CN106435241A - Preparation method for metal-matrix composite enhanced by porous Si3N4/SiC multiphase ceramic - Google Patents

Preparation method for metal-matrix composite enhanced by porous Si3N4/SiC multiphase ceramic Download PDF

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CN106435241A
CN106435241A CN201610726196.1A CN201610726196A CN106435241A CN 106435241 A CN106435241 A CN 106435241A CN 201610726196 A CN201610726196 A CN 201610726196A CN 106435241 A CN106435241 A CN 106435241A
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porous
ceramic
metal
complex phase
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CN106435241B (en
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叶枫
金义程
丁俊杰
马杰
杨春萍
高晔
刘强
张标
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
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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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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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    • 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
    • C04B41/5025—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 with ceramic materials
    • C04B41/5031—Alumina
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    • 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
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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
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/658—Atmosphere during thermal treatment

Abstract

The invention provides a preparation method for a metal-matrix composite enhanced by porous Si3N4/SiC multiphase ceramic, and relates to a preparation method for a ceramic-enhanced metal-matrix composite. By adoption of the preparation method for the metal-matrix composite enhanced by the porous Si3N4/SiC multiphase ceramic, the technical problems that an existing ceramic-enhanced metal-matrix composite is high in thermal expansion coefficient, and reinforcement bodies are prone to agglomeration and cannot be dispersed evenly are solved. The preparation method for the metal-matrix composite enhanced by the porous Si3N4/SiC multiphase ceramic comprises the steps that firstly, slurry is prepared; secondly, the porous Si3N4/SiC multiphase ceramic is prepared; thirdly, surface modification of the porous multiphase ceramic is conducted; and fourthly, the composite is prepared. According to the preparation method for the metal-matrix composite enhanced by the porous Si3N4/SiC multiphase ceramic, the pore diameter of the porous multiphase ceramic is small, growth of metal grains in the composite is restrained, and the comprehensive mechanical property of the composite is effectively improved through fine crystal enhancement; Si3N4/SiC nanowires in the porous multiphase ceramic are evenly distributed; ceramic enhancement bodies in the metal-matrix composite are distributed continuously, so that the metal-matrix composite has a low thermal expansion coefficient; and the metal content is high, so that the composite has high thermal conductivity.

Description

A kind of porous Si3N4/ SiC complex phase ceramic strengthens the preparation method of metal-base composites
Technical field
The present invention relates to a kind of preparation method of Ceramic Reinforced MMCs.
Background technology
Ceramic Reinforced MMCs have low-density, high intensity, high elastic modulus, high heat conductance, low-thermal-expansion Coefficient and good anti-wear performance, before Aero-Space, Electronic Packaging, machine-building, the field such as wear-resistant are widely used Scape.
In Ceramic Reinforced MMCs, the form of reinforcement mainly has several classes：Particle, lamella, fiber, crystalline substance Palpus and continuous phase.Wherein, ceramic particle reinforced metal base composites are classes of most study, due to its low raw-material cost And process is simple, be widely used in the industrial production, but with fiber, whisker reinforcement composite phase specific strength relatively Low.Ceramic particle, lamella, fiber, whisker belong to discontinuous phase, in order to mix raw material, need for raw material to enter every trade Celestial body mill or high-energy ball milling, easily introduce impurity in mixed process.At present, nano particle, nano wire strengthen metal-base composites Get the attention, due to the high mechanical property of nano-scale reinforcement, only add a small amount of (<10vol.%) can be very big Improve the comprehensive mechanical property of material, but nano particle, nano wire are easily reunited in raw material mixed process, affect composite wood The structural homogenity of material.Continuous phase strengthens composite and there is not reinforcement problem pockety, and such material needs first Porous ceramics to be prepared, as precast body, can control metallic matrix in composite by the pore structure controlling porous ceramics Distributional pattern.
