WO2019080100A1 - 碳化硅铝基复合结构件及碳化硅增强预制件的制备方法 - Google Patents

碳化硅铝基复合结构件及碳化硅增强预制件的制备方法

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WO2019080100A1
WO2019080100A1 PCT/CN2017/108050 CN2017108050W WO2019080100A1 WO 2019080100 A1 WO2019080100 A1 WO 2019080100A1 CN 2017108050 W CN2017108050 W CN 2017108050W WO 2019080100 A1 WO2019080100 A1 WO 2019080100A1
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Prior art keywords
silicon carbide
aluminum
carbide particles
binder
particles
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PCT/CN2017/108050
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English (en)
French (fr)
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曾俊
庄后荣
袁亮亮
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深圳市大富科技股份有限公司
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Application filed by 深圳市大富科技股份有限公司 filed Critical 深圳市大富科技股份有限公司
Priority to PCT/CN2017/108050 priority Critical patent/WO2019080100A1/zh
Priority to CN201780036310.0A priority patent/CN109311769A/zh
Publication of WO2019080100A1 publication Critical patent/WO2019080100A1/zh

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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/515—Other specific metals
    • C04B41/5155—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time

Definitions

  • the present application relates to the field of composite materials, and in particular, to a method for preparing a silicon carbide aluminum-based composite structural member and a silicon carbide-reinforced preform.
  • High-performance lightweight structural materials play an important strategic role in economic and national defense construction.
  • lightweight structural materials as matrix are mainly composed of Al, Mg and Ti alloys.
  • the reinforcement materials mainly include silicon carbide SiC and Al 2 O 3 . , BC 4 , TiB 2, etc.
  • silicon carbide aluminum AlSiC composite materials are widely used in aerospace, electronic packaging, optical instruments, sports equipment and other fields due to their excellent thermophysical properties and mechanical properties.
  • the AlSiC composite material is prepared by mixing SiC powder with a paraffin-based binder to form a uniform feed, and the feed is granulated and then injection-molded on an injection molding machine to obtain a SiC preform. Then, after solvent and thermal degreasing, pre-sintering at a temperature of 1000 to 1150 ° C, and finally, a molten solution of the Al alloy is infiltrated into the SiC skeleton by a pressureless infiltration method at a temperature of 1100 to 1200 ° C in a N 2 atmosphere. SiC/Al composite parts with high volume fraction.
  • the inventors of the present application found in the long-term development process that in the above method, when powder injection molding is used to prepare complex parts, it is required that the injected powder has good fluidity, a large amount of organic binder needs to be added, and the binder is removed.
  • the process is the most difficult part of the whole process, the degreasing time is long, and a large amount of exhaust gas generated during degreasing causes pollution to the environment.
  • the powder particle size is generally 0.5-20 um, which is suitable for the powder injection molding process.
  • the technical problem mainly solved by the present application is to provide a preparation method of a silicon carbide aluminum-based composite structural member and a preparation method of the silicon carbide reinforced preform, which can prepare a complex part or provide technical support thereof, and the powder is Plasticity requirements are not high.
  • a technical solution adopted by the present application is to provide a method for preparing a silicon carbide aluminum-based composite structural member, the method comprising: providing at least two silicon carbide particles having different average particle sizes; The silicon carbide particles of different average particle sizes are uniformly mixed; the binder for the inert material is added to the uniformly mixed silicon carbide particles, kneaded, granulated, and passed through cold, etc.
  • the static pressure technique is performed to form a silicon carbide reinforced preform; and the aluminum-containing melt and the silicon carbide reinforced preform are formed into the SiC-aluminum-based composite structural member by a vacuum liquid phase infiltration method.
  • another technical solution adopted by the present application is to provide a method for preparing a silicon carbide reinforced preform, the method comprising: providing at least two silicon carbide particles having different average particle sizes; The silicon carbide particles having different average particle sizes are uniformly mixed; the binder for the inert material is added to the uniformly mixed silicon carbide particles, kneaded, granulated, and molded by cold isostatic pressing technology to prepare the product.
  • a silicon carbide reinforced preform A silicon carbide reinforced preform.
  • the beneficial effects of the present application are: different from the prior art, in the preparation method of the silicon carbide aluminum-based composite material of the present application, at least two silicon carbide particles having different average particle sizes are provided; and the predetermined average particle size of the predetermined average particle size is
  • the silicon carbide particles are uniformly mixed; the binder for the inert material is added to the uniformly mixed silicon carbide particles, kneaded, granulated, and formed by cold isostatic pressing technology to form a silicon carbide reinforced preform;
  • the aluminum-containing molten metal and the silicon carbide-reinforced preform are formed into the silicon carbide-aluminum-based composite structural member by a vacuum liquid phase infiltration method.
  • the particles and the particles can be filled with each other, so that the silicon carbide preform can obtain sufficient strength; and the adhesive used for the raw material for the bismuth can eliminate the degreasing and avoid polluting the environment;
  • cold isostatic pressing technology a large and complex shaped structural member can be obtained, and the mold is cheap, and the obtained preform has uniform density and high strength; vacuum pressurization can be performed by liquid phase aluminizing of the SiC preform. Strength of AlSiC structural members.
  • FIG. 1 is a flow chart of an embodiment of a method for preparing a silicon carbide aluminum-based composite structural member of the present application
  • FIG. 2 is a flow chart of another embodiment of a method for preparing a silicon carbide aluminum-based composite structural member of the present application
  • FIG. 3 is a flow chart of still another embodiment of a method for preparing a silicon carbide aluminum composite structural member of the present application
  • the lightweight of the car body is not simply to reduce the weight of the car, but to reduce the car body quality as much as possible while ensuring the strength and safety of the car body, while ensuring that the manufacturing cost of the car body is within a reasonable range.
  • the composite material has a low density (about 1/3 of aluminum alloy), high specific strength, impact resistance, good fracture toughness, good vibration and sound insulation performance, good design, corrosion resistance, etc. Industrial attention. See Table 1, Table 1 is a comparison of weight loss and relative cost after replacement of lightweight materials.
  • High-performance lightweight structural materials play an important strategic role in economic and national defense construction.
  • lightweight structural materials as matrix are mainly composed of three alloys of Al, Mg and Ti.
  • the reinforcement materials mainly include SiC, Al 2 O 3 and BC. 4 , TiB 2, etc.
  • the density of Mg alloy is lower than that of aluminum.
  • the composite material prepared from it has great potential in aerospace and automotive applications, but its high temperature stability is poor and it is difficult to be used as a key component.
  • Ti alloy matrix composites It has good oxidation resistance and high temperature mechanical properties, but its preparation cost is high and processing is difficult, which limits its wide use: the aluminum alloy is light in weight, the base alloy has a wide selection range, high strength, high toughness, heat resistance and corrosion resistance.
  • Aluminum is easy to recycle, can be recycled, and has good heat treatment properties. Therefore, aluminum alloy has become a widely used matrix material and has become the mainstream of current development and research work. Both pure aluminum and aluminum alloy can be used as the base metal, and the aluminum alloy base mainly has Al-Cu-Mg, Al-Mg-Si and Al-Zn-Mg alloys.
  • the reinforcing materials SiC has high strength, high hardness, good thermal stability and relatively low price, and has been widely used in reinforcing materials.
