CN116005027A - Method for preparing copper-based composite material by combining atomization and mechanical alloying - Google Patents
Method for preparing copper-based composite material by combining atomization and mechanical alloying Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 112
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 51
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 20
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- 239000007789 gas Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
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Abstract
A method for preparing copper-based composite material by combining atomization and mechanical alloying relates to the field of copper-based composite material preparation, which comprises the steps of firstly preparing dispersed phase element oversoluble Cu-based composite atomized powder by vacuum high-temperature smelting and atomization treatment, then preparing precursor powder by mechanical alloying process with deionized water as a process control agent and an oxidant under the protection of inert atmosphere, then removing a lubricating film formed on the surface of the precursor powder by drying, and finally obtaining the copper-based composite material by calcining reduction and vacuum hot-pressing sintering in sequence. The preparation process of the invention combines smelting, rapid atomization, mechanical alloying and vacuum hot-pressing sintering processes, and overcomes the phenomenon of element segregation, disperse phase enrichment shell layer in the traditional internal oxidation process; the limitation that the dispersion phase element needs to have certain solid solubility in the Cu matrix in the traditional internal oxidation process is eliminated, the types of the dispersion phases are widened, and the high-strength and high-conductivity characteristics of the copper-based composite material are realized.
Description
Technical Field
The invention relates to the field of copper-based composite material preparation, in particular to a method for preparing a copper-based composite material by combining atomization and mechanical alloying.
Background
The dispersion strengthening copper-based composite material greatly improves the high-temperature mechanical property of the material while not seriously affecting the electric conductivity and the heat conductivity of the material. In addition, the dispersion strengthened copper has excellent thermal stability at high temperature compared with processes such as work hardening and aging strengthening. Therefore, the dispersion strengthening copper-based composite material has very wide application prospects in a plurality of extreme environments, such as lead frames of integrated circuits, electric contact materials, self-cooling heat-conducting materials of high-power electron tube brackets and the like.
The main methods for preparing the dispersion strengthening copper at present are an internal oxidation process, a mechanical alloying process and the like. The mechanical alloying process inevitably introduces impurities, and is limited in large-scale popularization, so that the commercialization process is insufficient. The technology developed at present is an internal oxidation technology route which is used for preparing commercial dispersion strengthening copper-based composite material Glidcop (Al) 2 O 3 Dispersion strengthened copper). The preparation process is as follows: firstly, melting Cu base containing Al element with a certain component, and then atomizing to prepare Cu base powder containing Al elementThen carrying out high-temperature in-situ oxidation operation on the powder to generate Al 2 O 3 Dispersed phase, then high temperature reduction sintering molding to obtain Al 2 O 3 Dispersion strengthened copper composite material.
However, the high-temperature internal oxidation process is complex in process and strict in parameter requirement, is the most core step in the commercial preparation process, and needs to accurately control oxygen partial pressure so as to achieve the purpose of selectively oxidizing Al element in the Cu-based powder in situ. The kind and content of the disperse phase are strictly limited, and firstly, the disperse phase element must have certain solid solubility in the Cu matrix under the high temperature condition so as to avoid precipitation and polymerization of the disperse phase element under the high temperature condition; secondly, the content of the disperse phase elements cannot be too high, so that the elements are prevented from diffusing to the surface layer in the Cu-based powder particles to form an enriched disperse phase shell layer, and the disperse phase polymerization and the comprehensive performance are reduced due to uneven distribution of components of the dispersion-strengthening copper-based composite material.
Therefore, aiming at the above situation, new preparation process means are developed to avoid the segregation of dispersed phase elements, enrich dispersed phase shell layers and widen the types of dispersed phases, which has important significance for developing high-performance copper-based composite materials.