Gel casting forming is used for preparing the base substrate of high-compactness earliest, by causing the polymerization of monomer in slurry, obtains There is the gel of three-dimensional netted crosslinking, thus realizing the fixation in situ of powder in slurry.The feature of the method is gained base substrate Even tissue, gel strength is high, can carry out machining.Using low solid content slurry or the other pore-creating techniques of combination, can make Get everything ready and have the porous body of high porosity, be accurately controlled base substrate by controlling the solid concentration of slurry and the content of pore creating material The porosity.The pore being formed after solvent volatilization is intercommunicating pore, and the therefore porous ceramics of the method preparation can be used as compound The reinforcement of material.
The pore size distribution of the porous ceramics of Gel-casting process shaping is uniform, as the metal-base composites of reinforcement preparation In, metallic matrix and ceramic enhancement phase continuous uniform distribution.Continuous metallic matrix makes material have high thermal conductivity, continuously Ceramic phase makes material have low thermal coefficient of expansion.By adjusting the porosity, the pore structure of porous ceramics, you can adjustment composite wood The composition of matrix and reinforcement and distribution in material.Additionally, the tiny aperture of porous ceramics can limit growing up of metal grain, play The effect of " refined crystalline strengthening ".
Content of the invention
The present invention is high in order to solve current Ceramic Reinforced MMCs thermal coefficient of expansion, and reinforcement is easily rolled into a ball Poly- and difficult finely dispersed technical problem, and a kind of porous Si is provided3N4/ SiC complex phase ceramic strengthens the system of metal-base composites Preparation Method.
A kind of porous Si of the present invention3N4The preparation method that/SiC complex phase ceramic strengthens metal-base composites is by following Step is carried out：
First, prepare slurry：Organic solvent and water are uniformly mixed, obtains mixed solution, add ceramic powder, sintering to help Agent, dispersant, monomer and crosslinking agent, use Al2O3Ball ball milling mixing 11h～13h, obtains slurry；Described water and organic solution Volume ratio is 1:(3～5)；Described ceramic powder is Si3N4With the mixed powder of SiC, Si3N4Mass ratio with SiC is 1:(4 ～6)；Described ceramic powder is 1 with the volume ratio of mixed solution:(1.67～10)；Described sintering aid and ceramic powders Mass ratio be 1:(23～25)；Described dispersant is 1 with the mass ratio of ceramic powders:(200～400)；Described monomer Mass ratio with ceramic powders is 1:(5～7)；Described crosslinking agent is 1 with the mass ratio of ceramic powders:(110～130)；
2nd, prepare porous Si3N4/ SiC complex phase ceramic：Slurry prepared by step one is the bar of 100Pa in room temperature and air pressure Stir 5min～10min degasification under part, add initiator and catalyst in slurry with the degassed, put in mould, in room temperature Lower solidification 2h, after the demoulding from mould gel, be dried under conditions of the atmosphere of saturated vapor and temperature are 30 DEG C～50 DEG C Solvent volatilization to gel completely, places in air furnace with the heating rate of 0.5 DEG C/min～1 DEG C/min from room temperature To 600 DEG C and temperature be 600 DEG C under conditions of be incubated 2h dumping, then cool to room temperature with the furnace, obtain ceramic body, pottery Base substrate in a nitrogen atmosphere first with the heating rate of 10 DEG C/min～20 DEG C/min from room temperature to 1000 DEG C, then in nitrogen It is warming up to 1600 DEG C～1900 DEG C with the heating rate of 3 DEG C/min～10 DEG C/min under atmosphere and with temperature be in a nitrogen atmosphere It is incubated 1h～4h under conditions of 1600 DEG C～1900 DEG C, then cool to room temperature with the furnace in a nitrogen atmosphere, obtain porous Si3N4/ SiC complex phase ceramic；Described initiator is 1 with the mass ratio of the monomer described in step one:(40～60), described catalyst Mass ratio with the monomer described in step one is 1:(900～1100)；