  • AlSiC composite materials are widely used in aerospace, electronic packaging, optical instruments, sports equipment and other fields due to their excellent thermophysical properties and mechanical properties.
  • automotive industry it is mainly used in high-temperature brake pads, cylinder pistons, bearing bushes and other high-temperature service fields.
  • Silicon carbide particles still have high modulus and strength under high temperature conditions, so SiC-reinforced aluminum-based composite materials are added. It has better high temperature performance than the original aluminum alloy, and significantly increases the specific strength and specific modulus of the parts, greatly reducing the weight of the parts.
  • SiC-based preforms are first prepared and then composited with AlSiC materials.
  • the AlSiC composite material is prepared.
  • the powder injection molding technology is adopted, and when the powder injection molding is used to prepare the complicated parts, the injection powder is required to have good fluidity, and a large amount of organic bonding is required.
  • the removal process of the agent and the binder is the most difficult part in the whole process, the degreasing time is long, and a large amount of waste gas generated during degreasing causes pollution to the environment, and the powder particle size is generally 0.5 to 20 um, which is suitable for the powder injection molding process, and Injection molding can only produce smaller-sized devices.
  • injection molding methods cannot obtain SiC preforms that meet the requirements.
  • the present application selects at least two silicon carbide particles of different average particle sizes, and the particles and the particles can be filled with each other, so that the silicon carbide preform can obtain sufficient strength; and the adhesive used for the raw material can be used. It is free of degreasing and avoids polluting the environment.
  • it can be obtained by cold isostatic pressing technology, and can obtain large and complex shaped structural parts, and the mold is cheap, the obtained preform has uniform density and high strength; vacuum pressurizing SiC preforms Phase infiltration of aluminum can obtain high strength AlSiC structural parts.
  • FIG. 1 is a flow chart of an embodiment of a method for preparing a silicon carbide aluminum-based composite structural member according to the present application, the method comprising:
  • Step S101 providing at least two silicon carbide particles of different average particle sizes.
  • silicon carbide particles have different geometric shapes.
  • the silicon carbide particles have irregular geometric shapes, are multi-faceted, and some particles have sharp sharp corners.
  • the preparation of SiC preforms from an average particle size of SiC particles is liable to cause incomplete filling between the particles, resulting in insufficient strength of the preforms.
  • the strength of the AlSiC composites is insufficient to be used as a structural member of the body.
  • two or more silicon carbide particles having different average particle sizes are selected, such that SiC particles of different sizes and SiC particles can be filled with each other, so that the SiC preform obtains sufficient strength.
  • the silicon carbide particles have an average particle size ranging from 3 to 150 um, for example, a silicon carbide particle having an average particle size of 3 um, a silicon carbide particle having an average particle size of 50 um, and an average particle size of a silicon carbide particle.
  • a silicon carbide particle has an average particle size of 150 um, and the like.
  • the average particle size of two or more kinds of silicon carbide particles is selected such as the strength requirement and the plasticity requirement of the material.
  • Step S102 mixing silicon carbide particles of different average particle sizes in a predetermined ratio uniformly.
  • a predetermined ratio of two or more different average particle size silicon carbide particles is determined, and then a predetermined proportion of silicon carbide particles of different average particle sizes are uniformly mixed.
  • the silicon carbide particles having a particle size in the range of 4.0 um ⁇ D 50 ⁇ 11.0 um have a mass percentage of 65% to 80%, and the silicon carbide particles having a particle size in the range of 50.7 um ⁇ D 50 ⁇ 70.0 um.
  • the mass percentage of the silicon carbide particles having a mass percentage of 20% to 35% and a particle size of 100.0 um ⁇ D 50 ⁇ 115.0 um is 0% to 5%.
  • Step S103 kneading and granulating the binder for adding the inert raw material to the uniformly-contained silicon carbide particles, and molding by cold isostatic pressing technology to prepare a silicon carbide-reinforced preform.
  • the adhesive refers to a substance capable of bonding and bonding the surfaces of homogenous or heterogeneous objects.
  • the adhesive used for the bismuth-containing raw material is used, and the bismuth raw material refers to the silicate raw material.
  • the material which has no viscosity and is deuterated after mixing with water, is used in the production of ceramics and refractory materials, can reduce the plasticity of the batch material and reduce the shrinkage of the green body during drying and firing, and acts as a skeleton, quartz, long Stones, calcined clay (clinker) and refractory pieces can be used as inert materials.
  • the binder used for the inert material is, for example, paraffin wax, polyvinyl alcohol PVA, polyvinyl butyral PVB or the like.
  • a combination of a mixing method, a molding method, no introduction of impurities, a discharge temperature, a preform strength, and the like are used, and an aluminum dihydrogen phosphate-containing adhesive is used.
  • Aluminum dihydrogen phosphate is a colorless, odorless and viscous liquid or white powder, soluble in water; solidified at room temperature, strong combination of liquid and curing, high temperature resistance, vibration resistance, flaking resistance, high temperature airflow scouring; After mixing with refractory aggregates, hardeners, etc., it forms a high bond strength at a certain temperature for a certain period of time, and is therefore a good adhesive.
  • the use of an adhesive containing aluminum dihydrogen phosphate does not cause the problem of degreasing, and does not pollute the environment.
  • the binder is added to the uniformly mixed silicon carbide particles to be kneaded and granulated to facilitate subsequent molding.
  • the adhesive further comprises a plasticizer, and the amount of aluminum dihydrogen phosphate added is from 1% to 3% of the total amount of the silicon carbide particles after mixing, for example, 1%, 2%, 3%. and many more.
  • the isostatic pressing technology is an advanced technology of ultra-high pressure hydraulic pressure which is formed by using the products in a closed high-pressure vessel under uniform ultra-high pressure conditions.
  • Cold Isostatic Pressing is a material used to coat rubber molds at room temperature, usually with rubber or plastic. It is mainly used for molding powder materials for further sintering, forging or heat.
  • the isostatic pressing process provides a blank.
  • cold isostatic pressing technology has the following characteristics:
  • the working pressure is low; second, the density of the formed product is high; third, the density of the compact is uniform.
  • the pressure of the isostatically pressurized fluid medium is equal in all directions; the envelope is substantially consistent with the compression of the powder, and the powder and the sheath have no relative motion, the frictional resistance between them is small, and the pressure is only slightly decreased, therefore,
  • the density of the green body is uniform; fourthly, because the density is uniform, the aspect ratio can be unrestricted, which is favorable for producing a rod-shaped, tubular thin and long product; fifth, it is not necessary to add a lubricant to the powder, thereby reducing
  • the pollution of the product simplifies the manufacturing process; sixth, the product has excellent performance, short production cycle and wide application range.
  • the pressure to be formed by the cold isostatic pressing technique is 85 to 110 MPa
  • the mold used is a rubber mold.
  • the molding technology is suitable for preparing large and complex shaped structural parts, and the obtained preform has uniform density, and the sintered sample has good shrinkage consistency and near net shape.
  • the size of the rubber mold makes the size of the sintered silicon carbide reinforced preform slightly smaller than the size of the final product, which facilitates the subsequent processing of the final product.
  • the present application adopts a rubber mold, and the powder is filled and pressed by cold isostatic pressing.