Disclosure of Invention
In order to improve element segregation in the traditional internal oxidation process, the phenomenon of a diffuse phase enrichment shell layer; the limitation that the dispersion phase element needs to have certain solid solubility in the Cu matrix in the traditional internal oxidation process is eliminated, the types of the dispersion phases are widened, and the high-strength and high-conductivity characteristics of the copper-based composite material are realized. The invention provides a method for preparing a copper-based composite material by combining atomization and mechanical alloying, which can prepare a dispersion strengthening copper-based composite material with fine dispersion phase particles, high number density, uniform element distribution and excellent comprehensive performance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for preparing copper-based composite material by combining atomization and mechanical alloying comprises the steps of preparing dispersed phase element Y or Al over-solid solution Cu-based composite atomized powder Cu-Y or Cu-Al through vacuum high-temperature smelting and atomization treatment, and then controlling the dispersed phase element Y or Al over-solid solution Cu-based composite atomized powder Cu-Y or Cu-Al as a processPreparing precursor powder by a mechanical alloying process under the protection of inert atmosphere by deionized water serving as an oxidant, drying to remove a lubricating film formed on the surface of the precursor powder by the deionized water, and finally sequentially carrying out calcination reduction and vacuum hot-pressing sintering to obtain the Cu-Y composite material 2 O 3 Or Cu-Al 2 O 3 。
The preparation method comprises the following specific steps:
(1) high-temperature smelting: placing copper ingots and yttrium ingots or copper ingots and aluminum ingots into a vacuum smelting furnace of an air atomizing furnace for smelting, and then pouring smelting molten metal into a tundish crucible from the smelting furnace under vacuum condition for heat preservation;
(2) preparing ball compound gold powder by gas atomization: the casting solution is guided into a high-pressure gas atomizer after heat preservation, collected by a cyclone separator and screened to obtain dispersed phase elements Y or Al oversoluble Cu-based composite atomized powder Cu-Y or Cu-Al with different particle sizes;
(3) mechanical alloying: placing the prepared dispersed phase element Y or Al over-solid solution Cu-based composite atomized powder Cu-Y or Cu-Al powder and a proper amount of deionized water into a ball milling tank, placing the ball milling tank into a planetary ball mill for ball milling, taking out and grinding to obtain dispersed precursor powder;
(4) and (3) drying and purifying: drying the precursor powder in a drying oven to remove a lubricating film formed on the surface of ball-milled particles by the process control agent, thereby obtaining dispersed CuO-Y 2 O 3 、Cu 2 O-Y 2 O 3 Or CuO-Al 2 O 3 、Cu 2 O-Al 2 O 3 Mixing the precursor powders;
(5) and (3) calcining and reducing: placing the precursor powder obtained in the step (4) into a high-temperature tube furnace for hydrogen reduction calcination to obtain pure Cu-Y 2 O 3 Or Cu-Al 2 O 3 Cooling the copper-based composite powder along with a furnace;
(6) vacuum hot pressing sintering: the Cu-Y obtained in the step (5) is treated 2 O 3 Or Cu-Al 2 O 3 Loading copper-based composite powder into a graphite mold, prepressing, and placing into a vacuum hot-pressing sintering deviceAfter the preparation, the mixture is pumped into vacuum, and then the mixture is heated and kept for a certain time to ensure that particles obtain enough energy to migrate, and finally a uniform phase is obtained, namely the Cu-Y is obtained 2 O 3 Or Cu-Al 2 O 3 Copper-based composite materials.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
the purity of the copper ingot used in the step (1) is 99.99 percent, and the purity of the yttrium ingot or the aluminum ingot is 99.9 percent; in order to ensure that the ingot is completely melted, the total mass ratio of yttrium ingot or aluminum ingot is 1 percent, the melting temperature is 1400 ℃, the tundish temperature is 1250 ℃, and the heat preservation time is 8 minutes.
The atomization pressure in the step (2) is set to be 5Mpa, and the diameter of the diversion pipe is controlled to be 3mm for controlling the particle size of the powder.
The ball milling rotating speed in the step (3) is 400-600rpm, and the ball milling time is 48-72h; the model of the vacuum glove box is ZKX, the planetary ball mill is QM-QX4 omnibearing planetary ball mill, and the ball-material ratio is 7:3; the assembly of the ball milling tank is completed in a vacuum glove box under the protection of inert atmosphere, so that the pure ball milling environment is ensured; the spherical tank and the ball milling medium are both made of hard alloy, so that the probability of introducing impurities by mechanical alloying is greatly reduced.