3rd, the surface modification of porous complex phase ceramic：Porous Si prepared by step 23N4/ SiC complex phase ceramic puts into Al2O3 In crucible, add Ludox or Alumina gel to flooding porous Si completely3N4/ SiC complex phase ceramic, is 100Pa's in room temperature and air pressure Under the conditions of stand 1h～5h, then temperature be 50 DEG C under conditions of 24h is dried, subsequently from room under the atmosphere of nitrogen or argon gas Temperature is first warming up to 200 DEG C～600 DEG C and is incubated 1h under the atmosphere of nitrogen or argon gas, then heats up under the atmosphere of nitrogen or argon gas It is incubated 2h, finally along with the furnace cooling under the atmosphere of nitrogen or argon gas to 1000 DEG C～1400 DEG C and under the atmosphere of nitrogen or argon gas To room temperature, obtain the porous complex phase ceramic after surface modification；The mass concentration of described Ludox and Alumina gel is 10%；
4th, the porous complex phase ceramic after the surface modification preparing step 3 is inserted in graphite crucible, and metal alloy is put The top of the porous complex phase ceramic after surface modification, is then placed in sintering furnace, and in air pressure be 10Pa and heating rate is 5 DEG C/min～10 DEG C/min under the conditions of be warming up to 700 DEG C～900 DEG C, and air pressure be 10Pa and temperature be 700 DEG C～900 DEG C bars It is incubated 1h under part, then passing to argon gas to air pressure is 2MPa～8MPa, and be that 2MPa～8MPa and temperature are in the air pressure of argon gas It is incubated 2h～10h, finally the air pressure in argon gas is along with the furnace cooling under conditions of 2MPa～8MPa under conditions of 700 DEG C～900 DEG C To room temperature, obtain porous Si3N4/ SiC complex phase ceramic strengthens metal-base composites；The volume of described metallic matrix and step The volume of the porous complex phase ceramic pore after the surface modification of three preparations is equal.
The volume of the porous complex phase ceramic pore after the surface modification of step 3 preparation is to be surveyed by Archimedes's drainage ?.
The principle of the present invention：
First, use continuous phase strengthened metal base composite material：
The present invention prepares porous ceramics as reinforcement, because porous ceramics is a continuously entirety, and the heat of pottery The coefficient of expansion is very low, and (such as SiC is 4 × 10-6K-1), there is good effect of contraction to metallic matrix, so the composite wood of preparation Material thermal coefficient of expansion is very low；
The present invention can obtain the porous ceramics of even tissue by gel injection-moulding method, also solves enhancing phase constitution uneven Problem；
2nd, certainly grow Si in the way of vapor phase growth3N4Nano wire：
The present invention is prepared for the ceramic body of high porosity by gel injection-moulding, and the hole of high-volume fractional is Si3N4Gas Mutually growth provides good environment, and vapor phase growth can obtain the Si with high length-diameter ratio3N4Nano wire.
Main innovation point, feature：
1st, the Si of the present invention3N4Nano wire is that raw material is Si from growing in sintering process3N4Powder, price is relatively low, And generally prepare nano wire, whisker reinforced metal matrix composites, and need directly to buy nano wire, whisker, expensive；
2nd, generally prepare nano wire, whisker reinforced metal matrix composites, nano wire, whisker are easily reunited, be difficult to dispersion, And the present invention passes through gel injection-moulding method, first prepare finely dispersed ceramic powder slurry, after gel, obtain the SiC/ of even tissue Si3N4Powder base substrate, obtains the SiC/Si of even tissue after re-sintering3N4Complex phase ceramic, with the complex phase ceramic of gained as reinforcement Prepare metal-base composites, it is to avoid nano wire, the problem of whisker agglomeration, be nano wire, whisker reinforcedmetal base composite wood The preparation of material provides new approaches；
3rd, the present invention strengthens phase with the porous ceramics of even tissue for continuous, constrains the thermal expansion of metallic matrix, makes multiple Condensation material has low thermal coefficient of expansion；
4th, the aperture of the porous ceramics of the present invention is less, I to 0.5 μm, can limit growing up of metal grain, play The effect of " refined crystalline strengthening ", is greatly improved the mechanical property of composite.