  • the rubber mold is not limited by the complexity of the shape of the product, and the cost is low, and the cold is cold. Isostatic pressing makes the SiC body uniform and the green density is uniform. It is not easy to deform, and at the same time, the net shape of the reinforcement can be achieved. Therefore, in general, by cold isostatic pressing technology, a large and complicated structural member can be obtained, and the mold is inexpensive, and the obtained preform has uniform density and high strength.
  • step S103 the binder for the cerium-containing raw material is added to the uniformly mixed silicon carbide particles for kneading and granulating, and specifically includes sub-step S1031 and sub-step S1032.
  • Sub-step S1031 adding aluminum dihydrogen phosphate to the uniformly mixed silicon carbide particles, adding deionized water, heating to 90 to 110 ° C, and kneading to a humidity of 8% to 12% to obtain a mixture.
  • Sub-step S1032 The mixture is dried at a temperature of 100-140 ° C for 2 to 4 hours, granulated by a granulator, and sieved to obtain a granulated powder.
  • the silicon carbide reinforced preform has a porosity of from 36% to 38%.
  • the specificity of kneading and granulation can be used to make the porosity of the SiC-reinforced preforms in the range of 36% to 38%, thereby preparing a silicon carbide-aluminum-based composite material that satisfies the requirements later.
  • Step S104 The aluminum-containing molten liquid and the silicon carbide reinforced preform are formed into a silicon carbide aluminum-based composite structural member by a vacuum liquid phase infiltration method.
  • the vacuum liquid infiltration process is: firstly, the reinforcement material is made into a preform, and then the preform is placed in a mold located in the pressure vessel, and the gas in the preform is extracted, and the vacuum and the inert gas are combined. Pressure is applied to the molten metal from the passage into the mold to impregnate the preform.
  • the advantage of this method is that it has wide application range and is suitable for the preparation of a variety of composite materials.
  • the type, shape, size and volume fraction of the reinforcement material are basically not limited; the composite parts can be directly formed, especially the complicated shape.
  • the parts basically do not need subsequent processing; the immersion is carried out in vacuum, solidified under pressure, no defects such as pores, looseness, shrinkage, etc., compact structure, good material properties; simple process, easy to control parameters, according to reinforcement material and base metal The physical and chemical properties of the material, strict control of temperature, pressure and other parameters to avoid serious interface reactions.
  • the aluminum-containing aluminum alloy is melted and heated to 720 ° C to 780 ° C, and the temperature is 0.5 to 2 h, and the slag is removed to obtain an aluminum alloy melt; the prepared SiC preform (for example, SiC)
  • the body prefabricated parts are placed in the aluminizing chamber, and the aluminizing chamber and the SiC preform are vacuumed by a die-casting vacuum machine.
  • the vacuum degree in the aluminizing cavity is 500-700 Pa
  • the aluminum alloy melt is introduced into the aluminizing cavity to be infiltrated, and finally the pressure of 4-7 MPa is applied, so that the aluminum alloy molten solution is impregnated into the pores in the SiC preform, and the obtained AlSiC composite structural parts (for example, SiC body preforms are placed, and finally AlSiC composite automobile body parts are prepared).
  • the product can be further processed. According to the product design, only the aluminum alloy portion other than AlSiC needs to be machined and removed according to the final size.
  • the method may further include:
  • Step S105 sintering the silicon carbide reinforced preform, the sintering temperature is 650 to 850 ° C, and the sintering time is 2 to 4 hours.
  • the obtained SiC green body is sintered in a high-temperature furnace, in order to prevent deformation of a sample of a complicated shape during heating, a suitable bearing holder is selected when the green body is placed, and gravity strain is avoided, at a temperature of 650 to 850 ° C. After sintering for 2 to 4 hours, a SiC reinforcement preform having a certain strength is obtained.
  • the silicon carbide aluminum based composite structural member is used in automotive body structural members.
  • the low density of AlSiC composite structural parts can replace nearly two-thirds of the weight of low-carbon steel plates, and has high specific strength and specific modulus, high strength, high toughness, wear resistance, corrosion resistance, fatigue resistance, etc.
  • the row also enhances the safety and service life of the body.
  • FIG. 4 is a flow chart of an embodiment of a method for preparing a silicon carbide reinforced preform according to the present application, the method comprising:
  • Step S201 providing at least two silicon carbide particles of different average particle sizes.
  • Step S202 mixing silicon carbide particles of different average particle sizes in a predetermined ratio uniformly.
  • Step S203 adding a binder for the cerium-containing raw material to the uniformly mixed silicon carbide particles, kneading, granulating, and molding by cold isostatic pressing to prepare a silicon carbide reinforced preform.
  • the adhesive is a binder containing aluminum dihydrogen phosphate; the average particle size of the silicon carbide particles ranges from 3 to 150 um.
  • the mass percentage of the silicon carbide particles having a particle size in the range of 4.0 um ⁇ D 50 ⁇ 11.0 um is 65% to 80%
  • the mass percentage of the silicon carbide particles having a particle size in the range of 50.7 um ⁇ D 50 ⁇ 70.0 um The content of the silicon carbide particles having a content of 20% to 35% and a particle size of 100.0 um ⁇ D 50 ⁇ 115.0 um is 0% to 5% by mass.
  • the adhesive further comprises a plasticizer, and the amount of the aluminum dihydrogen phosphate added is 1% to 3% of the total amount of the silicon carbide particles after the mixing.
  • the binder for adding the cerium-containing raw material to the uniformly mixed silicon carbide particles is kneaded and granulated, comprising: adding aluminum dihydrogen phosphate to the uniformly mixed silicon carbide particles, adding deionized water, and heating To 90-110 ° C, knead to a humidity of 8%-12% to obtain a mixture; the mixture is dried at a temperature of 100-140 ° C for 2 to 4 hours, granulated by a granulator, sieved to obtain granulation powder.
  • the pressure by the cold isostatic pressing technology is 85-110 MPa
  • the mold used is a rubber mold.
  • the size of the rubber mold is such that the size of the sintered silicon carbide-reinforced preform is slightly smaller than the size of the final product, for example, after sintering.
  • the SiC-reinforced preform has an orientation dimension that is 0.1% to 2% smaller than the size of the final product.
  • the porosity of the silicon carbide reinforced preform is 36% - 38%.
  • At least two silicon carbide particles having different average particle sizes are selected, and the particles and the particles can be filled with each other, so that the silicon carbide preform can obtain sufficient strength; and by cold isostatic pressing technology, large complex shapes can be obtained.
  • the structural parts, and the mold is cheap, the obtained preform has uniform density and high strength; in this way, technical support can be provided for preparing the AlSiC composite material.
  • the B-pillar of the car body is prepared by using the AlSiC composite structural member as an example.
  • the traditional B-pillar cross-section shape is more complicated, and it is welded by multiple pieces of stamped steel plate.
  • the B-pillar Excluding the interior and the outer cover, the B-pillar is generally divided into an inner plate, a reinforcing plate and an outer plate from the inside to the outside, and basically belongs to a closed thin-walled beam structure, and The upper and lower joints are connected to the top side sill and the door frame by welding.
  • the reinforcing plate structure is usually a small assembly, and the seat belt and the door are installed through the B-pillar.
