CN114592138A - Nano alumina particle reinforced copper-based composite material and preparation method thereof - Google Patents
Nano alumina particle reinforced copper-based 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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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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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
- C22C32/001—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 only oxides
- C22C32/0015—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 only oxides with only single oxides as main non-metallic constituents
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Abstract
The invention provides a nano alumina particle reinforced copper-based composite material and a preparation method thereof, belonging to the technical field of metal-based composite materials. In the present invention, nano Al2O3The reinforcing phase is generated in situ, and solves the problem of Al2O3The problem of poor interface bonding of the reinforcing phase and the Cu matrix is solved, and the adverse effects of interface cavities and microcracks on mechanical properties and electrical conductivity are reduced; after in-situ internal oxidation reaction, reduction treatment is carried out, so that residual CuO is further removed, and the tissue defects such as cracks, holes, impurities and the like easily occurring in the material are avoided; simultaneously, as an oxygen source of the in-situ reaction, CuO is equivalently dispersed twice, polyacrylic acid is used for pre-dispersion for the first time, and ball milling dispersion is used for the second time, so that the copper oxide and the Cu-Al alloy powder are uniformly mixed, and the in-situ reaction is carried outAnd then the dispersion strengthening is carried out fully, so that the conductivity can not be obviously reduced while the mechanical property of the material is improved. The preparation method is simple in preparation process, suitable for industrial production and low in cost.
Description
Technical Field
The invention relates to the technical field of metal matrix composite materials, in particular to a nano alumina particle reinforced copper matrix composite material and a preparation method thereof.
Background
The research on alumina reinforced copper-based composite materials started earlier abroad and entered the industrial production stage in the 70 s of the 20 th century. For example, the KLF-1 and MF202 dispersion-strengthened copper products of the Japanese Panasonic electric apparatus, the C15715 and C15760 dispersion-strengthened copper products of the American SCM company, the Germany SIEMENS company, and the Korean LKENG company have been mass-produced. Wherein, the tensile strength of the C15760 type dispersion strengthened copper composite material is 540MPa, the softening temperature exceeds 900 ℃, meanwhile, the conductivity reaches 90 percent IACS, and the performance is in the international leading level. It is worth mentioning that this kind of products are listed as patent products abroad, and the technical process is in a confidential state.
The research on the alumina reinforced copper-based composite material in China is relatively late. In the 70 s of the 20 th century, a Luoyang copper processing factory established a production line for producing dispersion strengthened copper by an internal oxidation method, but the production line cannot be put into mass production formally due to the reasons of low product strength, substandard softening temperature resistance, high manufacturing cost and the like. Until the 80 s of the 20 th century, domestic colleges and scientific institutions were not beginning their research. However, domestic research is still in the laboratory research stage so far, and the industrial production level cannot be reached. The aluminum oxide dispersion strengthened copper material used in China at present still depends on import. In order to realize independent research, development and production, the aluminum oxide dispersion strengthened copper is still a material which needs to be attacked for a long time in China.
At present, the domestic preparation method of the dispersion strengthened copper mainly comprises an internal oxidation method, a coprecipitation method, a reaction spray deposition, a liquid phase reaction in-situ generation method, a mechanical alloying method, a powder metallurgy method, a self-propagating high-temperature synthesis method, a sol-gel method and the like. The traditional internal oxidation method can obtain dispersion strengthened copper with uniform distribution of strengthening phase and accurate and controllable content, but has the defects of difficult complete removal of oxidant, easy occurrence of structural defects such as cracks, holes, inclusions and the like in the material; the dispersion strengthened copper prepared by the coprecipitation method has coarse reinforced phase particles, and the particle size is generally 1-10 microns, so that the strengthening effect is not obvious; the self-propagating high-temperature synthesis method has the advantages of simple process, few impurities in finished products, fine tissue and the like, but high-density products are difficult to obtain, and the reaction is difficult to control. For example, the method disclosed in patent CN102031401A combines a sol-gel method and a self-propagating high-temperature synthesis method to prepare dispersion strengthened copper, and the preparation process is simple, but the strength and conductivity of the product are not satisfactory. The reaction jet deposition method can quickly prepare the composite material with fine grains and uniform tissue, but has expensive production equipment, poor process stability, difficulty in preparing large-scale workpieces and unsuitability for industrial application. The powder metallurgy method has simple preparation process, but the alumina reinforcing phase and the copper matrix are not wetted, so that the interface bonding is poor, and the performance of the product is not ideal. For example, patent CN108570630A prepares dispersion strengthened copper by powder metallurgy method, in order to improve the wettability of alumina and copper matrix, the surface modification of alumina reinforcing phase needs to be performed in advance, which increases the complexity of the process.
