CN114231812A - AlN-W-Cu composite material and preparation method thereof - Google Patents
AlN-W-Cu composite material and preparation method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- 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
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
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- 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
- B22F3/24—After-treatment of workpieces or articles
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0068—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only nitrides
Abstract
The invention provides an AlN-W-Cu composite material and a method for preparing the AlN-W-Cu composite material. The content of AlN is 1 to 20 weight percent based on 100 weight percent of the total weight of the composite material; the content of W is 50 wt% -85 wt%; and the Cu content is 10 wt% to 35 wt%. The AlN-W-Cu composite has a structure in which Cu is filled in a porous W-AlN skeleton. The AlN-W-Cu composite material overcomes the defect that the processing and application of the traditional W-Cu composite material are influenced by high density, so that the composite material has wider density range, the processability of the material is improved, the requirements of miniaturization and light weight of electronic elements are met, the application range of the W-Cu composite material is widened, and the AlN-W-Cu composite material can be applied to the fields of electronic packaging, semiconductor cooling fins and the like.
Description
Technical Field
The invention belongs to the field of metal matrix composite preparation, and particularly relates to an AlN-W-Cu composite material and a preparation method thereof.
Background
The W-Cu composite material has a plurality of excellent characteristics of tungsten and copper, has the characteristics of high strength, high hardness, good thermal conductivity, low thermal expansion coefficient, arc erosion resistance, high temperature oxidation resistance, fusion welding resistance and the like, is widely applied to the fields of national defense industry, aerospace, electronic information, machining and the like, and is commonly used as an electrical contact material, a microelectronic packaging material, a heat sink material of an integrated circuit and a high temperature corrosion resistant material. With the requirements of light weight and miniaturization of electronic products, the W-Cu composite material has higher density, so that the processability of the W-Cu composite material is influenced, and the application of the W-Cu composite material is limited. In order to further increase the heat transfer rate and reduce the density of the W-Cu composite, it is necessary to further increase the overall thermal conductivity of the W-Cu composite and widen the density range thereof. The addition of a second phase of other highly thermally conductive, low density components is one of the limited ways to improve the performance of W-Cu composites, such as the addition of graphene, diamond, silver, SiC, etc.
CN103382534A discloses a density-controllable W-Cu-SiC ternary composite material, wherein SiC is added into the W-Cu composite material, and the density-controllable W-Cu-SiC ternary composite material is prepared by adjusting the proportion of SiC and W in the W-Cu-SiC composite material. Weichenlong and the like add Diamond to a W-Cu composite material, mix tungsten-plated Diamond with Cu-coated W composite powder, and prepare a Diamond/W-Cu composite material by microwave sintering (Wei chemical et al, "Effect of Diamond surface treatment on microstructure and thermal conductivity of Diamond/W-30Cu compositions prepared by microwave sintering", Diamond & Related Materials, 2019).
AlN, as a novel ceramic material, has the advantages of low density, high thermal conductivity, low thermal expansion coefficient, high material strength and hardness at high temperature, excellent thermal shock resistance and the like, and is widely applied to the fields of microwave power devices, high-temperature packaging and the like. Because of poor wettability between AlN and Cu, surface of AlN is chemically plated with Cu by Liudebao, and then the copper-plated AlN and Cu powder are mixed to prepare the AlN/Cu composite material (Liudebao, Cuixiang, ma, surface of aluminum nitride particle is plated with copper and reinforced copper-based composite material thereof "[ J ]. weapon material science and engineering, 2005 (02): 8-11).
In the prior art, reports of AlN and W-Cu composite materials are not found yet.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an AlN-W-Cu composite material and a preparation method thereof. The composite material has the characteristics of low thermal expansion coefficient, high thermal conductivity and low density.
To incorporate AlN into a W — Cu composite, surface treatment of AlN is required to improve interfacial bonding between AlN and Cu. Therefore, the surface of the AlN particle is coated with tungsten, then the W particle and the AlN particle are mixed according to a certain proportion, a W-AlN framework is obtained by pressing and pre-sintering, and finally the AlN-W-Cu composite material is prepared by infiltration of Cu. The composite material has the characteristics of low thermal expansion coefficient, high thermal conductivity and small density, meets the requirement of light weight of electronic products, and can be applied to the fields of electronic packaging, semiconductor radiating fins and the like.