  • the position of the lock and other accessories is required to be relatively rigid, it is necessary to install a corresponding reinforcing plate.
  • the excessive reinforcing plate is not only disadvantageous to the weight reduction of the vehicle body, but also complicates the design of the vehicle body and the assembly of the entire vehicle.
  • the B-pillar structure of the inner and outer plates is still adopted, and the upper and lower joints of the B-pillar are respectively formed on the inner and outer plates, and are integrally formed in the production process, and are realized by the following process steps.
  • Rubber mold design According to the plan of integrally forming the B-pillar and the upper and lower joints, the net-formed SiC reinforcement preform is slightly smaller than the final product size after sintering, which is convenient for final machining.
  • the granulated powder obtained in the step 2 is filled into a rubber mold to ensure uniform filling of the powder and uniform bulk density, and is formed by cold isostatic pressing under a pressure of 90 MPa.
  • the aluminized cavity is selected not to be limited by shape, and is slightly larger than the preform.
  • the preform of step 4 is placed in an aluminizing chamber and preheated to 660 ° C for half an hour. Vacuuming to 650Pa, when the temperature in the aluminizing chamber reaches the aluminizing temperature, open the aluminum liquid channel to fill the aluminum aluminizing cavity with aluminum liquid, carry out appropriate heat preservation operation, and pass nitrogen gas, pressurize 5MPa, hold pressure for 15 minutes, Ensure that the aluminum liquid penetrates sufficiently into the voids of the SiC reinforcement preform and cools with the furnace.
  • the nitrogen here can also be replaced by other inert gases, but the cost of using nitrogen is lower.
  • the product obtained in the step 5 is further processed. According to the product design, only the aluminum alloy portion other than AlSiC needs to be removed by machining according to the final size.
  • the front side member of the car body is prepared by using an AlSiC composite structural member as an example.
  • thin-walled members stamped from low-carbon steel sheets are widely used and can be welded to other members through flanges. They are the main energy absorbing members in the collision of vehicles, including the front longitudinal beam and the body side of the automobile. In the surrounding parts such as the surrounding floor and the floor, the cross section of the front side of the conventional automobile is a thin-walled rectangular structure. When a car has a frontal collision, it mainly absorbs the kinetic energy of the collision by the plastic deformation of the front part of the vehicle body. The main role is the front longitudinal beam.
  • the aluminum SiC composite structural member Compared with the low carbon steel material of the traditional front sill of the automobile, the aluminum SiC composite structural member has higher yield strength and energy absorbing ability, and at the same time achieves the purpose of greatly reducing weight.
  • Rubber mold design According to the design of the front section of the slot section, the net-formed SiC reinforcement preform is slightly smaller than the final product size after sintering, which is convenient for final machining.
  • SiC particles with a particle size range of 4.0um ⁇ D 50 ⁇ 11.0um, 50.7um ⁇ D 50 ⁇ 70.0um, 100.0um ⁇ D 50 ⁇ 115.0um, 50% aluminum dihydrogen phosphate, 6063 aluminum alloy
