development. By 2007, the proportion of Asia in the total sales volume of composite materials in the world will increase from 18% to 25%. At present, the per capita consumption in Asia is only 0.29kg, while that in the United States is 6.8kg. Asia has great growth potential.
Development of polyacrylonitrile based fiber
The development of carbon fiber industry in China is slow. From the development review and characteristics of CF, the development process of domestic carbon fiber, the market situation and characteristics of PAN based CF in China, and the situation of tackling key scientific and technological problems in the tenth five year plan, it is possible and necessary to develop polyacrylonitrile based fiber.
Adjustment of glass fiber structure
More than 70% of China's glass fiber is used as reinforced base material, which has a cost advantage in the international market. However, there is still a gap between China and advanced countries in terms of varieties, specifications and quality. It is necessary to improve and develop yarn, woven fabric, non-woven felt, woven fabric, seam woven fabric and composite felt, promote the close cooperation between glass fiber and glass fiber reinforced plastic industries, and promote the new development of glass fiber reinforced materials.
Composite market
First, composite materials for clean and renewable energy, including composite materials for wind power generation, composite materials for flue gas desulfurization device, composite materials for power transmission and transformation equipment, and high-pressure containers for natural gas and hydrogen; Second, composite materials for automobile and urban rail transit, including automobile body, frame and body outer covering parts, rail transit body, door, seat, cable trough, cable rack, grille, electrical box, etc; Third, composite materials for civil aircraft, mainly carbon fiber composite materials. Thermoplastic composites account for about 10%, and the main products are wing parts, vertical tail, nose cover, etc. In the next 20 years, China will need to add 661 regional aircraft, which will form a large industry of civil aircraft. Composite materials can be built into a new industry to match it; Fourth, composite materials for boats, mainly yachts and fishing boats. Yachts, as high-grade entertainment and durable consumer goods, have a large market in Europe and America. Due to the reduction of fish resources in China and the slow development of fishing boats, the unique advantages of composite materials still have room for development.
Infrastructure applications
Composite materials are widely used in bridges, houses and roads at home and abroad. Compared with traditional materials, they have many advantages, especially in bridges, house reinforcement, tunnel engineering and large storage repair and reinforcement.
Treatment and regeneration
Focus on the development of physical recovery (crushing recovery), chemical recovery (pyrolysis) and energy recovery, strengthen the technical route, comprehensive treatment technology research, demonstration production line construction, recycling research, vigorously expand the application of recycled materials in gypsum, pultrusion products, SMC / BMC molded products and typical products.
In the 21st century, the technology of high-performance resin matrix composites is an intelligent material which endows composites with self repairing, self decomposing, self diagnosing and self-made functions. Focusing on the development of composite materials with high stiffness, high strength and high humidity and heat environment, a material system integrating materials, forming processing, design and inspection is constructed. The organization system will be alliance and collectivization, which will make full use of all kinds of resources (technical resources, material resources) and closely link with the advantages of all aspects, so as to promote the further development of composite materials industry.