Thus, according to a first aspect of the present invention, there is provided an AlN-W-Cu composite, wherein the content of AlN is 1 wt% to 20 wt%, preferably 1 wt% to 10 wt%, based on 100 wt% of the total weight of the composite; the content of W is 50 to 85 wt%, preferably 60 to 85 wt%; and the Cu content is 10 to 35 wt%, preferably 15 to 30 wt%.
Preferably, the AlN-W-Cu composite has a structure in which Cu is filled in a porous W-AlN skeleton.
Preferably, the AlN-W-Cu composite material is heated at 5 ℃/min at the temperature of between room temperature and 400 ℃ measured by a thermal mechanical analyzer, and has a thermal expansion coefficient of 6 x 10-6～10.5×10-6K, more preferably 6.5X 10-6～10×10-6K; the thermal conductivity at room temperature measured by a laser thermal conductivity meter is 180-250W/(mK), more preferably 190-250W/(mK); the density measured by an Archimedes drainage method is 8.30-15.40g/cm3More preferably 10.00 to 15.40g/cm3。
According to a second aspect of the present invention, there is provided a method of preparing an AlN-W-Cu composite material according to the present invention, including the steps of:
(1) performing hydrolysis resistance treatment on the AlN particles to obtain hydrolysis-resistant AlN particles; (ii) a
(2) Preparation of WO3·H2O sol: reacting the W particles with a hydrogen peroxide solution, filtering to remove precipitates after the reaction is finished, optionally adding a stabilizer, and uniformly stirring to obtain WO3·H2O sol;
(3) preparing tungsten-coated AlN particles: adding the hydrolysis-resistant AlN particles obtained in the step (1) into the WO obtained in the step (2)3·H2O sol, so that AlN particles are uniformly dispersed in the sol; then drying to obtain composite particles, and putting the dried composite particles in a container H2Reducing in the atmosphere, and then cooling along with the furnace to obtain tungsten-coated AlN particles;
(4) preparing a porous W-AlN framework: uniformly mixing the W particles, the tungsten-coated AlN particles obtained in the step (3) and a forming agent, pressing and forming in a steel die to obtain a W-AlN green body, and then adding N2-H2Sintering in mixed atmosphere to obtain a porous W-AlN framework;
(5) preparing an AlN-W-Cu composite material: pressing a Cu block or Cu particles into a compact, then placing the compact on the porous W-AlN framework obtained in the step (4), and adding N2-H2And (3) carrying out infiltration of Cu in a mixed atmosphere, then cooling along with the furnace, and polishing to remove the Cu layer to obtain the AlN-W-Cu composite material.
In step (1), the step of subjecting the AlN particles to hydrolysis-resistant treatment is not particularly limited as long as hydrolysis-resistant AlN particles can be obtained. For example, the AlN particles may be subjected to hydrolysis-resistant treatment by methods known in the art, such as adding the AlN particles to a solution of phosphoric acid and aluminum dihydrogen phosphate in anhydrous ethanol, stirring, ultrasonically dispersing, washing, and drying in an oven to obtain hydrolysis-resistant AlN particles. Preferably, the concentration of the phosphoric acid is 5-15 g/L, and the concentration of the aluminum dihydrogen phosphate is 10-30 g/L.
Furthermore, the AlN particles in the step (1) have a purity of 99.9% and a particle size of 0.1 to 10 μm.
Further, the molar ratio of W particles to hydrogen peroxide in step (2) is between 1: 1 and 1: 5, preferably between 1: 1 and 1: 3.
Further, the stabilizing agents in the step (2) are anhydrous ethanol and glacial acetic acid, and the dosage of the stabilizing agents is that 5-15 ml of anhydrous ethanol and 0.5-6 ml of glacial acetic acid are added into each 1g of tungsten particles.
Further, in the step (3), WO3·H2The amount of the O sol to be used is not particularly limited as long as the added AlN particles are completely immersed.
Furthermore, the purity of the W particles is 99.9%, and the particle size is 0.5-10 μm.
Further, in the step (3), the composite particles are reduced at a temperature of 700-900 ℃.
