CN112207281B - Layered gradient copper-based composite material and preparation method thereof - Google Patents
Layered gradient copper-based composite material and preparation method thereof Download PDFInfo
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
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- 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
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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- C22C1/0425—Copper-based alloys
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- 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
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- 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
- C22C32/0052—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 carbides
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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
- C22C32/0073—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 borides
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
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Abstract
The invention relates to a layered gradient copper-based composite material and a preparation method thereof, belonging to the technical field of metal-based composite materials. The invention provides a preparation method of a layered gradient copper-based composite material, which comprises the steps of filling mixed powder containing different amounts of reinforcing materials and copper base materials into a die in a layered mode, enabling the content of the reinforcing materials in the mixed powder to be in gradient distribution from bottom to top, and obtaining a layered gradient copper-based composite material blank through pressing and sintering; and (3) smelting the layered gradient copper-based composite material blank serving as a consumable electrode by a vacuum consumable arc smelting method, and cooling to obtain the copper-based composite material. The method has the advantages of simple process, conventional equipment, strong operability and strong controllability, and the number of layers, the thickness of each layer, the content of the reinforcing material in the mixed powder of each layer and the like can be adjusted according to requirements, so that the gradient distribution of the layered gradient copper-based composite material is adjusted, the smelting is favorable for improving the uniformity of a transition layer, and the layered gradient copper-based composite material is uniform in transition and better in continuity.
Description
Technical Field
The invention relates to a layered gradient copper-based composite material and a preparation method thereof, belonging to the technical field of metal-based composite materials.
Background
Copper is widely applied to industrial production as a material with the functions of electric conduction and heat conduction. However, copper is low in strength, poor in heat resistance and wear resistance and easy to soften and deform at high temperature, and the copper-based composite material prepared by adding the reinforcing material into copper can improve the strength, heat resistance and wear resistance of the copper-based composite material and relieve the defect of easy softening and deformation of copper at high temperature, but can reduce the electric conductivity or thermal conductivity of copper. Under the condition, the copper-based gradient composite material is produced at the same time, one end of the composite material is pure copper or copper alloy, the other end of the composite material is a particle reinforced copper-based material with low expansion coefficient, high strength and high wear resistance, and the components change continuously or quasi-continuously. The performance of the material shows gradient change in space, thereby meeting the special performance requirements of the corresponding parts of the member and achieving the purpose of optimizing the overall use performance of the structure.
The preparation method of the metal gradient material is various, and mainly comprises powder metallurgy, a plasma spraying method, a self-propagating combustion high-temperature synthesis method, a centrifugal casting method, a vapor deposition method and the like. The powder metallurgy method has high reliability and is suitable for manufacturing functional gradient material parts with simpler shapes, but the prepared gradient material has certain porosity. The gradient coating prepared by the plasma spraying method has low bonding strength with a matrix, and has the defects of uneven coating tissue, loose holes, rough surface and the like. The self-propagating combustion high-temperature synthesis method is only suitable for material systems with high exothermic reactions, and the metal and ceramic have large calorific value difference, different sintering degrees and difficult control, so that the compactness of the material is influenced, the porosity is high, and the mechanical strength is low. The centrifugal casting method can prepare gradient materials with high density and large size, but the method is limited to tubular or annular parts and the like.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of the layered gradient copper-based composite material, which has simple process, conventional equipment and strong operability.
The second purpose of the invention is to provide a layered gradient copper-based composite material which has higher density.
The technical scheme of the invention is as follows:
a preparation method of a layered gradient copper-based composite material comprises the following steps:
(1) Loading mixed powder containing different amounts of reinforcing materials and copper base materials into a die in a layered manner, enabling the content of the reinforcing materials in the mixed powder to be in gradient distribution from bottom to top, and pressing and sintering to obtain a layered gradient copper-based composite material blank;
wherein the reinforcing material is a metal oxide, a metal carbide, a metal boride or a refractory metal;
(2) And (2) smelting the layered gradient copper-based composite material blank obtained in the step (1) as a consumable electrode by a vacuum consumable arc smelting method, and cooling to obtain the layered gradient copper-based composite material.
The number of layers of the mixed powder which is loaded into the die in a layered mode can be 1 layer, 2 layers, 3 layers, 4 layers, 5 layers, 6 layers or 7 layers, and also can be more.