  • the granulated powder obtained in the step 2 is filled into a rubber mold to ensure uniform filling of the powder and uniform bulk density, and is formed by cold isostatic pressing under a pressure of 90 MPa.
  • the aluminized cavity is selected not to be limited by shape, and is slightly larger than the preform.
  • the preform of step 4 is placed in an aluminizing chamber and preheated to 660 ° C for half an hour. Vacuuming to 650Pa, when the temperature in the aluminizing chamber reaches the aluminizing temperature, open the aluminum liquid channel to fill the aluminum aluminizing cavity with aluminum liquid, carry out appropriate heat preservation operation, and pass nitrogen gas, pressurize 7MPa, hold pressure for 15 minutes, Ensure that the aluminum liquid penetrates sufficiently into the voids of the SiC reinforcement preform and cools with the furnace.
  • the nitrogen here can also be replaced by other inert gases, but the cost of using nitrogen is lower.
  • the product obtained in the step 5 is further processed. According to the product design, only the aluminum alloy portion other than AlSiC needs to be removed by machining according to the final size.
  • the above specific embodiment is a silicon carbide aluminum-based composite structural member for use in an automobile body structural member.
  • AlSiC composite structural members have low density and can replace nearly two-thirds of the weight of low-carbon steel plates, while having a high ratio.

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Abstract

一种碳化硅铝基复合结构件及碳化硅增强预制件的制备方法，该方法包括：提供至少两种不同平均粒度的碳化硅颗粒；将预定比例的所述不同平均粒度的碳化硅颗粒混合均匀；向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，并通过冷等静压技术进行成型，以制成碳化硅增强预制件；通过真空液相浸渗方法，使含铝的熔化液和所述碳化硅增强预制件制成所述碳化硅铝基复合结构件。通过这种方法，能够制备得到复杂零件或者为其提供技术支持，且对粉体的可塑性要求不高。

Description

碳化硅铝基复合结构件及碳化硅增强预制件的制备方法 【技术领域】
本申请涉及复合材料技术领域，尤其涉及一种碳化硅铝基复合结构件及碳化硅增强预制件的制备方法。
【背景技术】
高性能轻质结构材料在经济与国防建设中占有重要的战略地位，其中作为基体的轻质结构材料主要有Al、Mg、Ti三种合金，增强体材料主要有碳化硅SiC、Al2O3、BC4、TiB2等。目前碳化硅铝AlSiC复合材料以其优异的热物理性能和机械力学性能，广泛应用于航空航天、电子封装、光学仪器、运动器材等领域。
在一现有技术中，AlSiC复合材料的制备方法是：采用SiC粉末与石蜡基粘结剂混合成均匀的喂料，喂料经制粒后在注射成形机上注射成形，所得SiC预成形坯，然后经过溶剂和热脱脂后在1000～1150℃温度下预烧结，最后通过无压熔渗方法在1100～1200℃温度下、N2气氛中将Al合金熔融的溶液渗透到SiC骨架中，从而获得具有高体积分数的SiC/Al复合材料零件。
但是，本申请的发明人在长期的研发过程中发现，上述方法中，粉末注射成型制备复杂零件时，要求注射粉末具有良好的流动性，需要加入大量有机粘结剂，粘结剂的脱除过程是整个工艺中最困难的环节，脱脂时间长，脱脂时生成的大量废气对环境造成污染，同时粉末粒度一般在0.5～20um才适合粉末注射成型工艺要求。
【申请内容】
本申请主要解决的技术问题是提供一种碳化硅铝基复合结构件的制备方法和一种碳化硅增强预制件的制备方法，能够制备得到复杂零件或者为其提供技术支持，且对粉体的可塑性要求不高。
为解决上述技术问题，本申请采用的一个技术方案是：提供一种碳化硅铝基复合结构件的制备方法，所述方法包括：提供至少两种不同平均粒度的碳化硅颗粒；将预定比例的所述不同平均粒度的碳化硅颗粒混合均匀；向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，并通过冷等 静压技术进行成型，以制成碳化硅增强预制件；通过真空液相浸渗方法，使含铝的熔化液和所述碳化硅增强预制件制成所述碳化硅铝基复合结构件。
为解决上述技术问题，本申请采用的另一个技术方案是：提供一种碳化硅增强预制件的制备方法，所述方法包括：提供至少两种不同平均粒度的碳化硅颗粒；将预定比例的所述不同平均粒度的碳化硅颗粒混合均匀；向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，并通过冷等静压技术进行成型，以制成所述碳化硅增强预制件。
本申请的有益效果是：区别于现有技术的情况，本申请碳化硅铝基复合材料的制备方法中，提供至少两种不同平均粒度的碳化硅颗粒；将预定比例的所述不同平均粒度的碳化硅颗粒混合均匀；向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，并通过冷等静压技术进行成型，以制成碳化硅增强预制件；通过真空液相浸渗方法，使含铝的熔化液和所述碳化硅增强预制件制成所述碳化硅铝基复合结构件。由于选择至少两种不同粒度的碳化硅颗粒，颗粒与颗粒之间可以互相填充，使得碳化硅预制件得到足够的强度；采用含瘠性原料所用的粘接剂，可以免除脱脂，避免污染环境；而通过冷等静压技术进行成型，能得到大的复杂形状的结构件，而且模具便宜，得到的预制件密度均匀，强度高；真空加压对SiC预制件进行液相渗铝，可以得到高强度的AlSiC结构件。
【附图说明】
图1是本申请碳化硅铝基复合结构件的制备方法一实施方式的流程图；
图2是本申请碳化硅铝基复合结构件的制备方法另一实施方式的流程图；
图3是本申请碳化硅铝基复合结构件的制备方法又一实施方式的流程图；
图4是本申请碳化硅增强预制件的制备方法一实施方式的流程图。
【具体实施方式】