Further, in the porous W-AlN framework described in the step (4), the mass of the W particles is 80 to 99 wt% based on 100 wt% of the total weight of the W particles, the tungsten-coated AlN particles and the mass of the tungsten-coated AlN particles, and the mass of the W particles is 1 to 20 wt%.
Further, the forming agent in the step (4) is a forming agent commonly used in the art, such as stearic acid, PEG, paraffin, PVA, and is 0.2 wt% to 0.8 wt% based on 100 wt% of the total weight of the W particles and the tungsten-coated AlN particles.
Further, the pressing pressure in the step (4) is 200-800 MPa.
Further, the sintering temperature of the W-AlN framework in the step (4) is 1000-1600 ℃, and the sintering time is 60-180 min.
Furthermore, the volume percentage of the pores in the W-AlN framework in the step (4) in the W-AlN framework is 20-50%.
The W-AlN green body with the porosity of more than 30% can be obtained preliminarily by controlling the pressing pressure within the range of 200-800 MPa.
For the W-AlN framework, the sintering densification process mainly consists of the combination between the W particles and the combination of the W-AlN particles. And obtaining tungsten-coated AlN particles by a sol-gel method to realize the combination of the W-AlN particles. Therefore, it can be considered that the W particles are bonded to each other during the preparation of the porous W-AlN skeleton. The decomposition and removal of the former during the initial stages of sintering of the skeleton increases the porosity of the green body. As the sintering temperature increases, sintering necks form between particles. Along with the formation and growth of the sintering neck, atoms migrate at the early stage to reduce the spacing between particles to form a continuous pore network, grains grow at the later stage, the pore network collapses, and pores further shrink along with the migration of crystal boundaries. Finally, the pore conduit is divided into a series of small pores to form closed pores, which are further reduced to reduce the pore size and percentage. Therefore, for the W-AlN framework, the sintering temperature is changed to be in different sintering densification processes, so that the porous W-AlN framework with controllable porosity is obtained.
Further, the Cu block or Cu particle compact in step (5) should meet the requirement of excessive infiltration of copper during infiltration, and the amount of copper should be larger than the amount of copper filling all pores.
Further, the temperature range of the infiltration of Cu in the step (5) is 1200-1500 ℃, and the time of the infiltration of Cu is 60-180 min.
Compared with the prior art, the invention has the following advantages:
1. according to the method, the surface of AlN is coated with W by a sol-gel method, so that the interface combination among the phases of the composite material is improved, the AlN-W-Cu composite material with high density is obtained, and the comprehensive performance of the composite material is improved.
2. The AlN-W-Cu composite material overcomes the defect that the processing and application of the traditional W-Cu composite material are influenced by high density, so that the composite material has wider density range, the processability of the material is improved, the requirements of miniaturization and light weight of electronic elements are met, the application range of the W-Cu composite material is widened, and the AlN-W-Cu composite material can be applied to the fields of electronic packaging, semiconductor cooling fins and the like.
3. The method has simple process, can prepare the AlN-W-Cu composite materials with different shapes and sizes, and is suitable for large-scale production.
Drawings
FIG. 1 is a scanning electron micrograph of tungsten-coated AlN particles prepared according to example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a fracture of a porous W-AlN framework prepared according to example 1 of the present invention;
FIG. 3 is a schematic view of a process for infiltration of Cu into a porous W-AlN skeleton according to example 1 of the present invention;
FIG. 4 is a scanning electron micrograph of an AlN-W-Cu composite material prepared according to example 1 of the present invention;
FIG. 5 is a scanned elemental plane of an AlN-W-Cu composite material prepared according to example 2 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1
Preparation of AlN-W-Cu composite
And (3) performing hydrolysis resistance treatment on the AlN particles: adding 8g of AlN particles with the particle size of 5 mu m into a solution formed by 0.5g of phosphoric acid and 1g of aluminum dihydrogen phosphate in 50ml of absolute ethyl alcohol, stirring, ultrasonically dispersing for 20min, washing with the absolute ethyl alcohol, and drying in an oven at 50 ℃ to obtain the hydrolysis-resistant AlN particles;
weighing 10g of tungsten particles and 20g of hydrogen peroxide solution with the mass concentration of 30%, reacting for 5h in a cold water bath, filtering to remove precipitates, adding 100ml of absolute ethyl alcohol and 50ml of glacial acetic acid, and uniformly stirring to obtain light yellow WO3·H2And (4) O sol.