Porous Si of the present invention3N4In/SiC complex phase ceramic enhancing metal-base composites, the volume fraction of porous ceramics is 10～60vol.%, wherein, 10～50vol.% is equally distributed Si3N4Nano wire, as the porous complex phase pottery of reinforcement Porcelain, the porosity is 40～90vol.%, and aperture is 0.5-20 μm, and pore is intercommunicating pore, in uniformly three-dimensional netted distribution, gold The volume fraction belonging to matrix is 40～90vol.%；
Porous Si of the present invention3N4The porosity of/SiC complex phase ceramic, aperture controlled in a big way, as precast body The designability of the metal-base composites of preparation is good；
The aperture of the porous complex phase ceramic of the present invention is less, limits growing up of metal grain in composite, " fine grain is strong Change " effectively increases the comprehensive mechanical property of composite；
Si in the porous complex phase ceramic of the present invention3N4Nano wire is uniformly distributed, and efficiently solves nanoscale in composite and increases Strong body problem pockety；
In the metal-base composites of the present invention, ceramic phase reinforcement is in continuous distributed, limits the thermal expansion of metallic matrix, Metal-base composites is made to have low thermal coefficient of expansion, higher tenor makes composite have higher thermal conductivity again；
The density of the composite of the present invention is relatively low, and comprehensive mechanical property is excellent, the density of material<3g/cm3, after timeliness Bending strength>800MPa, fracture toughness>10MPa·m1/2, elastic modelling quantity>110GPa, also has high heat conductance and low-heat is swollen Swollen coefficient, thermal conductivity>120W·m-1·K-1, thermal coefficient of expansion<8×10-6K-1, when the porosity is 70vol.%, the compression of material Intensity>30MPa, excellent mechanics and thermal property make it have broad application prospects in Electronic Packaging field.
Brief description
Fig. 1 is porous Si of test one step 2 preparation3N4The XRD of/SiC complex phase ceramic, ◆ be α-SiC, ● be β- Si3N4；
Fig. 2 is porous Si of test one step 2 preparation3N4The Fracture scan figure of/SiC complex phase ceramic；
Fig. 3 is porous Si of test one step 2 preparation3N4The Fracture scan figure of/SiC complex phase ceramic；
Fig. 4 is porous Si of test one step 2 preparation3N4The pore size distribution curve figure of/SiC complex phase ceramic；
Fig. 5 is porous Si of test one step 4 preparation3N4/ SiC complex phase ceramic strengthens the scanning of metal-base composites Figure, 1 is alloy matrix aluminum, and 2 is α-SiC crystal grain, and 3 is β-Si3N4Nano wire.
Specific embodiment
Specific embodiment one：Present embodiment is a kind of porous Si3N4/ SiC complex phase ceramic strengthens metal-base composites Preparation method, specifically carry out according to the following steps：
First, prepare slurry：Organic solvent and water are uniformly mixed, obtains mixed solution, add ceramic powder, sintering to help Agent, dispersant, monomer and crosslinking agent, use Al2O3Ball ball milling mixing 11h～13h, obtains slurry；Described water and organic solution Volume ratio is 1:(3～5)；Described ceramic powder is Si3N4With the mixed powder of SiC, Si3N4Mass ratio with SiC is 1:(4 ～6)；Described ceramic powder is 1 with the volume ratio of mixed solution:(1.67～10)；Described sintering aid and ceramic powders Mass ratio be 1:(23～25)；Described dispersant is 1 with the mass ratio of ceramic powders:(200～400)；Described monomer Mass ratio with ceramic powders is 1:(5～7)；Described crosslinking agent is 1 with the mass ratio of ceramic powders:(110～130)；