下面将结合本发明实施方式中的附图，对本发明实施方式中的技术方案进行清楚、完整地描述，显然，所描述的实施方式仅仅是本发明一部分实施方式，而不是全部的实施方式。基于本发明中的实施方式，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式，均属于本发明保护的范围。
在详细介绍本申请之前，先介绍一下与本申请相关的现有技术的情况。
汽车轻量化作为降低原油消耗和尾气排放的重要手段，已被广泛关注，研究表明，汽车自重每降低10％，可降低油耗6％～8％，减少CO2排放13％，且当汽车自重降低时，其起步加速性能会更好，制动时的制动距离也会显著缩短。汽车车身占整车的30％～60％，汽车运行过程中约70％的燃料是消耗在车身质量上，使得车身成为汽车轻量化的关键。此外，车身减轻后，汽车的动力系统的功耗也会降低，从而有利于降低发动机和减速箱的尺寸，实现整车的进一步减重，因此车身减重对于汽车轻量化举足轻重。
汽车车身轻量化并非简单的将汽车重量减轻，而是在保证车身强度和安全的前提下，尽可能地降低汽车车身质量，同时保证汽车车身的制造成本在合理的范围内，目前主要有三种手段：(1)使用轻量化机构，以车身零件的强度和刚度要求为约束，优化设计方法，对零件的机构进行优化设计；(2)使用轻量化材料，通过大量使用轻质、高强度材料实现车身大幅减重；(3)使用轻量化结构材料，采用特种加工工艺制成的、具有轻量化结构特征的、车使用毛坯材料；(4)使用多材料混合车身，采用高性能轻质材料可以有效轻量化车身，但成本仍然较高，综合考虑成本与轻量化效果，德国学者提出“多材料轻量化结构”。其中，通过使用轻量化材料来降低汽车自重已经得到汽车工业的普遍关注，成为车身轻量化的主流技术，主要使用高强钢板、轻金属材料、复合材料替代普通钢材以及采用多材料混合车身结构。其中复合材料因为密度低(铝合金的1/3左右)，比强度高、耐撞击、抗断裂韧度好、减振隔音性能好、可设计行好、耐腐蚀等一系列有点，已经得到汽车工业的重视。参见表1，表1是轻质材料替代后的减重效果和相对成本对比。
表1 轻质材料替代的减重效果和相对成本对比
Figure PCTCN2017108050-appb-000001
高性能轻质结构材料在经济与国防建设中占有重要的战略地位，其中作为基体的轻质结构材料主要有Al、Mg、Ti三种合金，增强体材料主要有SiC、Al2O3、BC4、TiB2等。Mg合金的密度比铝低，以其为基体制备的复合材料在航空航天和汽车工业应用中有很大的潜力，但其高温稳定性较差，很难用做关键部件；Ti合金基复合材料具有很好的抗氧化性和高温力学性能，但其制备成本高、加工困难，限制了其广泛使用：而铝合金质量轻、基体合金选择范围广、高强、高韧、耐热、耐蚀，铝材易回收，可循环利用，可热处理性好等优点，所以铝合金成为一种广泛应用的基体材料，成为当前该类材料发展和研究工作的主流。纯铝和铝合金都可用作基体金属，铝合金基体主要有Al-Cu-Mg、Al-Mg-Si和Al-Zn-Mg合金。增强体材料中SiC的强度高、硬度高、热稳定性好、价格相对便宜，在增强体材料中得到了较为广泛的应用。
目前AlSiC复合材料以其优异的热物理性能和机械力学性能，广泛应用于航空航天、电子封装、光学仪器、运动器材等领域。在汽车工业领域，目前主要应用于高性能刹车片、气缸活塞、轴承轴瓦等高温服役领域，碳化硅颗粒在高温条件依然具有较高的模量以及强度，所以添加了碳化硅增强铝基复合材料比原铝合金高温性能更好，同时显著提升了零部件的比强度和比模量，大大减轻了零件重量。
对于AlSiC复合材料，首先要制备SiC基预制件，然后进行AlSiC材料复合。现有技术中，制备AlSiC复合材料，在SiC基预制件过程中，采用的是粉末注射成型技术，而粉末注射成型制备复杂零件时，要求注射粉末具有良好的流动性，需要加入大量有机粘结剂，粘结剂的脱除过程是整个工艺中最困难的环节，脱脂时间长，脱脂时生成的大量废气对环境造成污染，同时粉末粒度一般在0.5～20um才适合粉末注射成型工艺要求，且注射成型法只能制得尺寸较小的器件，对于汽车车身制备应用，注射成型方法无法得到满足要求的SiC预制件。
针对上述问题，本申请选择至少两种不同平均粒度的碳化硅颗粒，颗粒与颗粒之间可以互相填充，使得碳化硅预制件得到足够的强度；；采用含瘠性原料所用的粘接剂，可以免除脱脂，避免污染环境；而通过冷等静压技术进行成型，能得到大的复杂形状的结构件，而且模具便宜，得到的预制件密度均匀，强度高；真空加压对SiC预制件进行液相渗铝，可以得到高强度的AlSiC结构件。
下面结合附图和实施方式对本申请进行详细说明。
参见图1，图1是本申请碳化硅铝基复合结构件的制备方法一实施方式的流程图，该方法包括：
步骤S101：提供至少两种不同平均粒度的碳化硅颗粒。
不同粒度的碳化硅颗粒，其几何形状也不同，通常碳化硅颗粒的几何形状不规则，为多面形，有些颗粒还有很尖锐的尖角。用一种平均粒度的SiC颗粒制备SiC预制件，容易造成颗粒之间填充不完整，导致预制件强度不够，最后使得AlSiC复合材料的强度不够，无法作为车身结构件。本实施方式选择两种以上的不同平均粒度的碳化硅颗粒，这样使得不同尺寸的SiC颗粒与SiC颗粒之间可以互相填充，使得SiC预制件得到足够的强度。
在一实施方式中，碳化硅颗粒的平均粒度范围为3～150um，例如：一种碳化硅颗粒的平均粒度为3um，一种碳化硅颗粒的平均粒度为50um，一种碳化硅颗粒的平均粒度为100um，一种碳化硅颗粒的平均粒度为150um，等等。一般来说，当颗粒粒度较小时，颗粒间距较小，复合材料的强度会提高；当颗粒粒度较大时，颗粒间距较大，复合材料的塑性会提高；因此，在实际应用中，根据复合材料的强度要求和塑性要求等选择两种以上的碳化硅颗粒的平均粒度。
步骤S102：将预定比例的不同平均粒度的碳化硅颗粒混合均匀。
根据实际需求，确定两种以上的不同平均粒度的碳化硅颗粒的预定比例，然后将预定比例的不同平均粒度的碳化硅颗粒混合均匀。
在一实施方式中，粒度在4.0um≤D50≤11.0um范围内的碳化硅颗粒的质量百分含量为65％～80％，粒度在50.7um≤D50≤70.0um范围内的碳化硅颗粒的质量百分含量为20％～35％，粒度在100.0um≤D50≤115.0um范围内的碳化硅颗粒的质量百分含量为0％～5％。
步骤S103：向混合均匀后的碳化硅颗粒中添加瘠性原料所用的粘接剂进行混捏、造粒，并通过冷等静压技术进行成型，以制成碳化硅增强预制件。
粘接剂是指能够将同质或异质物体表面粘接连接在一起的物质，在本实施方式中，采用的是含瘠性原料所用的粘接剂，瘠性原料是指硅酸盐原料中与水混合后没有粘性而起瘠化作用的物料，用在陶瓷和耐火材料生产中，可降低配合料的可塑性以及减少坯体在干燥和烧成时的收缩，起骨架作用，石英、长石、煅烧过的粘土(熟料)和耐火材料的碎块，都可用作瘠性物料。瘠性原料所用的粘接剂，例如：石蜡、聚乙烯醇PVA、聚乙烯醇缩丁醛PVB等。
在一具体的实施方式中，综合考虑混料方式、成型方式、不引入杂质、排胶温度、预制件强度等因素，采用的是含磷酸二氢铝的粘接剂。磷酸二氢铝是无色无味及黏稠的液体或白色粉末，易溶于水；在常温上固化，液体和固化学结合力强，耐高温、抗震动、抗剥落、耐高温气流冲刷；在常温下与耐火骨料、硬化剂等混合后在一定的温度下一定时间内形成高粘接强度，因此，是很好的粘接剂。而且，采用含磷酸二氢铝的粘接剂，不存在脱脂的问题，也不会因此而污染环境。
向混合均匀后的碳化硅颗粒中添加粘接剂进行混捏、造粒，以便于后续的成型。
在一实施方式中，粘接剂还包含塑化剂，磷酸二氢铝的加入量为混合均匀后的碳化硅颗粒的总量的1％-3％，例如：1％、2％、3％等等。
等静压技术是一种利用密闭高压容器内制品在各向均等的超高压压力状态下成型的超高压液压先进技术。冷等静压技术(Cold Isostatic Pressing，CIP)是在常温下，通常用橡胶或塑料作包套模具材料，以液体为压力介质，主要用于粉体材料成型，为进一步烧结、煅造或热等静压工序提供坯体。
与常规成型技术相比，冷等静压技术具有以下特点：