The addition amount of deionized water in the step (3) is 15-25% of the mass of the powder.
And (3) the temperature of the oven in the step (4) is 110 ℃, and the drying time is 7 hours.
And (3) heating the model GSL-1200X of the tube furnace in the step (5) to 550-650 ℃, preserving heat for 1h, and then cooling along with the furnace, wherein the heating rate is 10 ℃/min, and the cooling rate is 10 ℃/min.
And (3) the model of the sintering furnace for vacuum hot-pressing sintering in the step (6) is HZK-270, the temperature is raised to 1000 ℃ after vacuumizing, the temperature is kept for 2 hours, the heating rate is 10 ℃/min, the highest pressure is 50MPa, and the furnace is cooled after the temperature is kept.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with a pure mechanical alloying process, the preparation process can ensure that disperse phase elements are uniformly distributed in copper-based composite powder to the greatest extent, achieves the aim of pre-dispersing, shortens the mechanical alloying time and greatly reduces the introduction of impurities.
(2) Firstly, uniformly distributing dispersed phase elements A in a Cu matrix by utilizing a smelting and rapid atomizing process to form Cu-based powder containing A; secondly, the non-thermodynamic equilibrium diffusion of O is promoted by mechanical alloying, under the condition that precipitation of a disperse phase element A is avoided, the O element is uniformly distributed in the whole Cu-based composite powder, deionized water is used as an oxidant, and O is uniformly distributed in the Cu matrix powder when a large amount of energy is provided by the mechanical alloying. Meanwhile, the deionized water can also play a role of a process control agent, a layer of water film is formed between the powders, powder agglomeration is reduced, and a fine dispersion phase is finally formed. And A, O elements which are uniformly distributed are subjected to in-situ reaction to generate oxide dispersion particles, and finally, the dispersion-strengthening copper-based composite material with fine dispersion phase particles, high number density, uniform element distribution and excellent comprehensive performance is prepared through vacuum hot-pressing sintering molding.
Drawings
FIG. 1 is a schematic flow chart of the preparation of an oxide dispersion strengthened copper-based composite material according to the present invention.
FIG. 2 shows the dispersion of Y in the copper matrix in the atomized powder prepared in example 1.
Fig. 3 is a block transmission diagram of the oxide dispersion strengthened copper-based composite prepared in example 1.
FIG. 4 is a diagram showing the precipitation of the Y element at high temperature in the oxide dispersion-strengthened copper-based bulk composite material prepared in comparative example 1.
Fig. 5 is a graph of bulk tensile properties of oxide dispersion strengthened copper matrix composites prepared in example 1, comparative example 1, and comparative example 2.
Detailed Description
The following detailed description of the preferred and comparative embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to make a clear and concise definition of the scope of the present invention.
Example 1
Cu-Y in the present embodiment 2 O 3 The composite material is prepared by high-temperature smelting, gas atomization preparation of spherical alloy powder, mechanical alloying, calcination reduction and vacuum hot-pressing sintering, wherein the yttrium ingot accounts for 1% of the total mass ratio.
Cu-Y in the present embodiment 2 O 3 The preparation method of the composite material comprises the following steps:
1. high-temperature smelting: the copper ingot and the yttrium ingot are placed in a vacuum smelting furnace of an air atomizing furnace, smelting molten metal is poured into a tundish crucible from the smelting furnace under the vacuum condition, and in order to ensure that the ingot is completely melted, the total mass ratio of the yttrium ingot is 1%, the smelting temperature is 1400 ℃, the tundish temperature is 1250 ℃, and the heat preservation time is 8min.
2. Preparing ball compound gold powder by gas atomization: the casting solution is guided into a high-pressure gas atomizer after heat preservation, collected by a cyclone separator and screened to obtain dispersed phase element Y oversoluble Cu-based composite atomized powder (Cu-Y); the atomization pressure is set to be 5Mpa, and the diameter of the flow guide pipe is controlled to be 3mm for controlling the particle size of the powder.