In conclusion, the above methods have advantages and disadvantages, but in general, it is difficult to meet various requirements such as simple and reliable process, excellent performance of the finished product, low manufacturing cost, and suitability for industrial production.
Disclosure of Invention
The invention aims to provide a nano alumina particle reinforced copper-based composite material and a preparation method thereof, which can meet various requirements of simple and reliable process, excellent finished product performance, low manufacturing cost, suitability for industrial production and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nano alumina particle reinforced copper-based composite material, which comprises the following steps:
mixing Al (NO)3)3Polyacrylic acid and micron CuO are dispersed in ethanol to obtain Al (NO)3)3-a suspension of CuO;
removing ethanol in the suspension, and decomposing the obtained solid to obtain CuO-Al2O3Powder;
the CuO-Al is added2O3Ball-milling and mixing the powder and Cu-Al alloy powder, and sequentially carrying out in-situ internal oxidation reaction and reduction treatment on the obtained mixed powder to obtain Cu-Al2O3Compounding powder;
the Cu-Al is added2O3Pressing the composite powder to obtain a prefabricated blank;
and carrying out vacuum hot-pressing sintering on the prefabricated blank to obtain the nano alumina particle reinforced copper-based composite material.
Preferably, the decomposition temperature is 300-320 ℃.
Preferably, the temperature of the in-situ internal oxidation reaction is 800-1000 ℃, and the heat preservation time is 4-8 h; the in-situ internal oxidation reaction is carried out under a protective atmosphere.
Preferably, the reduction treatment is performed in a hydrogen atmosphere; the temperature of the reduction treatment is 800-1000 ℃, and the time is 0.5-2 h.
Preferably, the temperature of the vacuum hot-pressing sintering is 900-1100 ℃, the time is 3-6 h, and the vacuum degree is 1 multiplied by 10- 3Pa～1×10-2Pa。
Preferably, the particle size of the micron CuO is 1-15 μm; the CuO-Al2O3The particle size of the powder is less than 48 mu m; the granularity of the Cu-Al alloy powder is less than 150 mu m.
Preferably, the mass ratio of the polyacrylic acid to the micron CuO is (5-15): 3.5.
Preferably, the pressing is isostatic pressing.
The invention provides a nano alumina particle reinforced copper-based composite material prepared by the preparation method in the scheme, which comprises a Cu matrix and nano Al dispersed in the Cu matrix2O3And (3) granules.
Preferably, the nano Al2O3The particle size of the particles is less than 30 nm; the nano aluminum oxide particle reinforced copper-based composite material contains nano Al2O3The mass content of the particles is 0.1-2%.
The invention provides a preparation method of a nano alumina particle reinforced copper-based composite material, which comprises the following steps: mixing Al (NO)3)3Polyacrylic acid and micron CuO are dispersed in ethanol to obtain Al (NO)3)3-a suspension of CuO; removing from said suspensionThe obtained solid is decomposed to obtain CuO-Al2O3Powder; the CuO-Al is added2O3Ball-milling and mixing the powder and Cu-Al alloy powder, and sequentially carrying out in-situ internal oxidation reaction and reduction treatment on the obtained mixed powder to obtain Cu-Al2O3Compounding powder; the Cu-Al is added2O3Pressing the composite powder to obtain a prefabricated blank; and carrying out vacuum hot-pressing sintering on the prefabricated blank to obtain the nano alumina particle reinforced copper-based composite material.