The height of the mixed powder in each layer can be 1/10, 1/9, 1/8, 1/7, 1/6, 1/5, 1/3, 1/2 or 2/3 of the total height of the gradient layer, and the like. The height of each layer of mixed powder can be the same, for example, the number of layers is 3, and the height of each layer of mixed powder is 1/3 of the total height of the die; the height of the mixed powder of each layer can also be different. If the number of the layers is 3, the height of the mixed powder of each layer is 1/5, 2/5 and 2/5 of the total height of the die in sequence. The total height of the gradient layer can be 100 μm, 1mm, 20mm, 30mm or 50mm, etc., or higher, such as 100mm, 300mm, etc., and the height of the gradient layer can be set according to actual needs.
It is understood that when the number of layers is greater than 2, the content difference of the reinforcing materials in the mixed powder of each two adjacent layers can be the same, for example, the number of layers is 4, and the content of the reinforcing materials in the mixed powder is 15%, 10%, 5% and 0% from bottom to top; the content difference of the reinforcing materials in the mixed powder of two adjacent layers can also be different, for example, the number of the layers is 4, and the content of the reinforcing materials in the mixed powder is 12 percent, 8 percent, 5 percent and 0 percent from bottom to top in sequence.
The preparation method of the layered gradient copper-based composite material only needs to load the mixed powder containing different amounts of reinforcing materials into powder layer by layer, and the layered gradient copper-based composite material can be prepared by pressing and sintering, and then smelting. The vacuum consumable arc melting can obtain a microstructure with metallurgical quality, improve the interface bonding of a matrix and a reinforcing phase and improve the performance of the composite material.
Preferably, in the step (1), the maximum content of the reinforcing material in the mixed powder is 25wt%. The highest content of the reinforcing material in the mixed powder is 25wt%, which is beneficial to ensuring that the copper-based composite material has good strength, heat resistance and wear resistance, and the processability of the copper-based composite material is not influenced.
It should be understood that the maximum content of the reinforcing material in the mixed powder is 25wt% means that the content of the reinforcing material in the mixed powder at any position in the mold is 25wt% or less. For example, if the content of the reinforcing material in the mixed powder is gradually decreased from bottom to top, and the content of the reinforcing material in the mixed powder at the lowermost layer is less than 25wt%, in this case, the content of the reinforcing material in the mixed powder at the uppermost layer may be 0%, or more than 0%, such as 2%; if the content of the reinforcing material in the mixed powder is distributed in a gradient increasing manner from bottom to top, the content of the reinforcing material in the mixed powder at the uppermost layer is less than 25wt%, and at this time, the content of the reinforcing material in the mixed powder at the lowermost layer can be 0% or more than 0%, such as 2%.
Preferably, in the step (1), the content difference of the reinforcing materials in two adjacent layers of the mixed powder is within 5%. When the content difference of the reinforcing materials in the two adjacent layers of mixed powder is within 5%, the content difference of the reinforcing materials in the two adjacent layers of mixed powder is smaller, and the transition layer is more gentle.
Preferably, in step (1), the metal oxide is Al 2 O 3 、ZrO 2 、TiO 2 、MgO、CeO 2 Or La 2 O 3 ；
The metal carbide is TiC, WC and B 4 C or Cr 3 C 2 ；
The metal boride is CrB 2 、TiB 2 Or ZrB 2 ；
The refractory metal is W or Mo.
The metal oxide, the metal carbide, the metal boride or the refractory metal is a copper-based composite material reinforcing phase, has a good reinforcing effect, and is favorable for improving the strength, the heat resistance and the wear resistance of the copper-based composite material.
Preferably, in the step (1), the copper base material is Cu powder or alloy powder composed of Cu powder and at least one metal powder of Cr powder, zr powder, ti powder and Fe powder.
Preferably, the alloy powder is Cu-Cr alloy powder, cu-Zr alloy powder, cu-Cr-Zr alloy powder, cu-Ti alloy powder or Cu-Fe alloy powder;
wherein the mass ratio of Cu powder to Cr powder in the Cu-Cr alloy powder is 100;
the mass ratio of Cu powder, cr powder and Zr powder in the Cu-Cr-Zr alloy powder is (100);
the mass ratio of Cu powder to Zr powder in the Cu-Zr alloy powder is 100;
the mass ratio of Cu powder to Ti powder in the Cu-Ti alloy powder is 100;
the mass ratio of Cu powder to Fe powder in the Cu-Fe alloy powder is (100).