3. Mechanical alloying: placing the prepared dispersed phase element Y over-solid solution Cu-based composite atomized powder (Cu-Y) powder and deionized water (powder mass 20%) into a ball milling tank, wherein the ball milling rotating speed (autorotation speed) is 500rpm, the ball milling time is 64h, and the ball-to-material ratio is 7: and 3, completing the assembly of the ball milling tank in a vacuum glove box under the protection of inert atmosphere, wherein the ball milling tank and the ball milling medium are both made of hard alloy, after the assembly is completed, placing the ball milling tank in a planetary ball mill for ball milling, taking out and grinding to obtain dispersed precursor powder.
4. And (3) drying and purifying: placing the precursor powder in a drying oven, setting the temperature of the drying oven to be 110 ℃, and the drying time to be 7 hours, and removing a lubricating film formed on the surface of ball-milling particles by a process control agent to obtain dispersed CuO-Y 2 O 3 Or Cu 2 O-Y 2 O 3 Mixing the precursor powders.
5. And (3) calcining and reducing: placing the precursor powder obtained in the step 4 into a high-temperature tube furnace for hydrogen reduction calcination to obtain pure Cu-Y 2 O 3 The copper-based composite powder was then furnace cooled, wherein the reduction temperature was 600 ℃.
6. Vacuum hot pressing sintering: the Cu-Y obtained in the step 5 is treated 2 O 3 Loading copper-based composite powder into a graphite mold, prepressing, placing into vacuum hot-pressing sintering equipment, vacuumizing, heating to 1000 ℃ and preserving heat for 2 hours to enable particles to obtain enough energy for migration, wherein the highest pressure is 50MPa, finally obtaining a uniform phase, cooling to room temperature after heat preservation is finished, and obtaining Cu-Y 2 O 3 Copper-based composite materials.
Example 2
Cu-Al in the present example 2 O 3 The composite material is prepared by high-temperature smelting, gas atomization preparation of spherical alloy powder, mechanical alloying, calcination reduction and vacuum hot-pressing sintering, wherein the aluminum ingot accounts for 1% of the total mass ratio.
Cu-Al in the present example 2 O 3 The preparation method of the composite material comprises the following steps:
1. high-temperature smelting: the copper ingot and the aluminum ingot are placed in a vacuum smelting furnace of an air atomizing furnace, smelting molten metal is poured into a tundish crucible from the smelting furnace under the vacuum condition, and in order to ensure that the ingot is completely melted, the total mass ratio of the aluminum ingot is 1%, the smelting temperature is 1400 ℃, the tundish temperature is 1250 ℃, and the heat preservation time is 8min.
2. Preparing ball compound gold powder by gas atomization: the casting solution is guided into a high-pressure gas atomizer after heat preservation, collected by a cyclone separator and screened to obtain dispersed phase element Al oversoluble Cu-based composite atomized powder (Cu-Al); the atomization pressure is set to be 5Mpa, and the diameter of the flow guide pipe is controlled to be 3mm for controlling the particle size of the powder.
3. Mechanical alloying: placing the prepared dispersed phase element Al over-solid solution Cu-based composite atomized powder (Cu-Al) powder and deionized water (powder mass 20%) into a ball milling tank, wherein the ball milling rotating speed (autorotation speed) is 500rpm, the ball milling time is 64h, and the ball-to-material ratio is 7: and 3, completing the assembly of the ball milling tank in a vacuum glove box under the protection of inert atmosphere, wherein the ball milling tank and the ball milling medium are both made of hard alloy, after the assembly is completed, placing the ball milling tank in a planetary ball mill for ball milling, taking out and grinding to obtain dispersed precursor powder.
4. And (3) drying and purifying: placing the precursor powder in a drying oven, setting the temperature of the drying oven to be 110 ℃, and the drying time to be 7 hours, and removing a lubricating film formed on the surface of ball-milling particles by a process control agent to obtain dispersed CuO-Al 2 O 3 Or Cu 2 O-Al 2 O 3 Mixing the precursor powders.
5. And (3) calcining and reducing: placing the precursor powder obtained in the step 4 into a high-temperature tube furnace for hydrogen reduction calcination to obtain pure Cu-Al 2 O 3 The copper-based composite powder was then furnace cooled, wherein the reduction temperature was 600 ℃.