第一、工作压力低；第二、成型的制品密度高；第三、压坯的密度均匀一致。等静压流体介质传递压力，在各方向上相等；包套与粉料受压缩大体一致，粉料与包套无相对运动，它们之间的摩擦阻力很少，压力只有轻微地下降，因此，坯体密度是均匀的；第四、因为密度均匀，制作长径比可不受限制，有利于生产棒状、管状细而长的产品；第五、可以不需要在粉料中添加润滑剂，既减少对制品的污染，又简化制造工序；第六、制品的性能优异，生产周期短，应用范围广。
在一实施方式中，通过冷等静压技术进行成型的压力为85～110MPa，使用的模具为橡胶模具。该成型技术适合制备大的复杂形状的结构件，得到的预制件密度均匀，烧结出来的样品收缩一致性好，近净成型。其中，橡胶模具的尺寸使得烧结后的碳化硅增强预制件的尺寸略小于最终产品的尺寸，这样便于最终产品的后续加工处理。
为了克服干粉模压受压机限制、模具制造复杂的缺点，本申请采用橡胶模具，粉料填充后使用冷等静压方式压制成型，橡胶模具不受产品形状复杂程度限制，且成本低廉，而冷等静压使SiC坯体受力均匀，生坯密度均匀，烧结时 不易发生形变，同时可以实现增强体净成型。因此，总体来说，通过冷等静压技术进行成型，能得到大的复杂形状的结构件，而且模具便宜，得到的预制件密度均匀，强度高。
参见图2，则步骤S103中，向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，具体可以包括：子步骤S1031和子步骤S1032。
子步骤S1031：向混合均匀后的碳化硅颗粒中添加磷酸二氢铝，加入去离子水，加热至90～110℃，混捏至湿度为8％-12％，得到混合料。
子步骤S1032：将混合料在100-140℃的温度下烘干2～4小时，经造粒机造粒过筛，得到造粒粉。
在一具体应用中，加入混合均匀后的碳化硅颗粒总量的2％的磷酸二氢铝和塑化剂，加入混合均匀后的碳化硅颗粒总量的10％～15％去离子水，加热至90～110℃后进行混捏至湿度为10％左右，得到混合料。将混合料于120℃烘干2～4小时，经造粒机造粒80目过筛，得到造粒粉。上述条件及参数的具体确定，需要根据具体的实际应用来确定。
在一实施方式中，碳化硅增强预制件的孔隙率为36％-38％。具体地，可以通过混捏、造粒的具体过程使碳化硅增强预制件的孔隙率在36％-38％范围内，从而制备得到后续满足要求的碳化硅铝基复合材料。
步骤S104：通过真空液相浸渗方法，使含铝的熔化液和碳化硅增强预制件制成碳化硅铝基复合结构件。
真空液相浸渗工艺是：先将增强体材料制成预制件，再将预制件放入位于承压容器的模具内，抽出预制件内的气体后，在真空和惰性气体的共同作用下，采用压力将金属熔体由通道压入模具内，使之浸渗预制件。其中，预制件的制备和工艺参数的控制是制得高性能复合结构件的关键。这种方法的优点是：适用面广，适用于多种复合材料的制备，增强体材料的类型、形状、尺寸、体积分数基本上不受限制；可直接制成复合零件，特别是形状复杂的零件，基本上无需后续加工；浸渍在真空中进行、压力下凝固，无气孔、疏松、缩孔等缺陷，组织致密，材料性能好；工艺简单，参数易控制，可根据增强体材料和基体金属材料的物理化学特性，严格控制温度、压力等参数，避免严重的界面反应。
在一实施方式中，将含铝的铝合金熔化并加热至720℃～780℃后，恒温0.5～2h，除气去渣，得铝合金熔化液；将已制备的SiC预制件(例如，SiC车身预制件)置于渗铝腔中，用压铸真空机对渗铝腔及SiC预制件进行抽真空，使 渗铝腔内的真空度为500～700Pa，将铝合金熔化液通入渗铝腔浸渗，最后施加4～7MPa的压力，使铝合金熔化液浸渗到SiC预制件中的孔隙中，得到AlSiC复合结构件(例如：放入的是SiC车身预制件，最后制备的是AlSiC复合汽车车身结构件)。
在实际应用中，如果最后制备的是AlSiC复合汽车车身结构件，可以对产品进一步加工，按产品设计，只需要将AlSiC以外的铝合金部分按最终尺寸通过机加工去掉即可。
结合参见图3，为了更好的制备得到后续满足要求的碳化硅铝基复合结构件，在一实施方式中，步骤S104之前，还可以包括：
步骤S105：对碳化硅增强预制件进行烧结，烧结温度为650～850℃，烧结时间为2～4小时。
在一实际应用中，所得SiC生坯置于高温炉中烧结，为防止复杂形状的样品在升温过程中变形，生坯放置时选择合适的承烧支架，避免重力应变，在650～850℃温度下烧结2～4小时，得到有一定强度的SiC增强体预制件。
在一实施方式中，碳化硅铝基复合结构件用于汽车车身结构件。AlSiC复合结构件的密度低，替代低碳钢板，可以减重近三分之二，同时具有高的比强度和比模量，高强、高韧、耐磨、耐蚀、耐疲劳等，节能减排的同时更增强了车身的安全性能和使用寿命。
参见图4，图4是本申请碳化硅增强预制件的制备方法一实施方式的流程图，该方法包括：
步骤S201：提供至少两种不同平均粒度的碳化硅颗粒。
步骤S202：将预定比例的不同平均粒度的碳化硅颗粒混合均匀。
步骤S203：向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，并通过冷等静压技术进行成型，以制成碳化硅增强预制件。
其中，粘接剂为含磷酸二氢铝的粘接剂；碳化硅颗粒的平均粒度范围为3～150um。
其中，粒度在4.0um≤D50≤11.0um范围内的碳化硅颗粒的质量百分含量为65％～80％，粒度在50.7um≤D50≤70.0um范围内的碳化硅颗粒的质量百分含量为20％～35％，粒度在100.0um≤D50≤115.0um范围内的碳化硅颗粒的质量百分含量为0％～5％。
其中，粘接剂还包含塑化剂，磷酸二氢铝的加入量为混合均匀后的碳化硅颗粒的总量的1％-3％。
其中，向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，包括：向混合均匀后的碳化硅颗粒中添加磷酸二氢铝，加入去离子水，加热至90～110℃，混捏至湿度为8％-12％，得到混合料；将混合料在100-140℃的温度下烘干2～4小时，经造粒机造粒过筛，得到造粒粉。
其中，通过冷等静压技术进行成型的压力为85～110MPa，使用的模具为橡胶模具，橡胶模具的尺寸使得烧结后的碳化硅增强预制件的尺寸略小于最终产品的尺寸，例如使得烧结后的碳化硅增强预制件的各向尺寸比最终产品的尺寸小0.1％-2％。
其中，碳化硅增强预制件的孔隙率为36％-38％。
相关内容的详细说明，请参见上述方法部分，在此不再赘叙。
本实施方式选择至少两种不同平均粒度的碳化硅颗粒，颗粒与颗粒之间可以互相填充，使得碳化硅预制件得到足够的强度；而通过冷等静压技术进行成型，能得到大的复杂形状的结构件，而且模具便宜，得到的预制件密度均匀，强度高；通过这种方式，能够为制备AlSiC复合材料提供技术支持。
下面以具体的实施例来说明碳化硅铝基复合结构件的制备。
实施例1：
本实施例以AlSiC复合结构件制备轿车车身B柱为例说明。
传统B柱截面形状比较复杂，由多件冲压钢板焊接而成，除去内饰与外覆件，B柱一般由内到外分为内板、加强板、外板，基本属于闭口薄壁梁结构，与上下接头通过焊接方式将B柱与顶盖侧梁及门框进行连接。要保证B柱具有足够的强度，甚至需要构建“外板-加强板-局部加强板-内板”的结构模式，而且加强板结构通常是一个小总成，通过B柱上安装安全带与门锁等附件的位置所需刚度较大，则需要安装相应的加强板，过多的加强板不仅不利于车身轻量化，且使车身设计和整车装配复杂化。
本实例依然采用内、外板B柱结构，同时将B柱的上下接头分别于内、外板形成构件，在生产过程中一体成型，并通过以下工艺步骤实现。
(1)橡胶模具设计：按照B柱与上下接头一体成型的规划，净成型的SiC增强体预制件烧结后略小于最终产品尺寸，方便最终机加工。
(2)以粒度范围4.0um≤D50≤11.0um，50.7um≤D50≤70.0um两种SiC颗粒、浓度为50％的磷酸二氢铝、6063铝合金为原材料，按照一定比例将SiC颗粒、粘接剂及去离子水投入混捏机，其中SiC颗粒粗细比例，粗∶细＝1∶3，加入量：2％的磷酸二氢铝，12wt％的去离子水，在90℃温度下混捏至湿度10％，出料烘干造粒。
(3)将步骤2所得的造粒粉填充至橡胶模具内，保证粉料填充均匀、松装密度一致，在90MPa的压力下使用冷等静压压制成型。
(4)将步骤3的SiC生坯进行预烧结，为防止复杂形状的样品在升温过程中变形，生坯放置时选择合适的承烧支架，避免重力应变，烧结温度820℃，保温3小时，得到有一定强度的SiC增强体预制件。