Adding the hydrolysis-resistant AlN particles prepared as described above to the WO prepared as described above3·H2And (4) ultrasonically dispersing for 30min in the O sol to ensure that AlN particles are uniformly dispersed in the sol. The sol in which the AlN particles were dispersed was dried in an oven at 150 ℃ for 12 hours. Drying the composite particles in H2Reducing for 2h at 800 ℃ in the atmosphere, and cooling along with the furnace to obtain the tungsten-coated AlN particles.
88g W g of particles (particle size 5 μm), 12g of the tungsten-coated AlN particles prepared above and 0.5g of the above-mentioned powder were weighed outMixing the shaping agent stearic acid uniformly, taking 15g of the mixture, pressing and shaping under the pressing pressure of 450MPa to obtain a W-AlN green compact with the diameter of 20mm, and then adding N2-H2And (3) preserving the temperature for 30min in the mixed atmosphere at 600 ℃, burning out the forming agent, and then heating to 1350 ℃ and sintering for 90min to obtain the porous W-AlN framework.
Placing 5g of Cu particle compact on the porous W-AlN framework obtained in the step (3) in the presence of N2-H2And infiltrating copper for 2 hours at 1300 ℃ in the mixed atmosphere, then cooling along with the furnace, and removing the Cu layer through polishing to obtain the AlN-W-Cu composite material.
Fig. 1 is a scanning electron microscope image of the tungsten-coated AlN particles prepared according to example 1, and it can be seen from fig. 1 that the W particles are coated on the surface of the AlN particles, resulting in tungsten-coated AlN particles, improving the interface bonding between the AlN particles and Cu, and increasing the compactness of the composite material. FIG. 2 is a scanning electron micrograph of a fracture of the porous W-AlN skeleton prepared according to example 1. As can be seen from fig. 2, the porous W — AlN skeleton is a porous structure, and is composed of a W phase, an AlN phase, and air holes, and AlN particles are uniformly distributed in the W matrix. FIG. 4 is a scanning electron microscope image of the AlN-W-Cu composite material prepared according to example 1, and it can be seen from FIG. 4 that the obtained AlN-W-Cu composite material has good interface bonding, no obvious holes in the sample, and uniform structure.
Example 2
Preparation of AlN-W-Cu composite
And (3) performing hydrolysis resistance treatment on the AlN particles: adding 10g of AlN particles with the particle size of 5 mu m into a solution formed by 1.2g of phosphoric acid and 2.5g of aluminum dihydrogen phosphate in 100ml of absolute ethyl alcohol, stirring, ultrasonically dispersing for 25min, washing with the absolute ethyl alcohol, and drying in an oven at 60 ℃ to obtain the hydrolysis-resistant AlN particles;
weighing 12.5g of tungsten particles and 25g of 30% hydrogen peroxide solution, reacting for 5h in a cold water bath, filtering to remove precipitate, adding 150ml of anhydrous ethanol and 15ml of glacial acetic acid, and stirring uniformly to obtain light yellow WO3·H2And (4) O sol.
Adding the AlN particles obtained in the step (1) into the sol, and performing ultrasonic dispersion for 30min to uniformly disperse the AlN particles in the sol. Will be dispersed with AlNThe sol of particles was dried in an oven at 150 ℃ for 12 h. Drying the composite particles in H2Reducing for 2h at 850 ℃ in the atmosphere, and cooling along with the furnace to obtain the tungsten-coated AlN particles.
Weighing 92g W particles (with the particle size of 5 μm), 8g of tungsten-coated AlN particles and 0.5g of stearic acid as a forming agent, uniformly mixing, pressing and forming 15g of the mixture under the pressing pressure of 550MPa to obtain a W-AlN green compact, and then carrying out N-layer sintering on the W-AlN green compact2-H2And (3) preserving the temperature for 30min at 600 ℃ in the mixed atmosphere to burn out the forming agent, and then heating to 1400 ℃ to sinter for 120min to obtain the porous W-AlN framework.