In the present invention, nano Al2O3The reinforcing phase is generated in situ, and solves the problem of Al2O3The problem of poor interface bonding of the reinforcing phase and the Cu matrix is solved, and the adverse effects of interface cavities and microcracks on mechanical properties and electrical conductivity are reduced; after in-situ internal oxidation reaction, reduction treatment is carried out, so that residual CuO is further removed, and the defects of cracks, holes, impurities and other structures in the material and the adverse effect on the conductivity are avoided; meanwhile, CuO is used as an oxygen source of the in-situ reaction, namely, the CuO is subjected to two-time dispersion, the polyacrylic acid is used for pre-dispersion for the first time, the ball milling dispersion is used for the second time, so that the copper oxide and the Cu-Al alloy powder are uniformly mixed, the in-situ reaction is fully dispersed and strengthened, and the conductivity cannot be obviously reduced while the mechanical property of the material is improved.
The preparation method has the advantages of simple preparation process, convenient control of process parameters, no limitation to laboratory scale, suitability for large-scale industrial production and low cost.
Detailed Description
The invention provides a preparation method of a nano alumina particle reinforced copper-based composite material, which comprises the following steps:
mixing Al (NO)3)3Polyacrylic acid and micron CuO are dispersed in ethanol to obtain Al (NO)3)3-a suspension of CuO;
removing ethanol in the suspension, and decomposing the obtained solid to obtain CuO-Al2O3Powder;
the CuO-Al is added2O3Ball milling and mixing the powder and Cu-Al alloy powderSequentially carrying out in-situ internal oxidation reaction and reduction treatment on the obtained mixed powder to obtain Cu-Al2O3Compounding powder;
the Cu-Al is added2O3Pressing the composite powder to obtain a prefabricated blank;
and carrying out vacuum hot-pressing sintering on the prefabricated blank to obtain the nano alumina particle reinforced copper-based composite material.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The invention mixes Al (NO)3)3Polyacrylic acid and micron CuO are dispersed in ethanol to obtain Al (NO)3)3-a suspension of CuO.
In the present invention, the particle size of the micro CuO is preferably 1 to 15 μm, more preferably 3 to 12 μm, and even more preferably 5 to 10 μm. The micron CuO is selected, so that the subsequent in-situ internal oxidation reaction can be fully carried out, and the uniform dispersion of powder can be ensured.
The invention selects Al (NO)3)3As an aluminum source, the aluminum salt has a lower decomposition temperature, and the process conditions are easier to control than other aluminum salts. In addition, the decomposition temperature of polyacrylic acid (PAA for short) is close to that of aluminum nitrate, and the PAA is selected as a dispersing agent, so that the preparation process is simpler.
In the invention, the mass ratio of the polyacrylic acid to the micro CuO is preferably 15: 3.5; the invention has no special requirement on the dosage of the ethanol, and can disperse all the substances uniformly. In the present invention, the Al (NO) is3)3The dosage of the nano Al in the Cu-Al alloy powder and the final nano alumina particle reinforced copper-based composite material2O3The content of the particles is determined. Al (NO)3)3Al element in the Cu-Al alloy powder and Al element in the Cu-Al alloy powder can be finally converted into Al in the nano alumina particle reinforced copper-based composite material2O3。
In the present invention, the reaction of Al (NO)3)3The dispersion of polyacrylic acid and micro CuO into ethanol preferably comprises: mixing Al (NO)3)3Dissolving in ethanol, and adding polyacrylic acidMicron CuO is added while stirring.
Al (NO) is obtained3)3After the suspension of the CuO, the invention removes the ethanol in the suspension and decomposes the obtained solid to obtain the CuO-Al2O3And (3) powder.
In the present invention, the method for removing ethanol from the suspension preferably comprises: and stirring and heating the suspension to 70-90 ℃ to completely volatilize the ethanol.