(5)采用6063铝合金为铝基原料，选择渗铝腔不受形状限制，略大于预制件即可，将步骤4的预制件置于渗铝腔内预热至660℃，保温半小时，抽真空至650Pa，当渗铝腔内温度到达渗铝温度后，打开铝液通道使铝液填满渗铝腔，进行适当的保温操作，并通入氮气，加压5MPa，保压15分钟，确保铝液充分渗入碳化硅增强体预制件的空隙中，随炉冷却。此处的氮气还可以选用其他的惰性气体代替，但选用氮气成本较低。
(6)将步骤5所得产品进一步加工，按产品设计，只需要将AlSiC以外的铝合金部分按最终尺寸通过机加工去掉即可。
实施例2：
本实施例以AlSiC复合结构件制备轿车车身前纵梁为例说明。
在汽车结构中，由低碳钢板冲压而成的薄壁构件被广泛采用，可以经过翻边与其他构件焊接在一起，是车辆碰撞时的主要吸能构件，包括汽车的前纵梁、车身侧围、地板等许部位，传统的汽车前纵梁横切面是薄壁矩形结构。汽车发生正面碰撞时，主要是由车身前部的塑性形变来吸收碰撞动能，其中起主要作用的是前纵梁。
相较于传统汽车前纵梁的低碳钢材质，铝碳化硅复合结构件具有更高的屈服强度和吸能能力，同时达到大幅度减重的目的。综合考虑吸能能力、碰撞减速度、位移侵入量，并方便于橡胶模具填粉和压制成型，本实例选用槽型截面汽车前纵梁进行制备，并通过以下工艺步骤实现。
(1)橡胶模具设计：按照槽型截面汽车前纵梁设计，净成型的SiC增强体预制件烧结后略小于最终产品尺寸，方便最终机加工。
(2)以粒度范围4.0um≤D50≤11.0um，50.7um≤D50≤70.0um，100.0um≤D50≤115.0um三种SiC颗粒、浓度为50％的磷酸二氢铝、6063铝合金为原材料，按照一定比例将SiC颗粒、粘接剂及去离子水投入混捏机，其中SiC颗粒粗细比例，粗∶细∶超细＝1∶7∶12，加入量：2％的磷酸二氢铝，15％的去离子水，在95℃温度下混捏至湿度10％，出料烘干造粒。
(3)将步骤2所得的造粒粉填充至橡胶模具内，保证粉料填充均匀、松装密度一致，在90MPa的压力下使用冷等静压压制成型。
(4)将步骤3的SiC生坯进行预烧结，为防止复杂形状的样品在升温过程中变形，生坯放置时选择合适的承烧支架，避免重力应变，烧结温度800℃，保温3小时，得到有一定强度的SiC增强体预制件。
(5)采用6063铝合金为铝基原料，选择渗铝腔不受形状限制，略大于预制件即可，将步骤4的预制件置于渗铝腔内预热至660℃，保温半小时，抽真空至650Pa，当渗铝腔内温度到达渗铝温度后，打开铝液通道使铝液填满渗铝腔，进行适当的保温操作，并通入氮气，加压7MPa，保压15分钟，确保铝液充分渗入碳化硅增强体预制件的空隙中，随炉冷却。此处的氮气还可以选用其他的惰性气体代替，但选用氮气成本较低。
(6)将步骤5所得产品进一步加工，按产品设计，只需要将AlSiC以外的铝合金部分按最终尺寸通过机加工去掉即可。
上述具体的实施例，是碳化硅铝基复合结构件用于汽车车身结构件。AlSiC复合结构件的密度低，替代低碳钢板，可以减重近三分之二，同时具有高的比 强度和比模量，高强、高韧、耐磨、耐蚀、耐疲劳等，节能减排的同时更增强了车身的安全性能和使用寿命。
以上所述仅为本发明的实施方式，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围。

Claims (17)

  1. 一种碳化硅铝基复合结构件的制备方法，其中，所述方法包括：
    提供至少两种不同平均粒度的碳化硅颗粒；
    将预定比例的所述不同平均粒度的碳化硅颗粒混合均匀；
    向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，并通过冷等静压技术进行成型，以制成碳化硅增强预制件；
    通过真空液相浸渗方法，使含铝的熔化液和所述碳化硅增强预制件制成所述碳化硅铝基复合结构件。
  2. 根据权利要求1所述的制备方法，其中，所述粘接剂为含磷酸二氢铝的粘接剂；所述碳化硅颗粒的平均粒度范围为3～150um。
  3. 根据权利要求2所述的制备方法，其中，粒度在4.0um≤D50≤11.0um范围内的碳化硅颗粒的质量百分含量为65％～80％，粒度在50.7um≤D50≤70.0um范围内的碳化硅颗粒的质量百分含量为20％～35％，粒度在100.0um≤D50≤115.0um范围内的碳化硅颗粒的质量百分含量为0％～5％。
  4. 根据权利要求2所述的制备方法，其中，所述粘接剂还包含塑化剂，所述磷酸二氢铝的加入量为所述混合均匀后的碳化硅颗粒的总量的1％-3％。
  5. 根据权利要求2所述的制备方法，其中，所述向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，包括：
    向混合均匀后的碳化硅颗粒中添加磷酸二氢铝，加入去离子水，加热至90～110℃，混捏至湿度为8％-12％，得到混合料；
    将所述混合料在100-140℃的温度下烘干2～4小时，经造粒机造粒过筛，得到造粒粉。
  6. 根据权利要求1所述的制备方法，其中，所述通过冷等静压技术进行成型的压力为85～110MPa，使用的模具为橡胶模具，所述橡胶模具的尺寸使得烧结后的碳化硅增强预制件的尺寸略小于最终产品的尺寸。
  7. 根据权利要求1所述的制备方法，其中，所述碳化硅增强预制件的孔隙率为36％-38％。
  8. 根据权利要求1所述的方法，其中，所述通过真空液相浸渗方法，使含铝的熔化液和所述碳化硅增强预制件制成所述碳化硅铝基复合结构件之前，包括：
    对所述碳化硅增强预制件进行烧结，烧结温度为650～850℃，烧结时间为2～4小时。
  9. 根据权利要求1所述的制备方法，其中，所述通过真空液相浸渗方法，使含铝的熔化液和所述碳化硅增强预制件制成所述碳化硅铝基复合结构件包括：
    将所述碳化硅增强预制件置于渗铝腔中，抽真空至真空度为500-700Pa；
    将含铝的熔化液通入所述渗铝腔，并充入氮气或惰性气体，使气压达到4-7MPa，从而使含铝的融化液浸渗到所述碳化硅增强预制件的空隙中。
  10. 根据权利要求1所述的制备方法，其中，所述碳化硅铝基复合结构件用于汽车车身结构件。
  11. 一种碳化硅增强预制件的制备方法，其中，所述方法包括：
    提供至少两种不同平均粒度的碳化硅颗粒；
    将预定比例的所述不同平均粒度的碳化硅颗粒混合均匀；
    向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，并通过冷等静压技术进行成型，以制成所述碳化硅增强预制件。
  12. 根据权利要求11所述的制备方法，其中，所述粘接剂为含磷酸二氢铝的粘接剂；所述碳化硅颗粒的平均粒度范围为3～150um。
  13. 根据权利要求12所述的制备方法，其中，粒度在4.0um≤D50≤11.0um范围内的碳化硅颗粒的质量百分含量为65％～80％，粒度在50.7um≤D50≤70.0um范围内的碳化硅颗粒的质量百分含量为20％～35％，粒度在100.0um≤D50≤115.0um范围内的碳化硅颗粒的质量百分含量为0％～5％。
  14. 根据权利要求12所述的制备方法，其中，所述粘接剂还包含塑化剂，所述磷酸二氢铝的加入量为所述混合均匀后的碳化硅颗粒的总量的1％-3％。
  15. 根据权利要求12所述的制备方法，其中，所述向混合均匀后的碳化硅颗粒中添加含瘠性原料所用的粘接剂进行混捏、造粒，包括：
    向混合均匀后的碳化硅颗粒中添加磷酸二氢铝，加入去离子水，加热至90～110℃，混捏至湿度为8％-12％，得到混合料；
    将所述混合料在100-140℃的温度下烘干2～4小时，经造粒机造粒过筛，得到造粒粉。
  16. 根据权利要求11所述的制备方法，其中，所述通过冷等静压技术进行 成型的压力为85～110MPa，使用的模具为橡胶模具，所述橡胶模具的尺寸使得烧结后的碳化硅增强预制件的尺寸略小于最终产品的尺寸。
  17. 根据权利要求11所述的制备方法，其中，所述碳化硅增强预制件的孔隙率为36％-38％。
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