2nd, prepare porous Si3N4/ SiC complex phase ceramic：Slurry prepared by step one is the bar of 100Pa in room temperature and air pressure Stir 5min～10min degasification under part, add initiator and catalyst in slurry with the degassed, put in mould, in room temperature Lower solidification 2h, after the demoulding from mould gel, be dried under conditions of the atmosphere of saturated vapor and temperature are 30 DEG C～50 DEG C Solvent volatilization to gel completely, places in air furnace with the heating rate of 0.5 DEG C/min～1 DEG C/min from room temperature To 600 DEG C and temperature be 600 DEG C under conditions of be incubated 2h dumping, then cool to room temperature with the furnace, obtain ceramic body, pottery Base substrate in a nitrogen atmosphere first with the heating rate of 10 DEG C/min～20 DEG C/min from room temperature to 1000 DEG C, then in nitrogen It is warming up to 1600 DEG C～1900 DEG C with the heating rate of 3 DEG C/min～10 DEG C/min under atmosphere and with temperature be in a nitrogen atmosphere It is incubated 1h～4h under conditions of 1600 DEG C～1900 DEG C, then cool to room temperature with the furnace in a nitrogen atmosphere, obtain porous Si3N4/ SiC complex phase ceramic；Described initiator is 1 with the mass ratio of the monomer described in step one:(40～60), described catalyst Mass ratio with the monomer described in step one is 1:(900～1100)；
3rd, the surface modification of porous complex phase ceramic：Porous Si prepared by step 23N4/ SiC complex phase ceramic puts into Al2O3 In crucible, add Ludox or Alumina gel to flooding porous Si completely3N4/ SiC complex phase ceramic, is 100Pa's in room temperature and air pressure Under the conditions of stand 1h～5h, then temperature be 50 DEG C under conditions of 24h is dried, subsequently from room under the atmosphere of nitrogen or argon gas Temperature is first warming up to 200 DEG C～600 DEG C and is incubated 1h under the atmosphere of nitrogen or argon gas, then heats up under the atmosphere of nitrogen or argon gas It is incubated 2h, finally along with the furnace cooling under the atmosphere of nitrogen or argon gas to 1000 DEG C～1400 DEG C and under the atmosphere of nitrogen or argon gas To room temperature, obtain the porous complex phase ceramic after surface modification；The mass concentration of described Ludox and Alumina gel is 10%；
4th, the porous complex phase ceramic after the surface modification preparing step 3 is inserted in graphite crucible, and metal alloy is put The top of the porous complex phase ceramic after surface modification, is then placed in sintering furnace, and in air pressure be 10Pa and heating rate is 5 DEG C/min～10 DEG C/min under the conditions of be warming up to 700 DEG C～900 DEG C, and air pressure be 10Pa and temperature be 700 DEG C～900 DEG C bars It is incubated 1h under part, then passing to argon gas to air pressure is 2MPa～8MPa, and be that 2MPa～8MPa and temperature are in the air pressure of argon gas It is incubated 2h～10h, finally the air pressure in argon gas is along with the furnace cooling under conditions of 2MPa～8MPa under conditions of 700 DEG C～900 DEG C To room temperature, obtain porous Si3N4/ SiC complex phase ceramic strengthens metal-base composites；The volume of described metallic matrix and step The volume of the porous complex phase ceramic pore after the surface modification of three preparations is equal.
Specific embodiment two：Present embodiment from unlike specific embodiment one：Organic molten described in step one Agent is isopropanol.Other are identical with specific embodiment party one.
Specific embodiment three：Present embodiment from unlike specific embodiment one:Sintering described in step one Auxiliary agent is Y2O3And Al2O3Mixed powder, Y2O3And Al2O3Mass ratio be 3:2.Other identical with specific embodiment one.
Specific embodiment four：Present embodiment from unlike specific embodiment one：Dispersant described in step one For TMAH.Other identical with specific embodiment one.
Specific embodiment five：Present embodiment from unlike specific embodiment one：Monomer described in step one is Acrylamide.Other identical with specific embodiment one.
Specific embodiment six：Present embodiment from unlike specific embodiment one：Crosslinking described in step one Agent is N,N methylene bis acrylamide.Other identical with specific embodiment one.
Specific embodiment seven：Present embodiment from unlike specific embodiment one：Initiation described in step 2 Agent is ammonium persulfate.Other identical with specific embodiment one.
Specific embodiment eight：Present embodiment from unlike specific embodiment one：Catalysis described in step 2 Agent is tetramethylethylenediamine.Other identical with specific embodiment one.
Specific embodiment nine：Present embodiment from unlike specific embodiment one：Metal described in step 4 Alloy is aluminium alloy or copper alloy.Other identical with specific embodiment one.