Car applicationWith the development of modern science and technology, more and more non-metallic materials with the advantages of light weight, high strength, corrosion resistance and easy forming replace the traditional metal materials and are applied in automobiles. In the automotive industry, non-metallic materials include plastics, rubber, friction materials, coatings, adhesives, composite materials, glass, textile materials, sealing materials and lubricants. Among them, composite materials for automobile are more and more widely used in automobile industry, and have a certain market development prospect. Characteristics of automotive composite materials Generally called composite material, it is composed of two or more kinds of materials with different properties, such as fiber reinforcement and substrate (matrix), through various processes. It is equivalent to fiber reinforced plastic (FRP), fiber reinforced metal (FRM) and metal plastic laminated materials, and has the characteristics of light weight, high strength and good stiffness. These composite materials are widely used in automotive parts. Composite is a kind of heterogeneous material, which has the following outstanding characteristics compared with other materials 1) The specific strength and specific modulus are high. Specific strength and specific modulus refer to the strength of materials and the ratio of modulus to density. The higher the specific strength is, the smaller the self weight of parts is; The higher the specific modulus, the greater the rigidity of the part. Therefore, it is of great significance for the high-speed running structural parts or the transport tools that need to reduce the self weight. 2) The interface between fiber and matrix in fiber reinforced composites can effectively prevent the propagation of fatigue crack, and the external load is borne by the reinforced fiber. The fatigue strength limit of most metal materials is 30% - 50% of their tensile strength, while that of composite materials is 60% - 80%. 3) Adding a small amount of chopped carbon fiber into thermoplastic can greatly improve its wear resistance, which can be increased several times as much as the original. For example, PVC reinforced with carbon fiber is 3.8 times of itself, PTFE is 3 times of itself; Polypropylene is 2.5 times of itself; 2 times of polyamide itself; Polyester is twice as big as itself. Suitable plastic and steel plate composite can be used as wear-resistant materials, such as bearing materials. A three-layer composite material with polytetrafluoroethylene (or polyoxymethylene) as the surface layer, porous bronze and steel plate as the inner layer can be made into a good material for sliding bearing. 4) Good chemical stability. Fiber reinforced phenolic plastics can be used in acid medium containing chloride ions for a long time. Glass fiber reinforced plastics can be used to manufacture chemical pipes, pumps, valves and containers resistant to strong acids, salts, esters and some solvents. If alkali resistant fiber is compounded with plastic, it can also be used in strong alkali medium. Alkali resistant fiber can be used to replace steel and cement composite. 5) Good high temperature ablation resistance. The melting point (or softening point) of fiber reinforced composites is generally above 2000 ℃ except that the softening point of glass fiber is relatively low (700 ~ 900 ℃). The strength and modulus of composites composed of these fibers and metal matrix are improved at high temperature. For example, the strength and modulus of carbon fiber or boron fiber can be maintained at room temperature at 400 ℃. In the same way, carbon fiber reinforced nickel not only reduces density but also improves high temperature performance. FRP can be used as ablation resistant material because of its extremely low thermal conductivity and instantaneous ultra-high temperature resistance. 