In the invention, the decomposition temperature is preferably 300-320 ℃, and more preferably 305-315 ℃; the time for decomposition is preferably 0.5-1 h. The present invention has no particular requirement for the rate of temperature rise to the decomposition temperature. In the embodiment of the present invention, the temperature increase rate is 2 ℃/min. In the decomposition process, the PAA is decomposed, and simultaneously, the aluminum nitrate is decomposed to form Al2O3。
After the decomposition is completed, the obtained decomposition product is preferably ground and sieved to obtain CuO-Al with uniform granularity2O3And (3) powder. In the present invention, the CuO-Al2O3The particle size of the powder is preferably less than 48 μm.
Obtaining CuO-Al2O3After being powdered, the CuO-Al is mixed by the invention2O3Ball-milling and mixing the powder and Cu-Al alloy powder, and sequentially carrying out in-situ internal oxidation reaction and reduction treatment on the obtained mixed powder to obtain Cu-Al2O3And (3) compounding powder.
In the present invention, the particle size of the Cu-Al alloy powder is preferably less than 150. mu.m. In the invention, the Cu-Al alloy powder preferably consists of Cu and Al, and the mass content of Al in the Cu-Al alloy powder is 0.1-0.5%. In the embodiment of the present invention, the Cu — Al alloy powder is preferably Cu-0.3 wt.% Al alloy powder.
The invention is also directed to the CuO-Al2O3The mass ratio of the powder to the Cu-Al alloy powder is not particularly required, as long as the content of alumina in the final composite material is 0.1-2 wt.%. In the present invention, if Cu-Al alloy powder is directly oxidized to prepare Cu-Al2O3Composite powders, i.e. producedAl2O3The content is controlled by oxygen partial pressure, but at present, the Al with uniform and required components is difficult to obtain by accurately controlling the oxygen partial pressure in China2O3Content of Cu-Al2O3And (3) compounding the powder. The method utilizes CuO as an oxygen source, and the CuO and Cu-Al powder are subjected to in-situ reaction after dispersion, so that the process is better controlled, and ideal powder is easily obtained.
In the invention, the ball-material ratio of the ball-milling mixing is preferably 1:1, and the rotating speed is preferably 250-350 r/min; the time for ball milling and mixing is preferably 0.5-1 h. In the invention, the grinding balls used for ball-milling mixing are preferably alumina balls; the diameter of the alumina balls is preferably 4 mm. In the present invention, the ball-milling mixing is preferably carried out in a planetary ball mill.
In the invention, the temperature of the in-situ internal oxidation reaction is preferably 800-1000 ℃, more preferably 850-950 ℃, and the heat preservation time is preferably 4-8 h, more preferably 5-7 h; the in-situ internal oxidation reaction is preferably carried out under a protective atmosphere. In the present invention, the protective atmosphere is preferably an argon atmosphere or a nitrogen atmosphere. In the in-situ internal oxidation reaction process, CuO is used as an oxygen source of the in-situ reaction and is decomposed into Cu, and Al is oxidized into Al2O3The specific reaction equation is as follows:
CuO(s)＝Cu2O(s)+1/2O2(g)
Cu2O(s)＝2Cu(s)+1/2O2(g)
4Al(s)+3O2(g)＝2Al2O3(s)。
in the present invention, nano Al2O3The reinforcing phase is generated in situ, and solves the problem of Al2O3The poor combination of the interface of the reinforcing phase and the Cu matrix reduces the adverse effects of interface cavities and microcracks on mechanical properties and electrical conductivity.
After the in-situ internal oxidation reaction is finished, the invention directly reduces the obtained reaction product to obtain Cu-Al2O3And (3) compounding the powder.
In the invention, the temperature of the reduction treatment is preferably 800-1000 ℃, and is more preferably the same as the temperature of the in-situ internal oxidation reaction; the heat preservation time is preferably 0.5-2 h. In the present invention, the reduction treatment is preferably performed under a hydrogen atmosphere. The method further removes the residual CuO by reduction treatment, thereby avoiding the occurrence of structural defects such as cracks, holes, inclusions and the like in the material and adverse effects on the electrical conductivity.