Effect of the present invention is verified by tests below：
Test one：This is tested as a kind of porous Si3N4/ SiC complex phase ceramic strengthens the preparation method of metal-base composites, Specifically carry out according to the following steps：
First, prepare slurry：Organic solvent and water are uniformly mixed, obtains mixed solution, add ceramic powder, sintering to help Agent, dispersant, monomer and crosslinking agent, use Al2O3Ball ball milling mixing 12h, obtains slurry；Described water and the volume of organic solution Than for 1:4；Described ceramic powder is Si3N4With the mixed powder of SiC, Si3N4Mass ratio with SiC is 1:5；Described pottery Porcelain powder is 1 with the volume ratio of mixed solution:6.67；Described sintering aid is 1 with the mass ratio of ceramic powders:24；Described The mass ratio of dispersant and ceramic powders be 1:300；Described monomer is 1 with the mass ratio of ceramic powders:6；Described friendship Connection agent is 1 with the mass ratio of ceramic powders:120；
2nd, prepare porous Si3N4/ SiC complex phase ceramic：Slurry prepared by step one is the bar of 100Pa in room temperature and air pressure Stir 5min degasification under part, add initiator and catalyst in slurry with the degassed, put in mould, solidify at room temperature 2h, after the demoulding from mould gel, molten in being dried to gel under conditions of the atmosphere of saturated vapor and temperature are 40 DEG C Agent volatilization completely, places in air furnace with the heating rate of 1 DEG C/min from room temperature to 600 DEG C and in temperature for 600 DEG C Under conditions of be incubated 2h dumping, then cool to room temperature with the furnace, obtain ceramic body, ceramic body is in a nitrogen atmosphere first with 10 DEG C/heating rate of min from room temperature to 1000 DEG C, be then warming up to the heating rate of 10 DEG C/min in a nitrogen atmosphere 1700 DEG C and in a nitrogen atmosphere with temperature be 1700 DEG C under conditions of be incubated 2h, then cool to room in a nitrogen atmosphere with the furnace Temperature, obtains porous Si3N4/ SiC complex phase ceramic；Described initiator is 1 with the mass ratio of the monomer described in step one:50, institute The catalyst stated is 1 with the mass ratio of the monomer described in step one:1000；
3rd, the surface modification of porous complex phase ceramic：Porous Si prepared by step 23N4/ SiC complex phase ceramic puts into Al2O3 In crucible, add Alumina gel to flooding porous Si completely3N4/ SiC complex phase ceramic, quiet under conditions of being 100Pa in room temperature and air pressure Put 5h, then under conditions of temperature is 50 DEG C, 24h is dried, subsequently under the atmosphere of nitrogen, is first warming up to 400 DEG C simultaneously from room temperature It is incubated 1h under the atmosphere of nitrogen, then be warming up to 1400 DEG C under the atmosphere of nitrogen and be incubated 2h under the atmosphere of nitrogen, finally Cool to room temperature with the furnace under the atmosphere of nitrogen, obtain the porous complex phase ceramic after surface modification；The quality of described Alumina gel Concentration is 10%；
4th, the porous complex phase ceramic after the surface modification preparing step 3 is inserted in graphite crucible, and metal alloy is put The top of the porous complex phase ceramic after surface modification, is then placed in sintering furnace, and in air pressure be 10Pa and heating rate is 10 DEG C/min under the conditions of be warming up to 800 DEG C, and be incubated 1h under the conditions of air pressure is 800 DEG C for 10Pa and temperature, then pass to argon gas It is 5MPa to air pressure, and is to be incubated 5h under conditions of 5MPa and temperature are 800 DEG C in the air pressure of argon gas, finally in the air pressure of argon gas Cool to room temperature with the furnace under conditions of 5MPa, obtain porous Si3N4/ SiC complex phase ceramic strengthens metal-base composites；Described The volume of metallic matrix equal with the volume of the porous complex phase ceramic pore after surface modification prepared by step 3；
Organic solvent described in step one is isopropanol；
Sintering aid described in step one is Y2O3And Al2O3Mixed powder, Y2O3And Al2O3Mass ratio be 3:2；
Dispersant described in step one is TMAH；
Monomer described in step one is acrylamide；
Crosslinking agent described in step one is N,N methylene bis acrylamide；
Initiator described in step 2 is ammonium persulfate；
Catalyst described in step 2 is tetramethylethylenediamine；
Metal alloy described in step 4 is aluminium alloy.
