CN113355550A - Doped Y2O3Preparation method of reinforced CuCrZr alloy - Google Patents
Doped Y2O3Preparation method of reinforced CuCrZr alloy Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 67
- 238000000498 ball milling Methods 0.000 claims abstract description 50
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 7
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 238000010348 incorporation Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 abstract description 9
- 239000010949 copper Substances 0.000 abstract description 8
- 229910052804 chromium Inorganic materials 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 1
- 229910052727 yttrium Inorganic materials 0.000 description 12
- 229910001093 Zr alloy Inorganic materials 0.000 description 9
- 239000011651 chromium Substances 0.000 description 7
- 238000013329 compounding Methods 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000005275 alloying Methods 0.000 description 1
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- 238000005266 casting Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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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
- 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
Doped Y2O3The preparation method of the reinforced CuCrZr alloy comprises the following steps: the method comprises the following steps: mechanical alloying; step two: second phase particles Y2O3Doping; step three: spark plasma sintering; step four: and (6) homogenizing and annealing. The invention combines Cu, Cr and Zr powder at atomic level by a ball milling method, ensures the uniformity of the structure, and avoids generating pores and loosening shrinkage cavity in the smelting processAnd the like. Second phase particles Y by wet chemical means2O3The CuCrZr powder is introduced into the CuCrZr powder to achieve the state of dispersion distribution. The electric conductivity is maintained at a higher level of 84.3-74.9% IACS, the strength and hardness of the material are further improved, and the hardness is increased along with Y2O3The content is increased, and the hardness and the strength are respectively increased to 185.2-272.3 HV0.1And 378.3-460.6 MPa, the wear rate of the material is reduced, and the service life of the copper alloy is prolonged.
Description
Technical Field
The invention belongs to the technical field of alloy preparation, and particularly relates to a doped Y2O3A preparation method of reinforced CuCrZr alloy.
Background
The copper, chromium and zirconium alloy has high hardness and strength, electrical conductivity and thermal conductivity, and various mechanical properties are obviously improved after aging treatment, so that the copper, chromium and zirconium alloy is a typical aging strengthening type alloy. Therefore, the method is widely applied to the fields of high-speed rail lead frame materials, electrical contact materials and the like. However, with the rapid development of modern society, the requirement for applying copper alloy materials in the electrical field is higher and higher. At present, a dispersion strengthening method is an important method for preparing a high-strength and high-conductivity copper alloy, so that the strength and the thermal stability of the CuCrZr alloy are expected to be further improved on the basis of not remarkably reducing the conductivity by adding a second phase.
For the CuCrZr alloy, the traditional preparation method is to add Zr in a simple substance form, and then integrally smelt the CuCr alloy and the Zr simple substance. However, since Zr is easily oxidized and both densities are lower than those of copper, Zr is greatly burned off during alloy melting, and Zr floats on the surface of molten copper, which causes non-uniformity of structure and is easy to generate defects such as porosity and porosity.
Disclosure of Invention
Aiming at the problems brought forward by the background technology, the invention designs a doped Y2O3The preparation method of the reinforced CuCrZr alloy aims at: provides a method for adding moisture by ball millingPreparation of CuCrZr-Y by chemical method2O3The method for preparing the CuCrZr ternary alloy powder by adopting a ball milling mode avoids the problems of great burning loss and casting defects of Zr and uneven alloy structure and components in the process of a smelting method, and introduces second-phase particles Y into the CuCrZr alloy powder by a wet chemical method2O3Further improves the mechanical property of the CuCrZr alloy.
The technical solution of the invention is as follows:
doped Y2O3The preparation method of the reinforced CuCrZr alloy comprises the following steps:
the method comprises the following steps: mechanical alloying
And (3) putting quantitative copper powder, chromium powder and zirconium powder into a ball milling tank, and replacing air in the ball milling tank with argon in a glove box to prevent oxidation of the powder in the ball milling process. And (3) putting stainless steel grinding balls into the ball milling tank according to the ball-material ratio of 10: 1-15: 1, sealing the ball milling tank in a glove box, and then putting the ball milling tank into a high-energy ball mill for ball milling to obtain the CuCrZr alloy powder.
Step two: second phase particles Y2O3Incorporation of
Taking the CuCrZr alloy powder obtained in the step one and Y (NO)3)3·6H2And dissolving O together in a beaker filled with 100-300 ml of deionized water, and adding a polytetrafluoroethylene stirrer into the beaker after the glass rod is uniformly stirred. Placing the beaker in a magnetic stirrer, heating the beaker to 120-140 ℃ in an oil bath, placing the beaker in an oven for drying at 120-140 ℃ for 12-24 h after deionized water in the beaker is completely evaporated, removing residual water, and obtaining the CuCrZr-Y (NO)3)3The precursor powder is placed in a high-temperature tube furnace for calcination and reduction to finally obtain the CuCrZr-Y2O3And (3) composite powder.
Step three: spark plasma sintering
Weighing 10-15 g of CuCrZr-Y prepared in the second step2O3And (3) putting the composite powder into a graphite die with the diameter of 20mm, and putting graphite pressure heads at two ends of the composite powder. Pre-pressing the powder, placing the powder into a sintering furnace, pumping the pressure in the furnace cavity to be below 20Pa,sintering is started, and the temperature is quickly reduced to room temperature after the heat preservation is finished, so that compact CuCrZr-Y can be obtained2O3And (3) alloy blocks.