6. Vacuum hot pressing sintering: the Cu-Al obtained in the step 5 is treated 2 O 3 15g of copper-based composite powder is put into a graphite mold, pre-pressed, placed into vacuum hot-pressing sintering equipment, vacuumized, then heated to 1000 ℃ and kept for 2 hours to ensure that particles obtain enough energy to migrate, the highest pressure is 50MPa, finally a uniform phase is obtained, and the temperature is reduced to room temperature after the heat preservation is finished, thus obtaining the Cu-Al alloy 2 O 3 Copper-based composite materials.
Comparative example 1
Cu-Y in the present embodiment 2 O 3 The composite material is prepared by high-temperature smelting, gas atomization preparation of spherical alloy powder, internal oxidation, calcination reduction and vacuum hot-pressing sintering, wherein the yttrium ingot accounts for 1% of the total mass ratio.
Cu-Y in the present embodiment 2 O 3 The preparation method of the composite material comprises the following steps:
1. high-temperature smelting: the copper ingot and the yttrium ingot are placed in a vacuum smelting furnace of an air atomizing furnace, smelting molten metal is poured into a tundish crucible from the smelting furnace under the vacuum condition, and in order to ensure that the ingot is completely melted, the total mass ratio of the yttrium ingot is 1%, the smelting temperature is 1400 ℃, the tundish temperature is 1250 ℃, and the heat preservation time is 8min.
2. Preparing ball compound gold powder by gas atomization: the casting solution is guided into a high-pressure gas atomizer after heat preservation, collected by a cyclone separator and screened to obtain dispersed phase element Y oversoluble Cu-based composite atomized powder (Cu-Y); the atomization pressure is set to be 5Mpa, and the diameter of the flow guide pipe is controlled to be 3mm for controlling the particle size of the powder.
3. Internal oxidation process: the prepared dispersed phase element Y is subjected to solid solution Cu-based composite atomized powder (Cu-Y) powder and a proper amount of oxidant Cu 2 O is placed in a muffle furnace, the temperature is increased to 650 ℃ at a rate of 10 ℃ per second, the internal oxidation time is 12h, and the precursor powder is obtained after being taken out and ground.
4. And (3) calcining and reducing: placing the precursor powder obtained in the step 3 into a high-temperature tube furnace for hydrogen reduction calcination to obtain pure Cu-Y 2 O 3 The copper-based composite powder was then furnace cooled, wherein the reduction temperature was 600 ℃.
5. Vacuum hot pressing sintering: the Cu-Y obtained in the above step is treated 2 O 3 Loading copper-based composite powder into a graphite mold, prepressing, placing into vacuum hot-pressing sintering equipment, vacuumizing, heating to 1000 ℃ and preserving heat for 2 hours to enable particles to obtain enough energy for migration, wherein the highest pressure is 50MPa, finally obtaining a uniform phase, cooling to room temperature after heat preservation is finished, and obtaining Cu-Y 2 O 3 Copper-based composite materials.
Comparative example 2
Cu-Y in the present embodiment 2 O 3 The composite material is prepared by a mechanical alloying, drying and purifying, calcining and reducing and vacuum hot-pressing sintering processing technology, wherein yttrium powder accounts for 1% of the total mass of the total initial powder.
Cu-Y in the present embodiment 2 O 3 The preparation method of the composite material comprises the following steps:
1. mechanical alloying: placing copper powder and yttrium powder into a ball milling tank, wherein the mass ratio of the yttrium powder is 1%, adding deionized water (20% of the total mass of the powder) into the ball milling tank, the ball milling rotating speed is 500rpm, the ball milling time is 64h, and completing the assembly of the ball milling tank in a vacuum glove box under the protection of inert atmosphere, wherein the ball milling tank and the ball milling medium are made of hard alloy, and after the assembly is completed, placing the ball milling tank into a planetary ball mill for installation and fixation, and then performing ball milling to obtain 30g of dispersed precursor powder.