Preferably, in the step (1), the pressing pressure is 180-300 MPa, and the pressing time is 6-8 min. Pressing for 6-8 min under the pressure of 180-300 MPa, which is beneficial to improving the densification of the blank, and the overhigh pressure has higher requirement on equipment and higher energy consumption. The most economical at this pressure and time.
Preferably, in the step (1), the sintering temperature is 950-1060 ℃, the sintering time is 1-5 h, and the sintering vacuum degree is 1 × 10 -3 ～1×10 -1 Pa. At 950-1060 deg.c and 1 × 10 -3 ～1×10 -1 And Pa sintering for 1-5 h, which is favorable for obtaining the high-densification copper-based composite material. Sintering under vacuum condition is beneficial to reducing the gas content in the composite material and improving the density of the composite material.
Preferably, in the step (2), the smelting current is 2500-4500A, and the smelting voltage is 23-28V. Smelting under the current of 2500-4500A and the voltage of 23-28V is beneficial to forming stable melting speed, and the reinforcing phase is ensured to be uniformly distributed in the copper matrix.
Preferably, in the step (2), the arc stabilizing current of the smelting is 5-10A. The arc stabilizing current of 5-10A is more beneficial to matching the electrode feeding amount and the melting speed, and the ingot with uniform tissue is obtained.
A layered gradient copper-based composite material is prepared by the preparation method of the layered gradient copper-based composite material.
The layered gradient copper-based composite material has the advantages that the content of the reinforcing material in the material at one end of the layered gradient copper-based composite material is higher, the content of the reinforcing material in the material at the other end of the layered gradient copper-based composite material is less, even the reinforcing material (a copper matrix) is not contained completely, the transition of a gradient layer is uniform, the continuity is good, the content of the reinforcing material in the material at one end of the layered gradient copper-based composite material is higher than that of the copper matrix, the strength is higher, the heat resistance and the wear resistance are better, the defect that the copper matrix is easy to soften and deform at high temperature is relieved, the content of the reinforcing material in the material at the other end of the layered gradient copper-based composite material is less, even the reinforcing material is not contained, and the layered gradient copper-based composite material has higher electrical conductivity and thermal conductivity. The layered gradient copper-based composite material can meet the special performance requirements of corresponding parts of a component, and achieves the purpose of optimizing the overall use performance of the structure.
Drawings
FIG. 1 is a schematic view showing the gradient distribution after powdering in example 1;
FIG. 2 is a schematic diagram of a layered gradient copper-based composite material obtained by melting in example 1.
Detailed Description
The present invention will be further described with reference to the following embodiments.
In the preparation method of the layered gradient copper-based composite material, the mixed powder is loaded into a die in layers, and then vibration, material rolling and reverse material upsetting are carried out, and then pressing is carried out.
Preferably, the vibration is mechanical vibration. The vibration time is 30-70 s.
Preferably, the material rolling time is 4-8 min.
Preferably, the reverse heading times are 4-6.
In the preparation method of the layered gradient copper-based composite material, the pressing method is a cold isostatic pressing method.
In the preparation method of the layered gradient copper-based composite material, the particle size of the copper base material is 10-200 μm. The particle size of the reinforcing material is 0.5-100 mu m.
In the preparation method of the layered gradient copper-based composite material, the preparation method of the mixed powder of the reinforcing material and the copper base material comprises the following steps: and (3) mixing the reinforcing material and the copper base material in a mixer for 2-16 h.
In the preparation method of the layered gradient copper-based composite material, the smelting is carried out in protective gas. The protective gas is helium.
1. The specific embodiment of the preparation method of the layered gradient copper-based composite material is as follows:
example 1
The preparation method of the layered gradient copper-based composite material of the embodiment takes the layered gradient copper-based composite material composed of W and Cu as an example, the mass percentage content of W is 10%, 5% and 0% from bottom to top in sequence, and the steps are as follows:
powder filling
(1) Weighing W and Cu powder to enable the weight ratio of the W to the Cu powder to be 10, mixing the powder in a mixer for 5 hours, and marking as mixed powder I.
And weighing W and Cu powder to ensure that the weight ratio of the W to the Cu powder is 5.
And weighing copper powder, and marking as mixed powder III.