Obtaining Cu-Al2O3After the powder is compounded, the Cu-Al is mixed in the invention2O3And pressing the composite powder to obtain a prefabricated blank.
In the present invention, the pressing is preferably isostatic pressing. In the invention, the pressure of the isostatic pressing is preferably 300-500 MPa, and the dwell time is preferably 0.5-2 h.
After obtaining the pressed blank, the invention carries out vacuum hot-pressing sintering on the pressed blank to obtain the nano alumina particle reinforced copper-based composite material.
In the invention, the temperature of the vacuum hot-pressing sintering is preferably 900-1100 ℃, and more preferably 950-1050 ℃; the time is preferably 3-6 h, and more preferably 4-5 h; the degree of vacuum is preferably 1X 10-3Pa～1×10-2Pa. The invention further reduces the sintering temperature by utilizing vacuum hot-pressing sintering and efficiently discharges gas in micropores, promotes the densification of the material, and in addition, the reduction of the sintering temperature can effectively prevent the growth of crystal grains in the sintering process, thereby being very beneficial to stabilizing the final quality of the product.
After the vacuum hot-pressing sintering is completed, a person skilled in the art can also perform the processing processes of extrusion, forging, rolling, drawing and the like according to actual needs to process the nano alumina particle reinforced copper-based composite material into bars, plates, wires and the like.
The invention provides a nano alumina particle reinforced copper-based composite material prepared by the preparation method in the scheme, which comprises a Cu matrix and nano Al dispersed in the Cu matrix2O3And (3) particles. In the invention, the nano Al2O3The particle size of the particles is preferably less than 30 nm; the nano aluminum oxide particle reinforced copper-based composite material contains nano Al2O3The mass content of the granules is excellentPreferably 0.1 to 2%, more preferably 0.5 to 1.5%.
The nano alumina particle reinforced copper-based composite material provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) 735g of aluminum nitrate is completely dissolved in ethanol, 13.5Kg of PAA (polyacrylic acid) is added as a dispersing agent, and 6Kg of copper oxide particles with the average particle size of 10 mu m are slowly added while electromagnetic stirring, so as to prepare aluminum nitrate-copper oxide suspension; then stirring the suspension, heating to 70 deg.C to volatilize ethanol, heating the rest solid powder to 320 deg.C at 2 deg.C/min, keeping the temperature for 1h to decompose aluminum nitrate into aluminum oxide, grinding the decomposition product powder, and sieving with 300 mesh sieve to obtain CuO-Al with particle size less than 48 μm2O3And (3) powder.
(2) 6.5Kg of CuO-Al obtained2O3Mixing the powder with 50kg of Cu-0.3 wt.% Al alloy powder with the particle size of less than 150 mu m by using a planetary ball mill for 3h, and then placing the mixture in a vacuum furnace for in-situ internal oxidation reaction at 800 ℃, wherein the reaction time is 6 h; keeping the temperature unchanged after the reaction is finished, and introducing hydrogen to reduce for 30min to remove residual CuO to finally obtain 56kg of Cu-Al2O3And (3) compounding the powder.
(3) Adding Cu-Al2O3And (3) keeping the pressure of the composite powder at 500MPa for 1h, and pressing into a prefabricated blank by isostatic pressing.
(4) Carrying out vacuum hot-pressing sintering on the prefabricated blank, wherein the sintering temperature is 1000 ℃, the sintering time is 3h, and the vacuum degree is 1 multiplied by 10-2Pa, finally obtaining Cu-0.75 wt.% Al2O3The dispersion-strengthened copper-based composite material.
(5) The obtained composite material is extruded into a rod at 550 ℃, and then a corresponding product is prepared according to the requirement.