Placing 5g of Cu particle compact on the porous W-AlN framework obtained in the step (3) in the presence of N2-H2And carrying out infiltration copper for 1.5h at 1300 ℃ in a mixed atmosphere, and then cooling along with the furnace to obtain the AlN-W-Cu composite material.
FIG. 5 is a scanned elemental plane of the AlN-W-Cu composite material prepared according to example 2, from which it can be seen that AlN grains are uniformly distributed, the sample has no significant pores, and the interface bonding between AlN and W is good.
Example 3
And (3) performing hydrolysis resistance treatment on the AlN particles: adding 4g of AlN particles with the particle size of 5 mu m into a solution formed by 0.5g of phosphoric acid and 1g of aluminum dihydrogen phosphate in 50ml of absolute ethyl alcohol, stirring, ultrasonically dispersing for 20min, washing with the absolute ethyl alcohol, and drying in an oven at 50 ℃ to obtain the hydrolysis-resistant AlN particles;
weighing 5g of tungsten particles and 10g of hydrogen peroxide solution with the mass concentration of 30%, reacting for 5h in a cold water bath, filtering to remove precipitates, adding 100ml of absolute ethyl alcohol and 50ml of glacial acetic acid, and uniformly stirring to obtain light yellow WO3·H2And (4) O sol.
Adding the anti-hydrolysis AlN particles prepared in the step (1) into the WO3 & H2O sol prepared in the step (1), and performing ultrasonic dispersion for 30min to ensure that the AlN particles are uniformly dispersed in the sol. The sol in which the AlN particles were dispersed was dried in an oven at 150 ℃ for 12 hours. And reducing the dried composite particles in an H2 atmosphere at 800 ℃ for 2H, and cooling along with the furnace to obtain the tungsten-coated AlN particles.
96g W granules (particle size 5 μm) and 4g of the above-preparedCoating tungsten AlN particles and 0.5g of forming agent paraffin, uniformly mixing the tungsten-coated AlN particles and the forming agent paraffin, taking 15g of the mixture, pressing and forming the mixture under the pressing pressure of 350MPa to obtain a W-AlN green body with the diameter of 20mm, and then adding N to the W-AlN green body2-H2In the mixed atmosphere, firstly, burning out at 600 ℃ for 30min, keeping the temperature, burning out the forming agent, and then heating to 1300 ℃ and sintering for 90min to obtain the porous W-AlN framework.
Placing 5g of Cu particle compact on the porous W-AlN framework obtained in the step (3) in the presence of N2-H2And infiltrating copper for 2h at 1350 ℃ in a mixed atmosphere, then cooling along with the furnace, and removing the Cu layer through polishing to obtain the AlN-W-Cu composite material.
Example 4
And (3) performing hydrolysis resistance treatment on the AlN particles: adding 10g of AlN particles with the particle size of 5 mu m into a solution formed by 1.2g of phosphoric acid and 2.5g of aluminum dihydrogen phosphate in 100ml of absolute ethyl alcohol, stirring, ultrasonically dispersing for 20min, washing with the absolute ethyl alcohol, and drying in an oven at 50 ℃ to obtain the hydrolysis-resistant AlN particles;
weighing 12.5g of tungsten particles and 25g of 30% hydrogen peroxide solution, reacting for 5h in a cold water bath, filtering to remove precipitates, adding 100ml of anhydrous ethanol and 50ml of glacial acetic acid, and uniformly stirring to obtain light yellow WO3·H2And (4) O sol.
Adding the anti-hydrolysis AlN particles prepared in the step (1) into the WO3 & H2O sol prepared in the step (1), and performing ultrasonic dispersion for 30min to ensure that the AlN particles are uniformly dispersed in the sol. The sol in which the AlN particles were dispersed was dried in an oven at 150 ℃ for 12 hours. Drying the composite particles in H2Reducing for 2h at 800 ℃ in the atmosphere, and cooling along with the furnace to obtain the tungsten-coated AlN particles.