6) The technology and designability are good. By adjusting the shape, arrangement and content of reinforcing materials, the strength and stiffness of components can be met. The materials and components can be formed at one time, which reduces the number of parts, fasteners and joints, and greatly improves the utilization rate of materials. Functions and properties of composite materials Compared with traditional materials, composite materials have many advantages, such as high specific strength, light weight, high specific modulus, good fatigue resistance and vibration reduction performance. Each component of the composite material plays a synergistic role in the performance, and has superior comprehensive performance than a single material. Therefore, in the automotive industry, composite materials are widely used in the design and manufacture of body, lamp cover, front and rear guard, bumper, plate spring, seat frame and drive shaft. Three principles should be paid attention to in the design of composite materials in automobile industry: 1) high specific strength and high specific stiffness; 2) The materials adapt to the environment; 3) Cost effective. In addition, in the design of car body, there are some experience methods, such as: carbon fiber composite material is suitable for high stress area; In the area of high toughness and stiffness requirements, the composite material of plywood is used; Laminates can be used in areas of complex geometry. The performance of composite material is suitable for the requirement of light weight of car body and reduces fuel consumption. The traditional automobile body material is in the single state of thin steel plate, which can not meet the requirements of people's pursuit of high speed and lightweight. In order to reduce its quality, improve the drag coefficient and reduce fuel consumption, many automobile manufacturers are actively studying and using new materials to achieve the above requirements. The weight of the vehicle is reduced by 50kg, and the driving distance of 1l fuel can be increased by 2km; If the dead weight is reduced by 10%, the fuel economy can be improved by about 5.5%. Many types of composite materials have got the stage to show their talents in the process of car body lightweight, and show their talents in the process of car lightweight. The purpose of automobile lightweight is to save energy and reduce emission pollution. At the same time, environmental protection has become an essential condition for sustainable development strategy, and the development trend of composite materials is towards the extension of service life and renewable direction. Composite materials under development 1) Carbon fiber reinforced plastics (CFRP). Carbon fiber is made of fiber and polypropylene eye after high temperature heating treatment. It has high heat resistance, smaller specific gravity than aluminum and glass fiber, and its strength can match that of steel and aluminum when compounded with plastic. However, the cost of CFRP is much higher than that of GFRP (glass fiber reinforced plastic), and most of them are used in aerospace and sporting goods. In 1979, Ford Motor Company of the United States published a new idea of using GFRP to make a light experimental vehicle (see Figure 1), in which the use of CFRP is about 300kg, and the fuel cost can be reduced by about 35%. The experimental vehicle mainly uses CFRP material in the body panel, and other functional parts such as transmission shaft and leaf spring. At the same time, it also tries to apply it in engine body, connecting rod, piston and other parts. CFRP material is light in weight, high in stiffness and strength. Due to the anisotropy of the material, it can maintain its strength and rigidity in the required direction. The elastic modulus of CFRP is 4 ~ 9 times that of GFRP and 3 ~ 4 times that of metal materials. If mass production, the cost will be further reduced, so it will be a composite with high expectations. 