Example 2
(1) 3.5Kg of aluminum nitrate is completely dissolved in ethanol, 9.5Kg of PAA (polyacrylic acid) is added as a dispersing agent, 4Kg of copper oxide particles with the average particle size of 10 mu m are slowly added while electromagnetic stirring is carried out, and the aluminum nitrate-copper oxide is preparedThe suspension of (a); then stirring the suspension, heating to 80 deg.C to volatilize ethanol, heating the rest solid powder to 300 deg.C at 2 deg.C/min, keeping the temperature for 1h to decompose aluminum nitrate into aluminum oxide, grinding the obtained decomposition product, and sieving with 300 mesh sieve to obtain CuO-Al with particle size less than 48 μm2O3And (3) powder.
(2) 5.8kg of the obtained CuO-Al2O3Mixing the powder with 35kg of Cu-0.3 wt.% Al alloy powder with the particle size of less than 150 mu m by using a planetary ball mill for 5 hours, and then placing the mixture in a vacuum furnace for in-situ internal oxidation reaction at 900 ℃ for 7 hours; after the reaction is finished, the temperature is kept unchanged, and then hydrogen is introduced for reduction treatment for 1h to remove residual CuO, so that 40.5kg of Cu-Al is finally obtained2O3And (3) compounding powder.
(3) And (3) keeping the pressure of the composite powder at 500Mpa for 1h, and performing isostatic pressing to obtain a prefabricated blank.
(4) Carrying out vacuum hot-pressing sintering on the prefabricated blank, wherein the sintering temperature is 1100 ℃, the sintering time is 3h, and the vacuum degree is 1 multiplied by 10-3Pa, finally obtaining Cu-2.0 wt.% Al2O3The dispersion-strengthened copper-based composite material.
(5) The obtained composite material is extruded into a rod at 550 ℃, and then a corresponding product is prepared according to the requirement.
Example 3
(1) 735g of aluminum nitrate is completely dissolved in ethanol, 13.5Kg of PAA (polyacrylic acid) is added as a dispersing agent, and 6Kg of copper oxide particles with the average particle size of 10 mu m are slowly added while electromagnetic stirring, so as to prepare aluminum nitrate-copper oxide suspension; then stirring and heating the suspension to 90 ℃ to volatilize ethanol, continuously heating the residual solid powder to 320 ℃ at the speed of 2 ℃/min, preserving heat for 1h to decompose aluminum nitrate into aluminum oxide, grinding the obtained decomposition product, and sieving the ground decomposition product with a 300-mesh sieve to obtain CuO-Al with the particle size of less than 48 mu m2O3And (3) powder.
(2) 6.5Kg of CuO-Al obtained2O3Mixing the powder with 50kg of Cu-0.3 wt.% Al alloy powder with the particle size of less than 150 mu m by using a planetary ball mill for 3 hours, and then placing the mixture in a vacuum furnace for in-situ internal oxidation reaction at 1000 ℃ for 4 hours; cooling after the reaction is finishedReducing the temperature to 800 ℃ by introducing hydrogen for 2 hours to remove residual CuO, and finally obtaining 56kg of Cu-Al2O3And (3) compounding powder.
(3) And (3) carrying out isostatic pressing on the composite powder under the pressure of 500Mpa for 1h to obtain a preformed blank.
(4) Carrying out vacuum hot-pressing sintering on the prefabricated blank, wherein the sintering temperature is 900 ℃, the sintering time is 6h, and the vacuum degree is 1 multiplied by 10-2Pa, finally obtaining Cu-0.75 wt.% Al2O3The dispersion-strengthened copper-based composite material.
(5) The obtained composite material is extruded into a rod at 550 ℃, and then a corresponding product is prepared according to the requirement.
Example 4
(1) 735g of aluminum nitrate is completely dissolved in ethanol, 13.5Kg of PAA (polyacrylic acid) is added as a dispersing agent, and 6Kg of copper oxide particles with the average particle size of 10 mu m are slowly added while electromagnetic stirring, so as to prepare aluminum nitrate-copper oxide suspension; then stirring the suspension, heating to 90 deg.C to volatilize ethanol, heating the rest solid powder to 300 deg.C at 2 deg.C/min, keeping the temperature for 1h to decompose aluminum nitrate into aluminum oxide, grinding the obtained decomposition product, and sieving with 300 mesh sieve to obtain CuO-Al with particle size less than 48 μm2O3And (3) powder.