(2) The mixed powder I, the mixed powder II and the mixed powder III are sequentially laid in a mould, so that the content of W in the mixed powder is in gradient decreasing distribution from bottom to top, as shown in figure 1, figure 1 is a schematic diagram of gradient distribution after powder filling, 1 is a layer corresponding to the mixed powder I, 2 is a layer corresponding to the mixed powder II, and 3 is a layer corresponding to the mixed powder III, and then vibration is carried out for 40s, material rolling is carried out for 5min, and reverse material blocking is carried out for 4 times.
The height ratio of the corresponding layers of the mixed powder I, the mixed powder II and the mixed powder III is 1:1:1.
(II) pressing
And (3) pressing the gradient mixed powder obtained in the step (I) by using a cold isostatic press, wherein the pressing pressure is 250MPa, and the pressing time is 7min, so as to obtain the layered gradient blank.
(III) sintering
Sintering the blank obtained in the step (II) with the vacuum degree of 1 multiplied by 10 -2 Pa, the gas content in the composite material is effectively reduced by vacuum sintering, the density of the composite material is favorably improved, the temperature of the vacuum sintering is 1000 ℃, the time of the vacuum sintering is 3 hours, and a layered gradient copper-based composite material blank is obtained.
(IV) melting
And (3) putting the layered gradient copper-based composite material blank obtained in the step (three) into a vacuum consumable electric arc furnace, vacuumizing the vacuum consumable electric arc furnace after a furnace door is closed, filling protective gas helium, and smelting in the vacuum consumable electric arc furnace, wherein the smelting current is 3500A, the smelting voltage is 25V, under the action of an electric arc, a consumable electrode is molten and then drops into a water-cooled copper crucible, the molten consumable electrode is rapidly solidified into an ingot, the arc stabilizing current is 8A, so that the layered gradient copper-based composite material is obtained, as shown in figure 2, figure 2 is a schematic diagram of the layered gradient copper-based composite material obtained by smelting, black spots in figure 2 are reinforcing phase particles, and reinforcing phases are distributed from high to low along the direction of an arrow.
Example 2
The preparation method of the layered gradient copper-based composite material of the embodiment uses TiO 2 And a layered gradient copper-based composite material consisting of Cu-Ti as an example, tiO 2 The mass percentage of the components is 16 percent, 12 percent, 8 percent, 4 percent and 1 percent from bottom to top in sequence, and the steps are as follows:
powder filling
(1) Weighing TiO 2 With Cu-Ti alloy powder to make TiO 2 Mixing the powder and the Cu-Ti alloy powder for 5 hours in a mixer according to the weight ratio of 16.
Weighing TiO 2 With Cu-Ti alloy powder to make TiO 2 And mixing the powder with Cu-Ti alloy powder for 3 hours in a mixer according to the weight ratio of 12.
Weighing TiO 2 With Cu-Ti alloy powder to make TiO 2 And mixing the powder with the Cu-Ti alloy powder for 5 hours in a mixer according to the weight ratio of 8.
Weighing TiO 2 With Cu-Ti alloy powder to make TiO 2 With Cu-Ti alloy powderMixing the powder for 3 hours in a mixer according to the weight ratio of 4.
Weighing TiO 2 With Cu-Ti alloy powder to make TiO 2 And mixing the powder and the Cu-Ti alloy powder for 3 hours in a mixer according to the weight ratio of 1.
(2) Laying the mixed powder I, the mixed powder II, the mixed powder III, the mixed powder IV and the mixed powder V in a mould in sequence to ensure that TiO in the mixed powder 2 The content of the material is distributed in a gradient decreasing way from bottom to top, and then the material is shaken for 40s, rolled for 5min and reversely piled for 4 times.
The height ratio of the corresponding layers of the mixed powder I, the mixed powder II, the mixed powder III, the mixed powder IV and the mixed powder V is 1:1:1:1:1.
(II) pressing
And (3) pressing the gradient mixed powder obtained in the step (I) by using a cold isostatic press, wherein the pressing pressure is 180MPa, and the pressing time is 8min, so as to obtain the layered gradient blank.
(III) sintering
Sintering the blank obtained in the step (II) with the vacuum degree of 1 multiplied by 10 -3 Pa, the gas content in the composite material is effectively reduced by vacuum sintering, the density of the composite material is favorably improved, the temperature of the vacuum sintering is 950 ℃, the time of the vacuum sintering is 2.5h, and a layered gradient copper-based composite material blank is obtained.