2) Fiber reinforced metal (FRM). CFRP and GFRP have various superior mechanical properties, but their substrate is plastic, which has poor heat resistance compared with metal. Therefore, the research of frm as high temperature strength material is very popular, and the possibility of its application in automobile is revealed. Reinforced fibers are: carbon, silicon carbide, boron, alumina, etc. The substrate includes aluminum, copper and nickel at first, and then titanium, magnesium, zinc and tin for various purposes. The combination of reinforcing fiber and various metals will produce frm with various characteristics. At present, the application of frm to piston, connecting rod and other sliding parts is being studied. Because of its high price and not reaching the scale of mass production, this kind of fiber has a high utilization value as a high temperature strength material. 3) Metal plastic laminates. The material that combines high strength steel plate with aluminum, plastic and so on is an ideal light material, and it is also a kind of laminated material of sandwich structure. Because it is bonded on both sides of the plastic core with thin steel plate or aluminum plate, it has superior heat insulation and sound insulation performance. Laminated material, it is called to play with the steel plate to match the characteristics of good rigidity, it is by the plastic core on both sides of the metal plate to bear bending stress, by the plastic core material to bear shear stress. Under the same rigidity, the mass of the laminated steel plate is 30% - 70% compared with that of the ordinary steel plate. If there is a certain limit on the mass of the laminated plate, it can be solved by changing the thickness of the metal plate and the core plate on both sides of the core. The cost of laminated material is generally 1-3 times that of steel plate, but there are still some problems to be solved, such as: how to bond with each panel when it is used in car body panel; When the steel plate on its surface is corroded, the rigidity will be reduced. However, with the development of laminated materials, it is possible to make it practical. 4) Glass fiber reinforced composites for vehicles. Due to the variety of reinforcing materials and filling materials, the material using glass fiber as reinforcing material is called gfrr. As the addition of glass fiber greatly improves the physical and mechanical properties of plastics, the reinforced plastics can also be used as engineering materials. At present, glass fiber reinforced plastics used in automobile mainly include glass fiber reinforced PP, glass fiber reinforced PA66 or PA6, and a small amount of PBT and PPO materials. Glass fiber reinforced composites used in automobiles include glass fiber reinforced thermoplastic materials, glass fiber mat reinforced thermoplastic materials (GMT), sheet molding materials (SMC), resin transfer molding materials (RTM) and hand laid FRP products. Reinforced PP is mainly used to make engine cooling fan blades and timing belt upper and lower covers, but some products have defects such as poor appearance quality and warpage, so non-functional parts are gradually replaced by talcum powder filled PP. Reinforced PA materials have been used in cars, vans and trucks, and are generally used to make small functional parts, such as lock body protective cover, safety wedge, embedded nut, accelerator pedal, upper and lower gear guard protective cover and opening handle, etc. GMT is a kind of new, energy-saving and light-weight composite material with thermoplastic resin as the matrix and glass fiber felt as the reinforcement framework. Generally, it can produce semi-finished sheet materials, and then directly process them into products with the required shape. The fiber can be chopped glass fiber or continuous glass fiber felt. SMC is an important and widely used semi-finished product of molded composite products. Compared with steel auto parts, SC has short production cycle, convenient for auto modification and good investment benefit; Light weight, fuel saving; Freedom of design; The integrity of the