(2) 6.5Kg of CuO-Al obtained2O3Mixing the powder with 50kg of Cu-0.3 wt.% Al alloy powder with the granularity of less than 150 mu m by using a planetary ball mill for 3h, and then placing the mixture in a vacuum furnace for in-situ chemical reaction at 900 ℃ for 5 h; keeping the temperature unchanged after the reaction is finished, and introducing hydrogen for reduction treatment for 30min to remove residual CuO to finally obtain 56kg of Cu-Al2O3And (3) compounding powder.
(3) And (3) carrying out pressure maintaining on the composite powder at 500Mpa for 2h, and carrying out isostatic pressing to obtain a prefabricated blank.
(4) Carrying out vacuum hot-pressing sintering on the prefabricated blank, wherein the sintering temperature is 1000 ℃, the sintering time is 4h, and the vacuum degree is 1 multiplied by 10-3Pa, finally obtaining Cu-0.75 wt.% Al2O3The dispersion-strengthened copper-based composite material of (1).
(5) The obtained composite material is extruded into a rod at 550 ℃, and then a corresponding product is prepared according to the requirement.
Example 5
(1) Completely dissolving 40g of aluminum nitrate in ethanol, adding 4KgPAA (polyacrylic acid) serving as a dispersing agent, and slowly adding 1.5Kg of copper oxide particles with the average particle size of 10 mu m while electromagnetically stirring to prepare an aluminum nitrate-copper oxide suspension; then stirring the suspension, heating to 80 ℃ to volatilize ethanol, continuously heating the residual solid powder to 300 ℃ at the speed of 2 ℃/min, keeping the temperature for 1h to decompose aluminum nitrate into aluminum oxide, grinding the obtained decomposition product, and sieving the ground decomposition product with a 300-mesh sieve to obtain CuO-Al with the particle size of less than 48 mu m2O3And (3) powder.
(2) 1.52kg of the resultant CuO-Al2O3Mixing the powder with 35kg of Cu-0.1 wt.% Al alloy powder with the particle size of less than 150 mu m by using a planetary ball mill for 3h, and then placing the mixture in a vacuum furnace for in-situ internal oxidation reaction at 900 ℃ for 8 h; after the reaction is finished, the temperature is kept unchanged, and then hydrogen is introduced for reduction treatment for 1h to remove residual CuO, so that 36.2kg of Cu-Al is finally obtained2O3And (3) compounding powder.
(3) And (3) carrying out pressure maintaining on the composite powder at 500Mpa for 2h, and carrying out isostatic pressing to obtain a prefabricated blank.
(4) Carrying out vacuum hot-pressing sintering on the prefabricated blank, wherein the sintering temperature is 1100 ℃, the sintering time is 5h, and the vacuum degree is 1 multiplied by 10-3Pa, finally obtaining Cu-0.1 wt.% Al2O3The dispersion-strengthened copper-based composite material of (1).
(5) The obtained composite material is extruded into a rod at 550 ℃, and then a corresponding product is prepared according to the requirement.
Comparative example 1
The difference from the embodiment 1 is only that the existing internal oxidation method is adopted, and the specific steps are as follows:
(1) mixing 800g of CuO powder and 50kg of Cu-0.3 wt.% Al alloy powder with the particle size of less than 150 mu m for 3 hours by using a planetary ball mill, and then placing the mixture in a vacuum furnace for in-situ internal oxidation reaction at 800 ℃, wherein the reaction time is 6 hours; keeping the temperature unchanged after the reaction is finished, and introducing hydrogen for reduction treatment for 30min to remove residual CuO to finally obtain 50.5kg of Cu-Al2O3And (3) compounding powder.
(3) Adding Cu-Al2O3And (3) keeping the pressure of the composite powder at 500MPa for 1h, and pressing into a prefabricated blank by isostatic pressing.