(IV) melting
And (4) putting the layered gradient copper-based composite material blank obtained in the step (III) into a vacuum consumable electric arc furnace, vacuumizing the vacuum consumable electric arc furnace after a furnace door is closed, then filling protective gas helium, smelting in the vacuum consumable electric arc furnace, wherein the smelting current is 4500A, the smelting voltage is 23V, under the action of electric arc, a consumable electrode is molten and then drops into a water-cooled copper crucible, an ingot is rapidly solidified, and the arc stabilizing current is 10A, so that the layered gradient copper-based composite material is obtained.
Example 3
Taking a layered gradient copper-based composite material composed of TiC and Cu-Cr as an example, the preparation method of the layered gradient copper-based composite material of the embodiment sequentially comprises the following steps of, by mass, 25%, 20%, 15%, 10%, 5% and 0% of TiC from bottom to top:
(one) powder filling
(1) And (2) weighing TiC and Cu-Cr alloy powder, mixing the TiC and the Cu-Cr alloy powder for 5 hours in a mixer according to the weight ratio of 25.
And (3) weighing TiC and Cu-Cr alloy powder, mixing the TiC and the Cu-Cr alloy powder for 3 hours in a mixer, and marking as mixed powder II, wherein the weight ratio of the TiC to the Cu-Cr alloy powder is 20.
And (3) weighing TiC and Cu-Cr alloy powder, mixing the TiC and the Cu-Cr alloy powder for 5 hours in a mixer, and marking as mixed powder III, wherein the weight ratio of the TiC to the Cu-Cr alloy powder is 15.
And (3) weighing TiC and Cu-Cr alloy powder, mixing the TiC and the Cu-Cr alloy powder for 3 hours in a mixer, and marking as mixed powder IV, wherein the weight ratio of the TiC to the Cu-Cr alloy powder is 10.
And (3) weighing TiC and Cu-Cr alloy powder, mixing the TiC and the Cu-Cr alloy powder for 3 hours in a mixer according to the weight ratio of 5.
Weighing Cu-Cr alloy powder and marking as mixed powder VI.
(2) And sequentially paving the mixed powder I, the mixed powder II, the mixed powder III, the mixed powder IV, the mixed powder V and the mixed powder VI in a mould to ensure that the TiC content in the mixed powder is in gradient distribution from bottom to top, and then vibrating for 40s, rolling for 5min and reversely upsetting for 4 times.
The height ratio of the corresponding layers of the mixed powder I, the mixed powder II, the mixed powder III, the mixed powder IV, the mixed powder V and the mixed powder VI is 1:1:1:1:1:2.
(II) pressing
And (2) pressing the gradient mixed powder obtained in the step (I) by using a cold isostatic press, wherein the pressing pressure is 300MPa, and the pressing time is 6min, so as to obtain the layered gradient blank.
(III) sintering
Sintering the blank obtained in the step (II) with the sintering vacuum degree of 1 multiplied by 10 -1 Pa, the gas content in the composite material is effectively reduced by vacuum sintering, the density of the composite material is favorably improved, the temperature of the vacuum sintering is 1060 ℃, and the time of the vacuum sintering is 3 hours, so that a layered gradient copper-based composite material blank is obtained.
(IV) melting
And (5) putting the layered gradient copper-based composite material blank obtained in the step (III) into a vacuum consumable electric arc furnace, vacuumizing the vacuum consumable electric arc furnace after a furnace door is closed, then filling protective gas helium, smelting in the vacuum consumable electric arc furnace, wherein the smelting current is 2500A, the smelting voltage is 28V, under the action of electric arc, the consumable electrode is molten and then drops into a water-cooled copper crucible, the cast ingot is rapidly solidified, and the arc stabilizing current is 5A, so that the layered gradient copper-based composite material is obtained.
Example 4
The preparation method of the layered gradient copper-based composite material of the embodiment uses TiB 2 And Cu-Cr-Zr, tiB 2 The mass percentage of the components is 5 percent, 3 percent and 0 percent from bottom to top in sequence, and the steps are as follows:
(one) powder filling
(1) Weighing TiB 2 With Cu-Cr-Zr alloy powder to make TiB 2 And mixing the powder with Cu-Cr-Zr alloy powder for 5 hours in a mixer according to the weight ratio of 5.