parts is good, and the number of parts is small; Good durability and heat insulation. However, SMC can not be recycled and pollutes the environment; Although the performance and price are relatively good, the one-time investment is often higher than the corresponding steel parts, such as the lower radiator bracket in the front wall of Ford Taurus and Mercury Sable cars. The original steel part has 22 parts, while the SMC part has only 2 parts. The quality is greatly reduced and the cost is reduced by 14%. Although many automobile factories have replaced the relatively heavy metal with glass fiber reinforced material in the production of automobile body, glass fiber is drawn from molten glass, which is very easy to re solidify after melting at high temperature, which brings great difficulties to the recycling of waste automobiles. For this reason, the French National Center for scientific research is studying a kind of synthetic material based on hemp and polyurethane. This material is characterized by cheaper price, lighter weight, stronger toughness and biodegradation, besides the advantages of metal and glass fiber. Now, the center is testing the strength and other properties of this material. The first phase is to produce car doors with this material. Metal matrix composites in automobile MMC is mainly used in particle reinforced and short fiber reinforced aluminum matrix composites in automobile industry. MMC has been widely used in industry due to its high specific strength and stiffness, good wear resistance, good thermal conductivity and low coefficient of thermal expansion. MMC used in automobile industry is reinforced by aluminum or magnesium matrix and powder or chip fiber. The brake disc, brake drum, brake caliper, piston, transmission shaft and tire bolt are made of MMC. At present, Al Si alloy is generally used in aluminum matrix composites. The commonly used fillers are ceramic fibers and particles. Compared with aluminum alloy, it has the advantages of light weight, high specific strength, high elastic modulus, good heat resistance and wear resistance. It is an ideal material for automobile lightweight. Piston is one of the main parts of engine, it works under high temperature and high pressure, so it is very important to choose the right piston material. At present, the composite material used in piston is composed of low density metal and reinforced ceramic fiber, which is mainly used in high performance aluminum piston. In recent years, fiber reinforced metal (FRM) has been developed. Aluminum alloy based frm has high tensile strength, wear resistance and heat resistance. Fiber reinforced light metals can be used in the parts where the strength and wear resistance can not be satisfied only by light alloys, so they are promising materials. On this basis, the aluminum piston with alumina fiber reinforced piston crown and the piston made of alumina reinforced magnesium alloy are introduced, which further expands its application in piston. Aluminum matrix composites have been used in brake wheels in the United States. Its characteristics are that the mass of aluminum matrix composite material is reduced by 30% ~ 60%, the thermal conductivity is good, the maximum service temperature is 450 ℃, and its thermal performance has reached the original level of cast iron. MMC must be manufactured in a new way, and the principle of limiting application is that matching brake pedal must be developed. When the brake caliper is made of metal matrix composite material, besides reducing the quality, the main benefit is the stiffness. MMC brake calipers are used in high-performance sports cars, but the high cost limits its wide application. MMC piston is mainly used in diesel engine, but it can also be used in gasoline engine. Because alumina and silica short fiber reinforced, but thermal fatigue easily lead to fracture. Using ceramic fiber preform can weaken this problem and improve the service life of piston. The tire bolts are made of