Fig. 1 is porous Si of test one step 2 preparation3N4The XRD spectrum of/SiC complex phase ceramic, ◆ be α-SiC, ● be β- Si3N4, as can be seen from the figure porous complex phase ceramic is mainly by α-SiC and β-Si3N4Two phase compositions, are not introduced in preparation process Other impurity.
Fig. 2 and Fig. 3 is porous Si of test one step 2 preparation3N4The Fracture scan figure of/SiC complex phase ceramic, can from figure To find out porous complex phase ceramic mainly by equiax crystal and the β-Si of α-SiC3N4Nano wire forms, and two-phase is uniformly distributed, porous ceramics Hole be intercommunicating pore, in uniformly three-dimensional netted distribution.
Fig. 4 is porous Si of test one step 2 preparation3N4The pore size distribution curve figure of/SiC complex phase ceramic, can from figure With find out porous complex phase ceramic pore-size distribution as Unimodal Distribution, the even pore distribution of porous complex phase ceramic is described, it is average Aperture is 1.62 μm.
Fig. 5 is porous Si of test one step 4 preparation3N4/ SiC complex phase ceramic strengthens the scanning of metal-base composites Figure, 1 is alloy matrix aluminum, and 2 is α-SiC crystal grain, and 3 is β-Si3N4Nano wire, as can be seen from the figure composite is mainly by aluminium Alloy substrate, α-SiC crystal grain, β-Si3N4Nano wire forms, and matrix is alternate with enhancing to be tightly combined and do not exist pore, strengthens phase It is evenly distributed, reunite.

Claims (9)

1. a kind of porous Si3N4/ SiC complex phase ceramic strengthens the preparation method of metal-base composites it is characterised in that porous Si3N4The preparation method that/SiC complex phase ceramic strengthens metal-base composites is carried out according to the following steps：
First, prepare slurry：Organic solvent and water are uniformly mixed, obtains mixed solution, add ceramic powder, sintering aid, divide Powder, monomer and crosslinking agent, use Al2O3Ball ball milling mixing 11h～13h, obtains slurry；Described water and the volume of organic solution Than for 1:(3～5)；Described ceramic powder is Si3N4With the mixed powder of SiC, Si3N4Mass ratio with SiC is 1:(4～ 6)；Described ceramic powder is 1 with the volume ratio of mixed solution:(1.67～10)；Described sintering aid and ceramic powders Mass ratio is 1:(23～25)；Described dispersant is 1 with the mass ratio of ceramic powders:(200～400)；Described monomer with The mass ratio of ceramic powders is 1:(5～7)；Described crosslinking agent is 1 with the mass ratio of ceramic powders:(110～130)；
2nd, prepare porous Si3N4/ SiC complex phase ceramic：Slurry prepared by step one is under conditions of room temperature and air pressure are 100Pa Stirring 5min～10min degasification, adds initiator and catalyst in slurry with the degassed, puts in mould, solid at room temperature Change 2h, after the demoulding from mould gel, be dried under conditions of the atmosphere of saturated vapor and temperature are 30 DEG C～50 DEG C to solidifying Solvent volatilization in glue completely, place in air furnace with the heating rate of 0.5 DEG C/min～1 DEG C/min from room temperature to 600 DEG C and temperature be 600 DEG C under conditions of be incubated 2h dumping, then cool to room temperature with the furnace, obtain ceramic body, ceramic blank Body in a nitrogen atmosphere first with the heating rate of 10 DEG C/min～20 DEG C/min from room temperature to 1000 DEG C, then in nitrogen gas It is warming up to 1600 DEG C～1900 DEG C with the heating rate of 3 DEG C/min～10 DEG C/min under atmosphere and with temperature be in a nitrogen atmosphere It is incubated 1h～4h under conditions of 1600 DEG C～1900 DEG C, then cool to room temperature with the furnace in a nitrogen atmosphere, obtain porous Si3N4/ SiC complex phase ceramic；Described initiator is 1 with the mass ratio of the monomer described in step one:(40～60), described catalyst Mass ratio with the monomer described in step one is 1:(900～1100)；