Weighing 84g W particles (with particle size of 5 μm), 16g of the tungsten-coated AlN particles and 0.5g of forming agent paraffin, mixing uniformly, taking 15g of the mixture, pressing and forming under the pressing pressure of 450MPa to obtain a W-AlN green compact with the diameter of 20mm, and then pressing and forming under the pressure of N2-H2And (3) preserving the temperature for 30min at 600 ℃ in the mixed atmosphere to burn out the forming agent, and then heating to 1400 ℃ to sinter for 120min to obtain the porous W-AlN framework.
Placing 5g of Cu particle compact on the porous W-AlN framework obtained in the step (3) in the presence of N2-H2And infiltrating copper for 2h at 1350 ℃ in a mixed atmosphere, then cooling along with the furnace, and removing the Cu layer through polishing to obtain the AlN-W-Cu composite material.
Example 5
And (3) performing hydrolysis resistance treatment on the AlN particles: adding 4g of AlN particles with the particle size of 5 mu m into a solution formed by 0.5g of phosphoric acid and 1g of aluminum dihydrogen phosphate in 50ml of absolute ethyl alcohol, stirring, ultrasonically dispersing for 20min, washing with the absolute ethyl alcohol, and drying in an oven at 50 ℃ to obtain the hydrolysis-resistant AlN particles;
weighing 5g of tungsten particles and 10g of hydrogen peroxide solution with the mass concentration of 30%, reacting for 5h in a cold water bath, filtering to remove precipitates, adding 100ml of absolute ethyl alcohol and 50ml of glacial acetic acid, and uniformly stirring to obtain light yellow WO3·H2And (4) O sol.
Adding the hydrolysis-resistant AlN particles prepared as described above in step (1) to the WO prepared as described above3·H2And (4) ultrasonically dispersing for 30min in the O sol to ensure that AlN particles are uniformly dispersed in the sol. The sol in which the AlN particles were dispersed was dried in an oven at 150 ℃ for 12 hours. And reducing the dried composite particles in an H2 atmosphere at 800 ℃ for 2H, and cooling along with the furnace to obtain the tungsten-coated AlN particles.
Weighing 96g W particles (with particle size of 5 μm), 4g of the tungsten-coated AlN particles and 0.5g of forming agent paraffin, mixing uniformly, pressing 15g of the mixture under 650MPa to obtain W-AlN green compact with diameter of 20mm, and then pressing in N2-H2And (3) preserving the temperature for 30min at 600 ℃ in the mixed atmosphere to burn out the forming agent, and then heating to 1400 ℃ to sinter for 120min to obtain the porous W-AlN framework.
Placing 5g of Cu particle compact on the porous W-AlN framework obtained in the step (3) in the presence of N2-H2And infiltrating copper for 2h at 1350 ℃ in a mixed atmosphere, then cooling along with the furnace, and removing the Cu layer through polishing to obtain the AlN-W-Cu composite material.
The contents of the respective components of the AlN-W-Cu composite material were analyzed by an EDS spectrometer, the density of the AlN-W-Cu composite material was measured by an Archimedes drainage method, the thermal conductivity of the AlN-W-Cu composite material at room temperature was measured by a laser thermal conductivity meter, and the average thermal expansion coefficient from room temperature to 400 ℃ was measured by a thermomechanical analyzer. The specific component contents and physical property parameters of the AlN-W-Cu composite material are shown in the following table.
Table 1: specific component contents and physical Property parameters of AlN-W-Cu composites prepared according to examples 1 to 5
Comparative example 1
The prior art literature reports that the density of W-20Cu composites is about 15.25g/cm3The thermal conductivity is about 200.04W/(m.K) (Tao, J., Shi, X.Properties, phases and microstructure of microwave localized W-20Cu compositions from dispersed suspended solids treated powders. J. Wuhan Univ. technol. -Mat.Sci.Edit.27,38-44 (2012)).
Compared with the W-20Cu composite material in the comparative example 1, the AlN-W-Cu composite material prepared by the invention has the advantages of obviously reduced density and high thermal conductivity, and can meet the requirement of light weight of products.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. An AlN-W-Cu composite, wherein the AlN is contained in an amount of 1 to 20 wt%, preferably 1 to 10 wt%, based on 100 wt% of the total weight of the composite; the content of W is 50 to 85 wt%, preferably 60 to 85 wt%; and a Cu content of 10 to 35 wt%, preferably 15 to 30 wt%;
preferably, the AlN-W-Cu composite has a structure in which Cu is filled in a porous W-AlN skeleton.