MMC, and the weight is reduced by 50%. In 2000, the consumption of metal matrix composites in the world automobile industry reached 6000 tons. With the continuous improvement of preparation technology and properties of composite materials, as well as the decreasing price, MMC will be more and more widely used in automobile industry. Composite materials and body suspension system After the 1960s, due to the in-depth study of composite materials, such as glass fiber reinforced materials, carbon fiber reinforced materials and high elastic matrix composites, it is possible to greatly reduce the vehicle mass. Among them, glass fiber reinforced materials are widely used, because although the mechanical properties of carbon fiber reinforced composites are stable, they are expensive. Considering the economy, it is a design criterion to use glass fiber reinforced materials as much as possible. In recent years, many automobile companies begin to use a kind of composite material called SMC sheet metal composite forming. The density of low-density SMC is only 1.3g/cm, but its coefficient of thermal expansion is the same as steel. At the same time, it is superior to steel in corrosion resistance, damage resistance and acoustic properties. For example, the C5 car of Chevrolet and the metal roof of Ford have achieved great commercial success since it was produced in 1999. The frame is 140 cm long, 1.47 cm wide, 0.168 cm thick at the top and 0.178 cm thick at the inner plate. The top is ordinary SMC, and the side and inner plate are composed of low-density SMC. It only weighs 10.5 kg. However, SMC also has some disadvantages, such as high price, low wear resistance compared with carbon fiber composites. In addition, the bearing capacity will be partially lost at high temperature. In view of these weaknesses, many new types of SMC have been developed. Among them, smc3374 is a typical material. Its density is still about 1.3 g / cm. However, it can maintain 75% of the mechanical properties at 93.3 ℃, which is significantly higher than that of the original SMC only at 65.5 ℃. Therefore, smc3374 was used in 2001 Aode Aurora, Pontiac Bonneville 2000 and Buick Salo 2000. From the above analysis, it is not difficult to see that SMC is only applicable to the areas where the temperature is not high and the load is not large, such as the top and side. And the bottom and high temperature area, need to be able to resist high temperature and high pressure composite materials. In 1981, Delphi produced the first leaf spring made of composite material with small bending. Small bending material has high stiffness, that is to say, under great pressure, its strain can be kept in a very small range. At the same time, its density is very small, only 50% ~ 70% of steel. Therefore, the ratio of bearing capacity to its own mass of small bending material is 5 times of steel. In addition, the experimental data show that it is 3.5 times harder than steel. These advantages are directly brought by the material properties. In addition, the structure of the composite plate spring is much simpler than that of the leaf spring, which is easy to assemble, repair and take anti-corrosion measures. Moreover, due to its much smaller thickness than the leaf spring, it is called closer to the ground, thus saving the effective space of the car. If necessary, it can be used to reduce the chassis of the car and improve the comfort performance of the car. The performance of materials at high temperature has always been a factor in material selection. The test results show that the maximum temperature of the leaf spring under the car can reach 130 ℃, and the performance of the small bending material is stable at this temperature. Based on the above advantages, small bending material is widely used in the manufacture of automobile leaf spring, from cars to light trucks, and even heavy commercial transport vehicles. Composite materials and future automobile The future car is a green car to adapt to environmental