Weighing TiB 2 With Cu-Cr-Zr alloy powder to make TiB 2 And mixing the powder with Cu-Cr-Zr alloy powder for 3 hours in a mixer, and marking as mixed powder II, wherein the weight ratio of the mixed powder to the Cu-Cr-Zr alloy powder is 3.
Weighing Cu-Cr-Zr alloy powder, and marking as mixed powder III.
(2) Sequentially laying the mixed powder I, the mixed powder II and the mixed powder III in a mould to ensure that the TiB in the mixed powder 2 The contents of the materials are distributed in a gradient decreasing way from bottom to top, and then the vibration is carried out for 40s, the materials are rolled for 5min, and the reverse material upsetting is carried out for 4 times.
The height ratio of the corresponding layers of the mixed powder I, the mixed powder II and the mixed powder III is 1:1:2.
(II) pressing
And (2) pressing the gradient mixed powder obtained in the step (I) by using a cold isostatic press, wherein the pressing pressure is 260MPa, and the pressing time is 6min, so as to obtain the layered gradient blank.
(III) sintering
Sintering the blank obtained in the step (II)Vacuum degree of (2) is 1X 10 -3 Pa, the gas content in the composite material is effectively reduced by vacuum sintering, the density of the composite material is favorably improved, the temperature of the vacuum sintering is 1010 ℃, and the time of the vacuum sintering is 3 hours, so that a layered gradient copper-based composite material blank is obtained.
(IV) melting
And (5) putting the layered gradient copper-based composite material blank obtained in the step (III) into a vacuum consumable electric arc furnace, vacuumizing the vacuum consumable electric arc furnace after a furnace door is closed, then filling protective gas helium, smelting in the vacuum consumable electric arc furnace, dropping the consumable electrode into a water-cooled copper crucible after the consumable electrode is molten under the action of electric arc, quickly solidifying into an ingot, and obtaining the layered gradient copper-based composite material with the arc stabilizing current of 4A, wherein the smelting current is 2800A and the smelting voltage is 26V.
Examples 5 to 14
Examples 5-14 differ from example 1 only in the reinforcing material or copper substrate, and the remaining steps are as shown in table 1 for the reinforcing material and copper substrate of examples 1 and 5-14.
TABLE 1 reinforcing materials and copper substrates of examples 5-14 and example 1
2. The embodiments of the layered gradient copper-based composite material of the present invention correspond to the final products of the preparation methods of the layered gradient copper-based composite materials of embodiments 1 to 14, respectively.
3. Description of the comparative examples
Comparative example 1
The preparation method of the layered gradient copper-based composite material of the comparative example is different from that of example 1 in that the layered gradient copper-based composite material obtained by sintering is not smelted. The powder loading, pressing and sintering steps were the same as in example 1.
4. Examples of the experiments
The above exemplary embodiment of the layered gradient copper-based composite material was subjected to performance tests, which included electrical conductivity, hardness, and friction rate. Specifically, the electric conductivity is detected according to a GB/T32791-2016 copper and copper alloy electric conductivity eddy current test method; detecting the hardness according to a GB/T231.1-2009 metal Brinell hardness test method; the detection of the wear resistance is carried out by adopting a high-speed current-carrying friction wear testing machine under the conditions of pressure of 60N and current of 70A, and the detection results are shown in table 2.