3rd, the surface modification of porous complex phase ceramic：Porous Si prepared by step 23N4/ SiC complex phase ceramic puts into Al2O3Crucible Interior, add Ludox or Alumina gel to flooding porous Si completely3N4/ SiC complex phase ceramic, is the condition of 100Pa in room temperature and air pressure Lower standing 1h～5h, is then dried 24h, subsequently under the atmosphere of nitrogen or argon gas from room temperature first under conditions of temperature is 50 DEG C It is warming up to 200 DEG C～600 DEG C and is incubated 1h under the atmosphere of nitrogen or argon gas, then be warming up under the atmosphere of nitrogen or argon gas 1000 DEG C～1400 DEG C and under the atmosphere of nitrogen or argon gas be incubated 2h, finally cool to the furnace under the atmosphere of nitrogen or argon gas Room temperature, obtains the porous complex phase ceramic after surface modification；The mass concentration of described Ludox and Alumina gel is 10%；
4th, the porous complex phase ceramic after the surface modification preparing step 3 is inserted in graphite crucible, and metal alloy is placed on table The top of the modified porous complex phase ceramic in face, is then placed in sintering furnace, and in air pressure be 10Pa and heating rate is 5 DEG C/min It is warming up to 700 DEG C～900 DEG C under the conditions of～10 DEG C/min, and protect under the conditions of air pressure is 700 DEG C～900 DEG C for 10Pa and temperature Warm 1h, then passing to argon gas to air pressure is 2MPa～8MPa, and argon gas air pressure be 2MPa～8MPa and temperature be 700 DEG C～ It is incubated 2h～10h under conditions of 900 DEG C, finally under conditions of the air pressure of argon gas is for 2MPa～8MPa, cool to room temperature with the furnace, Obtain porous Si3N4/ SiC complex phase ceramic strengthens metal-base composites；The volume of described metallic matrix and step 3 preparation The volume of the porous complex phase ceramic pore after surface modification is equal.
2. a kind of porous Si according to claim 13N4/ SiC complex phase ceramic strengthens the preparation side of metal-base composites Method is it is characterised in that the organic solvent described in step one is isopropanol.
3. a kind of porous Si according to claim 13N4/ SiC complex phase ceramic strengthens the preparation side of metal-base composites Method is it is characterised in that the sintering aid described in step one is Y2O3And Al2O3Mixed powder, Y2O3And Al2O3Mass ratio be 3:2.
4. a kind of porous Si according to claim 13N4/ SiC complex phase ceramic strengthens the preparation side of metal-base composites Method is it is characterised in that the dispersant described in step one is TMAH.
5. a kind of porous Si according to claim 13N4/ SiC complex phase ceramic strengthens the preparation side of metal-base composites Method is it is characterised in that the monomer described in step one is acrylamide.
6. a kind of porous Si according to claim 13N4/ SiC complex phase ceramic strengthens the preparation side of metal-base composites Method it is characterised in that the crosslinking agent described in step one be N, N- methylene-bisacrylamide.
7. a kind of porous Si according to claim 13N4/ SiC complex phase ceramic strengthens the preparation side of metal-base composites Method is it is characterised in that the initiator described in step 2 is ammonium persulfate.
8. a kind of porous Si according to claim 13N4/ SiC complex phase ceramic strengthens the preparation side of metal-base composites Method is it is characterised in that the catalyst described in step 2 is tetramethylethylenediamine.
9. a kind of porous Si according to claim 13N4/ SiC complex phase ceramic strengthens the preparation side of metal-base composites Method is it is characterised in that the metal alloy described in step 4 is aluminium alloy or copper alloy.
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