protection, so it is inevitable to mention the environmental awareness of composite materials. Composite materials can improve material properties, prolong service life and enhance functionality, which are beneficial to the environment. However, we should take seriously and try our best to overcome the recycling problem of composite materials, so as to make the composite materials develop in the direction of environmental coordination. The recycling of composite parts is very difficult, which will have some adverse effects on the environment. For example, most of the polymer matrix composites, which are the fastest developing and most widely used, are inflammables, which will emit a lot of toxic gases and pollute the environment; And in the molding, the volatile components in the matrix, that is, the solvent, will diffuse into the air, causing pollution. Composite material itself is composed of multi-component materials. It is a multi-phase material, which is difficult to crush, grind, melt and degrade. Composite parts are first decomposed into single material parts. However, the cost of decomposition process and regeneration is high, and it is very difficult to restore its original performance. Therefore, one of the main conditions for recycling is that the parts are easy to be disassembled, and the materials of single variety should be used as far as possible. Even for composite materials, the materials with less composite should be used as far as possible. Based on the above considerations, the application amount of thermoplastic polyolefin elastomer, polypropylene foaming material and GMT reinforced sheet will be greatly increased, on the contrary, the amount of thermosetting resin will be limited. At present, great progress has been made in the research of regeneration and degradation. In today's society, people's eyes gradually turn to the relationship between man and nature. The problem of environment and energy has become the key to the survival and development of every country in the world. With the continuous improvement of people's awareness of environmental protection and the introduction of environmental protection laws and regulations, green cars have become an inevitable trend of future automobile development. Therefore, how to make cars meet the requirements of environmental protection has been mentioned on the agenda of automobile manufacturers. As the mainstream of automotive material development in the future, composites will play a very important role in it. 复合材料:两种材料合二为一复合材料已然蓄势待发。复合材料在各领域的应用日渐普遍。一度应用于水上运动领域的复合材料现在已经拓展应用到了航空、汽车、风电和运动设备中。复合材料的优势是什么?将两种本无法融合的材料组合在一起,形成轻质、坚固的性能,且无论单独使用哪一种,都无法实现相同的性能。 这种复合材料含有增强体部分(如碳纤维或玻璃纤维),能够保证复合材料的机械强度,而基质可以为金属、矿物(陶瓷)或有机物—即热塑或热固性聚合树脂基塑料。目前工业上使用规模**是碳纤维或玻璃纤维加强的有机复合材料(OMC)。 有机复合材料的显著优势是它的"可定制"性,尤其是可以通过调整添加剂、改变加强纤维的类型(碳纤维、玻璃纤维)以及纤维在复合材料中的方向来改变性能。 这样,就可以通过各种工艺方法(成型、模压成型和注塑等),在考虑到材料将承受的机械应力的同时,制造出全尺寸的复杂部件,来实现真正意义上的“量身定制”。 有机复合材料对工业具有天然的吸引力目前全球每年生产1000万吨有机复合材料 (JEC数据)。这一数字还远远低于其他材料:3亿吨塑料,近17亿吨钢材。但是每年市场仍有约5%的增长。 复合材料为解决运输行业减重难题提供了解决方案这一增长主要归功于轻质和高性能材料所带来的价值增长。尤其是运输行业,因减重带来的收益意味着减少能量消耗和降低CO2排放。Michel Glotin 说明道 “为了使飞机更轻,制造商首先将目光投向了铝材。而如今他们发现复合材料更具吸引力,”。从空客A320neo系列的LEAP发动机叶片到最新设计的飞机机身,复合材料的使用使整个飞机减轻了好几吨。在一些现代飞机上,比如A350或波音787,使用的复合材料占总材料的50%。复合材料飞机结构件的全球市场总额在2014年仅仅超过70亿欧元,而在2020年甚至将超过140亿欧元。 (KEONYS 数据)。 复合材料可使飞机总重降低数吨。 在汽车领域,自20世纪80年代就已开始使用复合材料制造某些车身部件,如雪铁龙BX系列或雷诺Espace系列的汽车部件。因其投资规模相对小于传统材料所需投资,复合材料的生产规模也较小,故也用在了一些豪华系列车型上。英国跑车制造商McLaren甚至在2018年底建立了 复合材料技术中心。它的目标是:将未来旗下各系列车型的重量降到最轻。 复合材料的各类应用复合材料还用于很多其他产品:自行车框架或高尔夫球杆、电气设备等。南非运动员 Oscar Pistorius 的假肢采用环氧树脂浸渍碳纤维制造,这也使得该材料名声大震。它确保了能量的有效循环利用。此外,复合材料与(亚麻或大麻纤维增强材料)的生物兼容性,也开辟了更多的机遇。 建筑行业也开始关注这些材料的特性。对于桥梁设计师来说,复合材料的坚固性和抗性与重量之比要优于钢铁,如桥梁拉索。这类材料还可以赋予钢筋混凝土耐腐蚀性,因钢材腐蚀会造成钢筋混凝土强度降低。 最后,复合材料还促进了新能源的发展。例如,风力发电机的叶片均采用复合材料制成。同样,在未来的电动汽车上,我们也会看到复合材料制成的氢气罐或电池组。 建筑行业也开始关注这些材料的特性 热固性复合材料占主流的市场在绝大多数情况下,有机复合材料为工业需求提供了**的解决方案。热固性复合材料已经在市场占据了主导地位。“热固”是加热时基体-主要是环氧树脂或聚酯树脂-经历了不可逆的聚合过程,使其能够**成型。除了它们固有的性能外,复合材料还能制成结构和形状更复杂的部件,但使用起来仍相对简单。但是,Cetim Grand Est(公司)聚合和复合材料设计部负责人表示, “材料的产量已经达到了极限,而且也很难进一步降低单位生产成本”。 