(4) Carrying out vacuum hot-pressing sintering on the prefabricated blank, wherein the sintering temperature is 1000 ℃, the sintering time is 3h, the vacuum degree is 1 x 10 < -2 > Pa, and finally obtaining Cu-0.75 wt.% Al2O3The dispersion-strengthened copper-based composite material.
(5) The obtained composite material is extruded into a rod at 550 ℃, and then a corresponding product is prepared according to the requirement.
Performing performance test on the products obtained in the step (5) of the examples 1-5 and the comparative example 1, sampling according to GB6397-86, drawing in a room, wherein the sample is in an extrusion state, and the drawing speed is 2 mm/min; the conductivity measurement is carried out on a QJ19 type double-arm dual-purpose bridge, and the measurement current is 2A; softening temperature: the samples were processed into 1.5mm sheets and annealed at 30 ℃ intervals, tested for vickers hardness, and the softening temperature was determined when the hardness decreased to 80% of the initial hardness after annealing. The test results are shown in Table 1.
Cu-Al prepared in Table 12O3Properties of composite materials
From the results of example 1 and comparative example 1, it can be seen that the nano alumina particles prepared by the method of the present invention can enhance the mechanical properties of the material without reducing the conductivity, compared with the conventional internal oxidation method.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a nano alumina particle reinforced copper-based composite material is characterized by comprising the following steps:
mixing Al (NO)3)3Polyacrylic acid and micron CuO are dispersed in ethanol to obtain Al (NO)3)3-a suspension of CuO;
removing ethanol in the suspension, and decomposing the obtained solid to obtain CuO-Al2O3Powder;
the CuO-Al is added2O3Ball-milling and mixing the powder and Cu-Al alloy powder, and sequentially carrying out in-situ internal oxidation reaction and reduction treatment on the obtained mixed powder to obtain Cu-Al2O3Compounding powder;
the Cu-Al is added2O3Pressing the composite powder to obtain a prefabricated blank;
and carrying out vacuum hot-pressing sintering on the prefabricated blank to obtain the nano alumina particle reinforced copper-based composite material.
2. The method according to claim 1, wherein the decomposition temperature is 300 to 320 ℃.
3. The preparation method according to claim 1, wherein the temperature of the in-situ internal oxidation reaction is 800-1000 ℃, and the holding time is 4-8 h; the in-situ internal oxidation reaction is carried out under a protective atmosphere.
4. The production method according to claim 1, wherein the reduction treatment is performed under a hydrogen atmosphere; the temperature of the reduction treatment is 800-1000 ℃, and the time is 0.5-2 h.
5. The preparation method according to claim 1, wherein the temperature of the vacuum hot-pressing sintering is 900-1100 ℃, the time is 3-6 h, and the vacuum degree is 1 x 10-3Pa～1×10-2Pa。
6. The preparation method according to claim 1, wherein the particle size of the micro CuO is 1 to 15 μm; the CuO-Al2O3The particle size of the powder is smallAt 48 μm; the granularity of the Cu-Al alloy powder is less than 150 mu m.
7. The preparation method according to claim 1, wherein the mass ratio of the polyacrylic acid to the micro CuO is (5-15): 3.5.
8. The method of claim 1, wherein the pressing is isostatic pressing.
9. The nano alumina particle reinforced copper-based composite material prepared by the preparation method of any one of claims 1 to 8, which comprises a Cu matrix and nano Al dispersed in the Cu matrix2O3And (3) granules.
10. The nano alumina particle reinforced copper-based composite material according to claim 9, wherein the nano Al is2O3The particle size of the particles is less than 30 nm; the nano aluminum oxide particle reinforced copper-based composite material contains nano Al2O3The mass content of the particles is 0.1-2%.
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| CN115652174A (en) * | 2022-11-11 | 2023-01-31 | 宁波博威合金材料股份有限公司 | Aluminum oxide dispersion strengthened copper alloy and preparation method and application thereof |
| CN116640955A (en) * | 2023-05-30 | 2023-08-25 | 新疆合盛创新材料有限公司 | Al 2 O 3 Preparation method of dispersion strengthening copper alloy material |
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