2. And (3) drying and purifying: placing the precursor powder in a drying oven, setting the temperature of the drying oven to be 110 ℃, and the drying time to be 7 hours, and removing a lubricating film formed on the surface of ball-milling particles by a process control agent to obtain dispersed CuO-Y 2 O 3 Or Cu 2 O-Y 2 O 3 Mixing the precursor powders.
3. And (3) calcining and reducing: the dispersed CuO-Y obtained in the above step 2 O 3 Or Cu 2 O-Y 2 O 3 The mixed precursor powder is put into a high-temperature tube furnace for calcination reduction to obtain pure Cu-Y 2 O 3 The copper-based composite material is heated to 600 ℃ from room temperature at the rate of 10 ℃ per minute, is kept for 1 hour and is then cooled along with the furnace, wherein the atmosphere in the high-temperature tubular furnace uses reducing gas hydrogen, and finally Cu-Y is obtained 2 O 3 Copper-based composite powder.
4. Vacuum hot pressing sintering: the Cu-Y obtained in the above step is treated 2 O 3 Loading copper-based composite powder into a graphite mold, prepressing, placing into vacuum hot-pressing sintering equipment, vacuumizing, heating to 1000 ℃ and preserving heat for 2 hours to enable particles to obtain enough energy for migration, wherein the highest pressure is 50MPa, finally obtaining a uniform phase, cooling to room temperature after heat preservation is finished, and obtaining Cu-Y 2 O 3 Copper-based composite materials.
The copper-based composite materials prepared in examples 1 and 2 and comparative examples 1 and 2 were tested for electrical conductivity, tensile strength and elongation properties, and the results are shown in table 1.
Table 1 conductivity, tensile strength and elongation of copper-based composites in examples and comparative examples
As can be seen from FIG. 1, the present process is a bonding meltThe preparation method of the composite material comprises the steps of firstly preparing dispersed phase element Y or Al over-solid solution Cu-based composite atomized powder Cu-Y or Cu-Al through vacuum high-temperature smelting and atomization treatment, then preparing precursor powder by a mechanical alloying process with deionized water as a process control agent and an oxidant under the protection of inert atmosphere, then removing a lubricating film formed on the surface of the precursor powder by the deionized water through drying, and finally obtaining the Cu-Y composite material through calcination reduction and vacuum hot-pressing sintering in sequence 2 O 3 Or Cu-Al 2 O 3 。
As can be seen from FIG. 2, in the Cu-Y alloy powder obtained by atomization, the Y element is uniformly distributed in the copper matrix to form a uniformly dispersed strengthening phase Y for subsequent mechanical alloying 2 O 3 A solid foundation is laid.
As can be seen from fig. 3, the strengthening phase in the embodiment 1 processed by the process has smaller size and even distribution and dispersion, and the Y element after atomization is evenly distributed in the copper matrix, so that the energy of in-situ formation of the dispersion strengthening phase by mechanical alloying is reduced, and the functions of fine crystal strengthening and dispersion strengthening are comprehensively exerted; while the copper grains are thinned by direct mechanical alloying, the formed reinforced phases are not uniformly distributed, so that more fine crystal reinforcement plays a role in reinforcement, and the strength of the material is slightly higher but the plasticity is obviously reduced. In the comprehensive view, compared with direct mechanical alloying, mechanical alloying after atomization obviously improves the plasticity and the conductivity of the material on the premise of slightly lower strength, so that the comprehensive performance of the material is superior.
As can be seen from FIG. 4, since the Y element is hardly dissolved in the copper matrix at high temperature, the Y element is finally obtained by the agglomeration and precipitation of the Y element by the oxidation at high temperature after atomization 2 O 3 The coarse particle size is the main reason for poor mechanical properties.
As can be seen from fig. 5, compared with the conventional method of directly using mechanical alloying, the process significantly improves the plasticity of the composite material on the premise that the strength is hardly reduced; compared with the traditional method of internal oxidation after atomization, the dispersion strengthening copper prepared by the process has obviously improved tensile strength and plasticity.
As can be seen from Table 1, compared with the dispersion strengthening copper-based material prepared by the traditional methods of atomization, internal oxidation and direct mechanical alloying, the mechanical properties of the composite material obtained by the method of mechanical alloying after smelting and atomization are obviously improved under the condition that the conductivity is not obviously reduced, so that the comprehensive properties of the composite material are superior.