从热固性复合材料到热塑性复合材料这也是为什么大约10年前,阿科玛等各家工业企业开始倡导采用热塑基体,包括聚酰胺树脂(PA)、含氟聚合物树脂(如 PVDF)或聚醚酮酮(PEKK)。它们因会根据温度发生不可逆转的软化或固化的性质而得名。 Frédéric Ruch表示“从开发方法到部件生产技术,都需要重新开发”。但是专家认为,这样做还是值得的,因为热塑性复合材料带来了材料行业变革的希望,而且它的市场表现也愈发明朗。目前,热塑性复合材料市场的增长速度已经快于热固性复合材料市场。 热塑性复合材料的分水岭热塑性复合材料获得成功的首要条件是它们的性能,从机械性能方面看,它们至少与环氧树脂基复合材料等效。某些方面的性能则更优:它们具有更高的抗冲击性能和长期性能。 液态热固性复合树脂严格的储存条件使其有效期仅为几个月,而热塑性树脂则不然。在实施过程中,必须专门开发热塑性复合材料的制造工艺,并且使制造周期更短。最后,可以通过简单的热焊接实现此类材料的组装:因此热固性复合材料所需的复杂粘合操作次数更少。 这样的标准促使工作重心聚焦于部件生产工艺的成熟性和自动化程度。在环境温度下,热固性复合材料中的聚酯和环氧树脂以易于管理的自然液态形式存在。而热塑性复合材料是以固态形式存在的。它们是一些需要加热的粉末或颗粒,有时候需要加热到几百摄氏度才能成型。热塑性复合材料通常以树脂预浸渍碳纤维带材或聚合物预浸渍织物,即所谓的“预浸料”半成品形式在市场上销售。对于带材来说,可以采用最为普通的自动纤维铺放工艺,首先进行切割,然后叠放并加热,然后粘合,最后转移到成型机,进行巩固和冷却。 持续创新以赢得新市场但是,新技术将很快面世。例如,由 Cetim 开发的 QSP®® (Quilted Stratum Process)工艺是"一项塑料和复合材料行业的融合技术",Frédéric Ruch解释说。 该工艺可以实现每分钟5kg热塑性合成材料部件的生产速度,而且成本低廉。且所有产品性能等级都能得到保证。 业界也在探索其他的途径,比如阿科玛 Elium®系列热塑性树脂材料。这种树脂的优点是在环境温度下能够保持液态,就像热固性树脂一样。 “它因为此性质可以采用与热固性树脂相同的工艺”。Guillaume Clédat表示,“且有一个巨大的优势:同热固相比,Elium®的热塑特性能够实现可以完全回收再利用热成型。” 热塑性复合材料:可循环利用的材料最后,与热固性合成材料相比,热塑性合成材料的再循环性能是绝对不容小觑的优势。在寿命周期结束时,大部分材料只被送到了填埋场,因为人们认为循环利用不是经济性选择。Frédéric Ruch 认为 “在50年前,这根本不是问题。但是在未来,使用一种不可回收新材料简直无法想像”。这不仅是出于我们的生态意识,也是监管压力所致。在诸如汽车行业的某些领域,不可回收性已经成为阻碍材料投入应用的一大问题。在中国,风力发电机的废旧部件回收很快将成为一项法定义务。在这种情况下,能源领域的本地工业企业可能首先关注使用的合成材料的可循环性,特别是在叶片设计方面。 目前热塑性复合材料的回收工艺有两种。**种是 将部件研磨,然后将捣碎物与纯热塑性树脂混合,这种方法生产的具有一定机械强度的强化型热塑性材料仍然没有原本的复合材料受欢迎。但是还有更新、表现更好的解决方案,例如由法国机械技术工业中心 (Cetim) 提出的:将研磨后的材料重新聚结成特性与复合材料类似的板材 另一种工艺,即将 Elium® 树脂中的合成材料部件研磨后,解聚树脂并提取最初构成合成材料基体的单体,已经得到阿科玛公司的支持。Guillaume Clédat 宣布称:“在实验室中,我们能够获得纯度高于90%的单体”。一个量级达数吨的风力发电机叶片的回收项目正在持续进行。截止到2023年,阿科玛计划在荷兰建成一台每年复合材料处理能力可达到约 30,000 吨的试验机组。Guillaume Clédat 对此表示:“得益于热塑性树脂,复合材料的循环利用将成为现实”。 热塑性复合材料近年来的兴起是基于其自动化制造技术,特别是随着机器人时代的到来,实现了以工业生产速度分离和热粘合多层预浸渍带材。这一进展背后的驱动力来自于阿科玛通过与复合材料行业的专家如 Hexcel 和 Barrday 集团开展合作,开发了一种独特的带材。阿科玛材料科学总监 Michel Glotin 说道:“与这些公司的合作,使我们有能力开发出基于PEKK(聚醚酮酮)、PVDF(聚偏氟乙烯)和聚酰胺材料的单向带材解决方案—能够符合航空、石油和天然气以及汽车三大目标市场的要求和标准”。 与 Hexcel 集团合作开发的 PEKK 热塑性复合材料,可用于未来的飞机制造为寻求更轻巧的材料,航空业已经成为环氧树脂基热固性复合材料的主要消费群体。现在,在航空业掀起了以新一代热塑性复合材料应用为目标的创新,特别是阿科玛研发的 PEKK 基材料,以其出色的抗性成为热塑性材料中的佼佼者。阿科玛的 PEKK 研发经理 Philippe Bussi 解释说:“Kepstan® PEKK 带材远比环氧热固性树脂带材优越”。“与长丝碳纤维和短切碳纤维结合后, PEKK 因其重量仅为金属的一半,已成为各种金属部件的又一新替代材料”。 这一成功除了要归功于 PEKK 的轻量化以及耐热性能 (高达260°C)外,还有其**的机械性能: 近期阿科玛与 Hexcel 集团建立的战略合作关系是PEKK 兴起的一大例证,Hexcel 集团是一家高性能碳纤维和航空领域基准复合半成品生产商,可提供空客A350机身用热固性复合材料。Hexcel 集团与阿科玛公司合作开发了 PEKK Kepstan® 复合带材,并采用长丝碳纤维进行强化,将用于未来飞机制造。这些热塑性复合材料的应用最初**于二级元件(前缘、襟翼等),未来则可扩展到机身和机翼等应力更高的部件。Philippe Bussi 表示 “位于法国的联合实验室所开发的解决方案,为飞机制造商提供了适用于高生产效率下的兼容性生产方式”。 为了应对 PEKK 呈指数增长的需求,作为全球上仅有的两家 PEKK 生产商之一,阿科玛最近将法国国内产能提高了一倍,并且将在美国阿拉巴马州莫比尔市建造一个***工厂。PEKK 的成功仍无止境! 应用于海上油田柔性管道的热塑性带材得益于其在高性能聚合物方面的专长— Kynar® PVDF(聚偏氟乙烯) 和生物基材料 Rilsan® 聚酰胺—已经应用于深海采油机械柔性管道的密封,2018年阿科玛与 Barrday 集团成立了 BarrFlex TU LLC合资公司,这家公司必将成为石油和天然气行业所需的热塑性单向带材方面的开创性领航者。 这项合作旨在开发基于Kynar® PVDF,Rilsan 聚酰胺或 Kepstan® PEKK,同时结合碳纤维以及其他纤维材料的带材产品,并用于替代柔性管道上使用的金属部件 (立管和出油管线)。平台和海下油井之间的距离可达数千米。目前的安装技术需要将充气浮标沿管道走向布置,以承受其重量,并防止平台损坏。这些结构不仅复杂,而且安装费用高昂! 采用复合材料替代管道上的金属部分,无论是在减重还是在耐腐蚀性能方面,都可获得可观收益。 阿科玛公司石油与天然气市场部负责人 Olivier Merle 解释说:“我们的目标是帮助客户建设和验证能够承受120°C温度和700巴压力,同时能抵御极端腐蚀环境的管道”。 “采用复合材料的解决方案能够降低安装成本,并且能够满足结构、耐用性和环境方面的严格要求。能够为客户提供这些解决方案,为他们带来真正的附加价值,我们倍感骄傲。” Rilsan® Matrix——最新一代用于减轻机动车辆自重的复合带材面对着越来越严格的 CO2 排放限值,以至到2020年每辆车的**允许排放量将从130降低到95g/km,汽车制造商也逐渐开始更多的使用复合材料,这些都要归功于复合材料本身的重量和坚固性优势。汽车制造商也将更多的目光投向了可循环使用的热塑性复合材料。 在这项“减重计划”中,掌握了 Rilsan® Matrix 技术的阿科玛也是一家别具优势的合作伙伴——阿科玛与法国阿基坦的 Canoé 研发中心联合开发了一种全新的汽车专用热塑性复合材料。这种特别设计的带材将单向碳纤维与高性能热塑聚酰胺紧密结合以满足汽车领域结构件的要求。 为了实现 Rilsan® Matrix 产品的工业化生产,阿科玛还与复合材料工艺方面的专家 Coriolis 公司合作,以充分利用该公司的自动纤维定位技术,该技术已经在航空工业领域得到了良好验证。在高于聚酰胺熔点的温度下快速加热,带材可以快速粘合,形成扁平预制件。随后,采用法国机械行业技术中心(Cetim)的工艺,将这些预制件放入压力机中热冲压和注塑成型,最终得到3D部件。 阿科玛复合材料专家 Gilles Hochstetter 解释道:“我们能够证明通过采用 Rilsan® Matrix带材产品,汽车部件制造商能够以**竞争力的成本,实现复合材料部件的批量生产”。这些 Rilsan® Matrix 部件具有什么优势?它们具有高耐化学、耐机械和耐热性能,能够经受汽车生产线采用的金属防腐即“电泳”处理工艺。制造商可以在同一辆汽车上结合使用金属部件和复合材料部件,但不会牺牲整车抗性,特别是抗冲击性能。 Gilles Hochstetter 最后总结道:“结合浸渍碳纤维后的聚酰胺 Rilsan® Matrix带材产品,其抗性比一般的聚酰胺树脂材料(如聚酰胺6或6.6)更高。这种新型复合材料将成为汽车行业转型的关键!” |