2. The AlN-W-Cu composite according to claim 1, wherein,
the AlN-W-Cu composite material is measured by a thermal mechanical analyzer to be between room temperature and 400 DEG CThe temperature is raised at 5 ℃/min, and the thermal expansion coefficient is 6 multiplied by 10-6～10.5×10-6K, more preferably 6.5X 10-6～10×10-6/K；
Preferably, the thermal conductivity at room temperature measured by a laser thermal conductivity meter is 180-250W/(m.K), more preferably 190-250W/(m.K);
preferably, the density measured by an Archimedes drainage method is 8.30-15.40 g/cm3More preferably 10.00 to 15.40g/cm3。
3. A method for preparing an AlN-W-Cu composite material comprises the following steps:
(1) performing hydrolysis resistance treatment on the AlN particles to obtain hydrolysis-resistant AlN particles;
(2) preparation of WO3·H2O sol: reacting the W particles with a hydrogen peroxide solution, filtering to remove precipitates after the reaction is finished, optionally adding a stabilizer, and uniformly stirring to obtain WO3·H2O sol;
(3) preparing tungsten-coated AlN particles: adding the hydrolysis-resistant AlN particles obtained in the step (1) into the WO obtained in the step (2)3·H2O sol, so that AlN particles are uniformly dispersed in the sol; then drying to obtain composite particles, and putting the dried composite particles in a container H2Reducing in the atmosphere, and then cooling along with the furnace to obtain tungsten-coated AlN particles;
(4) preparing a porous W-AlN framework: uniformly mixing the W particles, the tungsten-coated AlN particles obtained in the step (3) and a forming agent, pressing and forming in a steel die to obtain a W-AlN green body, and then adding N2-H2Sintering in mixed atmosphere to obtain a porous W-AlN framework;
(5) preparing an AlN-W-Cu composite material: pressing a Cu block or Cu particles into a compact, then placing the compact on the porous W-AlN framework obtained in the step (4), and adding N2-H2And (3) carrying out infiltration of Cu in a mixed atmosphere, then cooling along with the furnace, and polishing to remove the Cu layer to obtain the AlN-W-Cu composite material.
4. The method of claim 3, wherein,
the AlN particles in the step (1) have the purity of 99.9 percent and the particle size of 0.1-10 mu m;
the molar ratio of the W particles to the hydrogen peroxide in the step (2) is between 1: 1 and 1: 5, preferably between 1: 1 and 1: 3;
preferably, the stabilizer in the step (2) is absolute ethyl alcohol and glacial acetic acid, and the dosage of the stabilizer is that 5-15 ml of absolute ethyl alcohol and 0.5-6 ml of glacial acetic acid are added into every 1g of tungsten particles;
preferably, in the step (3), the reduction of the composite particles is performed at a temperature of 700 to 900 ℃.
5. The method of claim 3 or 4,
in the porous W-AlN framework in the step (4), the mass of the tungsten-coated AlN particles is 1 to 20 wt% and the mass of the W particles is 80 to 99 wt% based on 100 wt% of the total weight of the W particles and the tungsten-coated AlN particles.
6. The method of any one of claims 3 to 5,
the forming agent in the step (4) is one or more selected from stearic acid, PEG, paraffin and PVA; the weight percentage of the forming agent is 0.2 wt% to 0.8 wt% based on 100 wt% of the total weight of the W particle and the tungsten-coated AlN particle.
7. The method of any one of claims 3 to 6,
and (4) the pressing pressure in the step (4) is 200-800 MPa.
8. The method of any one of claims 3 to 7,
the sintering temperature of the W-AlN framework in the step (4) is 1000-1600 ℃, and the sintering time is 60-180 min.
9. The method of any one of claims 3 to 8,
the volume percentage of the pores in the W-AlN framework in the step (4) in the W-AlN framework is 20-50%.
10. The method of any one of claims 3 to 9,
and (5) the temperature range of the infiltration of Cu is 1200-1500 ℃, and the time of the infiltration of Cu is 60-180 min.
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