TABLE 2 thermodynamic calculation results
As can be seen from Table 2, the oxidation reaction is verified by thermodynamic calculation, and in the preparation process, deionized water and the disperse phase precursor Y element undergo oxidation reaction to generate Y 2 O 3 The reaction equation is as follows:
2Y+3H 2 O——Y 2 O 3 +3H 2
for Y and H 2 The O reaction system was subjected to thermodynamic analysis, and the gibbs free energy of the reaction can be expressed as:
wherein,,
and->
Respectively represent H 2 、Y 2 O 3 Y and H 2 Molar atomic ratio of O. />
And->
Respectively represent H 2 、Y 2 O 3 Y and H 2 Gibbs free energy of O; Δg represents the gibbs free energy required for the above reaction.
In summary, the invention exploits a process flow for preparing the dispersion-strengthened copper-based composite material by combining atomization and mechanical alloying, promotes non-thermodynamic equilibrium diffusion of O element while avoiding polymerization of dispersed phase element in Cu-based powder, ensures that both dispersed phase element A and O are uniformly distributed in Cu-based powder, greatly refines dispersed phase and improves the number density thereof, thereby obtaining the dispersion-strengthened copper-based material with excellent comprehensive performance; compared with a simple internal oxidation process, the process of the invention not only can prevent the segregation, polymerization and other phenomena of dispersed phase elements in the internal oxidation process, but also is not limited by the solid solubility of the dispersed phase elements in a copper matrix, widens the variety of dispersed phases, and can prepare dispersion-strengthened copper-based composite materials which cannot be prepared by the conventional internal oxidation process, such as Cu-Y 2 O 3 、Cu-ZrO 2 、Cu-HfO 2 The method comprises the steps of carrying out a first treatment on the surface of the Compared with a simple mechanical alloying process, the invention can maximally ensure that the disperse phase elements are uniformly distributed in the copper-based composite powder, thereby achieving the purpose of pre-dispersing, shortening the mechanical alloying time and greatly reducing the introduction of impurities.
Meanwhile, deionized water is used as an oxidant and can be used as a process control agent, and a layer of deionized water film is formed on the surface layer of the Cu-based powder in the mechanical alloying process, so that the aim of inhibiting the growth of ductile Cu-based powder is fulfilled; the deionized water film on the surface layer of the Cu-based powder is easy to remove after mechanical alloying, can not remain on the surface layer of the particles, weakens the boundary problem of the original particles, and does not influence the adhesion between Cu-based particles in the subsequent sintering process.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (9)
1. A method for preparing copper-based composite material by combining atomization and mechanical alloying is characterized in that firstly dispersed phase element Y or Al over-solid solution Cu-based composite atomized powder Cu-Y or Cu-Al is prepared by vacuum high temperature smelting and atomization treatment, then precursor powder is prepared by mechanical alloying process with deionized water as process control agent and oxidant under the protection of inert atmosphere, then lubrication film formed on the surface of the precursor powder by deionized water is removed by drying, and finally copper-based composite material Cu-Y is obtained by calcination reduction and vacuum hot-press sintering in sequence 2 O 3 Or Cu-Al 2 O 3 。
2. The method of claim 1, characterized by the steps of:
(1) high-temperature smelting: placing copper ingots and yttrium ingots or copper ingots and aluminum ingots into a vacuum smelting furnace of an air atomizing furnace for smelting, and then pouring smelting molten metal into a tundish crucible from the smelting furnace under vacuum condition for heat preservation;
(2) preparing ball compound gold powder by gas atomization: the casting solution is guided into a high-pressure gas atomizer after heat preservation, collected by a cyclone separator and screened to obtain dispersed phase elements Y or Al oversoluble Cu-based composite atomized powder Cu-Y or Cu-Al with different particle sizes;
(3) mechanical alloying: placing the prepared dispersed phase element Y or Al over-solid solution Cu-based composite atomized powder Cu-Y or Cu-Al powder and a proper amount of deionized water into a ball milling tank, placing the ball milling tank into a planetary ball mill for ball milling, taking out and grinding to obtain dispersed precursor powder;
(4) and (3) drying and purifying: drying the precursor powder in a drying oven to remove a lubricating film formed on the surface of ball-milled particles by the process control agent, thereby obtaining dispersed CuO-Y 2 O 3 、Cu 2 O-Y 2 O 3 Or CuO-Al 2 O 3 、Cu 2 O-Al 2 O 3 Mixing the precursor powders;
(5) and (3) calcining and reducing: placing the precursor powder obtained in the step (4) into a high-temperature tube furnace for hydrogen reduction calcination to obtain pure Cu-Y 2 O 3 Or Cu-Al 2 O 3 Cooling the copper-based composite powder along with a furnace;
(6) vacuum hot pressing sintering: the Cu-Y obtained in the step (5) is treated 2 O 3 Or Cu-Al 2 O 3 Loading copper-based composite powder into a graphite mold, prepressing, placing into vacuum hot-pressing sintering equipment, vacuumizing, heating and maintaining for a certain time to obtain uniform phase, and obtaining Cu-Y 2 O 3 Or Cu-Al 2 O 3 Copper-based composite materials.