TABLE 2 Performance test results of the layered gradient copper-based composite of the exemplary embodiment
| Material | Conductivity/% IACS | hardness/HWB | Friction rate/mg/m |
| Example 1: W/Cu | 77 | 68 | 17 |
| Example 4: tiB 2 /Cu-Cr-Zr | 68 | 103 | 11 |
| Example 10: tiB 2 /Cu | 57 | 88 | 16 |
| Comparative example 1: W/Cu | 55 | 48 | 28 |
(Note: 1) when the substrate is an alloy substrate, such as the Cu-Cr-Zr alloy substrate of example 4, the article obtained by melting is subjected to aging treatment at 475 ℃ for 4 hours, and then to conductivity, hardness and current-carrying frictional rate tests. 2) The conductivity, hardness and current-carrying friction rate tests are all to measure the maximum end/face of the content of the enhanced phase, and the end face is the lower end face in the invention. )
The conductivity of pure copper in the sintered state was 75% IACS, and the hardness was 42HWB; the electrical conductivity of the pure copper in the as-cast state was 99% IACS and the hardness was 51HWB. As can be seen from the experimental results in Table 2, the layered gradient composite material of the present invention exhibits different properties at the pure copper end and the end with the maximum content of the reinforcing phase, and thus can be adapted to the connection requirements in special fields. For example, in the field of electronic industry, mo-Cu, W-Cu and other functional gradient composite materials have good mechanical properties, electric conduction and heat conduction properties, ablation resistance, thermal fatigue resistance and the like, meet the working requirements of electronic materials in integrated circuits under harsh working environments, and can be used as grid lead frames of large integrated circuits, electronic device packaging thermal control materials and the like. In the field of energy, the functional gradient composite materials such as W-Cu and the like gradually change along the thickness direction. Therefore, the thermal stress caused by the great difference of the performances of Cu and W can be well relieved, so that the material has better performances of electric conduction, thermal conductivity, mechanical property, high temperature resistance and the like on the whole, bears larger thermal stress and mechanical stress, fully exerts the characteristics of excellent thermal conductivity and room temperature plasticity of Cu and plasma scouring resistance of W, and is used as a plasma-oriented wall protection material in a nuclear reactor. Cu-B 4 The functional gradient materials such as C are also used as plasma materials in a new generation of thermonuclear fusion experimental devices.
Claims (7)
1. The preparation method of the layered gradient copper-based composite material is characterized by comprising the following steps of:
(1) Loading mixed powder containing different amounts of reinforcing materials and copper base materials into a die in a layered manner, enabling the content of the reinforcing materials in the mixed powder to be in gradient distribution from bottom to top, and pressing and sintering to obtain a layered gradient copper-based composite material blank;
wherein the reinforcing material is a metal oxide, a metal carbide, a metal boride or a refractory metal;
(2) Smelting the layered gradient copper-based composite material blank obtained in the step (1) as a consumable electrode by a vacuum consumable arc smelting method, and cooling to obtain the layered gradient copper-based composite material blank;
in the step (1), the copper base material is Cu powder or alloy powder consisting of Cu powder and at least one metal powder of Cr powder, zr powder, ti powder and Fe powder;
the alloy powder is Cu-Cr alloy powder, cu-Zr alloy powder, cu-Cr-Zr alloy powder, cu-Ti alloy powder or Cu-Fe alloy powder;
wherein the mass ratio of Cu powder to Cr powder in the Cu-Cr alloy powder is 100;
the mass ratio of Cu powder, cr powder and Zr powder in the Cu-Cr-Zr alloy powder is (100);
the mass ratio of Cu powder to Zr powder in the Cu-Zr alloy powder is 100;
the mass ratio of Cu powder to Ti powder in the Cu-Ti alloy powder is (100);
the mass ratio of Cu powder to Fe powder in the Cu-Fe alloy powder is 100;
in the step (2), the smelting current is 2500-4500A, and the smelting voltage is 23-28V; the arc stabilizing current for smelting is 5-10A.
2. The method for preparing the layered gradient copper-based composite material as claimed in claim 1, wherein in the step (1), the maximum content of the reinforcing material in the mixed powder is 25wt%.
3. The method for preparing the laminar gradient copper-based composite material according to claim 1, wherein in the step (1), the content difference of the reinforcing materials in the two adjacent layers of the mixed powder is within 5%.
4. The method for preparing the layered gradient copper-based composite material as claimed in claim 1, wherein in the step (1), the metal oxide is Al 2 O 3 、ZrO 2 、TiO 2 、MgO、CeO 2 Or La 2 O 3 ；
The metal carbide is TiC, WC and B 4 C or Cr 3 C 2 ；
The metal boride is CrB 2 、TiB 2 Or ZrB 2 ；
The refractory metal is W or Mo.
5. The method for preparing the layered gradient copper-based composite material as claimed in claim 1, wherein in the step (1), the pressing pressure is 180-300 MPa, and the pressing time is 6-8 min.
6. The method for preparing the layered gradient copper-based composite material according to claim 1, wherein in the step (1), the sintering temperature is 950-1060 ℃, the sintering time is 1-5 h, and the sintering vacuum degree is 1 x 10 -3 ～1×10 -1 Pa。
7. A layered gradient copper-based composite material produced by the method for producing a layered gradient copper-based composite material according to claim 1.
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