3. The method of claim 2, wherein the copper ingot used in step (1) has a purity of 99.99% and the yttrium or aluminum ingot has a purity of 99.9%; setting the total mass ratio of yttrium ingot or aluminum ingot to be 1%, smelting temperature to be 1400 ℃, tundish temperature to be 1250 ℃ and heat preservation time to be 8min.
4. The method according to claim 2, wherein the atomization pressure in the step (2) is set to 5Mpa, and the diameter of the draft tube is controlled to 3mm.
5. The method according to claim 2, wherein the ball milling rotation speed in the step (3) is 400-600rpm, and the ball milling time is 48-72 hours; the model of the vacuum glove box is ZKX, the planetary ball mill is QM-QX4 omnibearing planetary ball mill, and the ball-material ratio is 7:3; and (3) completing the assembly of the ball milling tank in a vacuum glove box under the protection of inert atmosphere, wherein the ball milling tank and the ball milling medium are both made of hard alloy.
6. The method of claim 2, wherein the deionized water is added in the amount of 15-25% of the powder mass in the step (3).
7. The method of claim 2, wherein the oven temperature in step (4) is 110 ℃ and the drying time is 7 hours.
8. The method of claim 2, wherein the tube furnace model GSL-1200X in step (5) is heated to 550-650 ℃ and incubated for 1h and then cooled with the furnace at a heating rate of 10 ℃/min and a cooling rate of 10 ℃/min.
9. The method of claim 2, wherein the sintering furnace model of the vacuum hot-pressed sintering in the step (6) is HZK-270, the temperature is raised to 1000 ℃ after vacuumizing and is kept for 2 hours, the temperature raising rate is 10 ℃/min, the highest pressure is 50MPa, and the furnace is cooled after the heat preservation is finished.
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| CN116607046A (en) * | 2023-04-27 | 2023-08-18 | 合肥工业大学 | Cu-Y-Ti copper-based composite material for electric vacuum device and preparation method thereof |
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| CN114807660A (en) * | 2022-05-18 | 2022-07-29 | 合肥工业大学 | Method for preparing copper-based composite material through copper-containing intermetallic compound |
| CN115044794A (en) * | 2022-06-08 | 2022-09-13 | 合肥工业大学 | Cu- (Y) with excellent performance 2 O 3 -HfO 2 ) Alloy and preparation method thereof |
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| CN114703391A (en) * | 2022-03-25 | 2022-07-05 | 华中科技大学 | Nano-oxide dispersion strengthened copper alloy and preparation method thereof |
| CN114807660A (en) * | 2022-05-18 | 2022-07-29 | 合肥工业大学 | Method for preparing copper-based composite material through copper-containing intermetallic compound |
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| CN116607046A (en) * | 2023-04-27 | 2023-08-18 | 合肥工业大学 | Cu-Y-Ti copper-based composite material for electric vacuum device and preparation method thereof |
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