Step four: homogenizing annealing
The CuCrZr-Y obtained in the third step2O3Placing the alloy block in a high-temperature tube furnace, heating to 700-800 ℃ at the speed of 5 ℃/min, and preserving heat for 3 h; cooling to 500 ℃ at a speed of 5 ℃/min, and finally cooling along with the furnace, wherein argon gas with a flow rate of 300-500 ml/min is introduced in the process.
In the first step, the ball milling speed is 200-400 rpm, and the ball milling time is 20-40 h.
In the first step, the copper powder, the chromium powder and the zirconium powder are mixed according to the proportion of Cu- (0.6-0.8) wt% of Cr- (0.1-0.3) wt% of Zr, and the copper powder, the chromium powder and the zirconium powder are all spherical particles with the granularity of 1-5 mu m.
In the second step, CuCrZr powder and Y (NO)3)3·6H2The content of O is in accordance with CuCrZr-1 wt% Y2O3，CuCrZr-2wt％Y2O3，CuCrZr-3wt％Y2O3And (4) proportioning.
In the second step, CuCrZr-Y (NO)3)3The calcination and reduction of the precursor powder in the high-temperature tube furnace have the following specific parameters: in a hydrogen atmosphere with a flow rate of 300-500 ml/min, raising the temperature to 600-800 ℃ at a speed of 5 ℃/min, preserving the heat for 2h, then lowering the temperature to 500 ℃ at a speed of 5 ℃/min, and finally cooling along with a furnace, wherein in the process, Y (NO) is obtained3)3Is decomposed into Y by heating2O3。
And in the third step, the pre-pressure of the powder is 3 MPa.
The sintering procedure in the third step is as follows: raising the temperature to 600 ℃ at the heating rate of 100 ℃/min, preserving the heat for 3-5 min, then raising the temperature to 900-1000 ℃ at the heating rate of 100 ℃/min, preserving the heat for 3-5 min, and raising the pressure from 0-10 MPa to 50-70 MPa during the heating.
The fourth step aims to further solve the problem of agglomeration of Cr and Zr, so that yttrium oxide is distributed more dispersedly, and the conductivity and the elongation of the sample are improved.
The invention has the beneficial effects that: compared with other technologies, the method has the advantages thatObviously, the three powders of Cu, Cr and Zr are combined at an atomic level by a ball milling method, so that the uniformity of the structure is ensured, and the defects of air holes, loosening and shrinkage cavities and the like generated in the smelting process are avoided. On the basis of this, the second phase particles Y are subjected to a wet chemical method2O3Is introduced into the CuCrZr powder and can achieve the state of dispersion distribution. The method further improves the strength and hardness of the material on the basis of ensuring that the conductivity is maintained at a higher level of 84.3-74.9% IACS, and along with Y2O3The content is increased, and the hardness and the strength are respectively increased to 185.2-272.3 HV0.1And 378.3-460.6 MPa, the wear rate of the material is reduced, and the service life of the copper alloy is prolonged.
Drawings
FIG. 1 is a morphology of Cu-0.75 wt% Cr-0.2 wt% Zr alloy powder after ball milling.
FIG. 2 is a graph of Cu-0.75 wt% Cr-0.2 wt% Zr-3.0 wt% Y2O3Surface SEM image of composite powder.
FIG. 3 is a Cu-0.75 wt% Cr-0.2 wt% Zr-3.0 wt% Y2O3Fracture morphology of the alloy block.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1
Cu-0.75 wt% Cr-0.2 wt% Zr-1.0 wt% Y in this example2O3The copper alloy material is prepared by ball milling, wet chemical method, spark plasma sintering and final homogenizing annealing.
Cu-0.75 wt% Cr-0.2 wt% Zr-1.0 wt% Y in this example2O3The preparation method of the alloy block body comprises the following steps:
1. mechanical alloying: copper powder, chromium powder and zirconium powder are proportioned and weighed according to the proportion of Cu-0.75 wt% Cr-0.2 wt% Zr, the weighed materials are all poured into a ball milling tank, stainless steel grinding balls are placed into the ball milling tank according to the ball-material ratio of 10:1, air in the ball milling tank is replaced by argon in a glove box, oxidation of the powder in the ball milling process is prevented, the ball milling tank is placed in a high-energy ball mill for ball milling after being packaged in the glove box, and the specific ball milling parameter is ball milling for 40 hours at the rotating speed of 200 rpm. Thus obtaining Cu-0.75 wt% Cr-0.2 wt% Zr alloy powder which is mixed evenly;
2. second phase particles Y2O3The doping of (2): taking the Cu-0.75 wt% Cr-0.2 wt% Zr alloy powder obtained in the step 1 and quantitative yttrium nitrate (Y (NO)3)3·6H2O) are dissolved in a beaker filled with 100ml of deionized water together, a glass rod is added with a polytetrafluoroethylene stirrer after being stirred uniformly, the beaker is placed in a magnetic stirrer, heated to 120 ℃ in an oil bath until the deionized water in the beaker is completely evaporated, the beaker is placed in a drying oven for drying for 12 hours at the temperature of 140 ℃ to remove residual water, and the obtained CuCrZr-Y (NO) is obtained3)3And (3) putting the precursor powder into a high-temperature tube furnace for calcining and reducing: heating to 600 deg.C at a speed of 5 deg.C/min in hydrogen atmosphere at a flow rate of 500ml/min, maintaining for 2h, cooling to 500 deg.C at 5 deg.C/min, and furnace cooling to obtain Cu-0.75 wt% Cr-0.2 wt% Zr-1.0 wt% Y2O3Compounding powder;
3. and (3) sintering: 12g of Cu-0.75 wt% Cr-0.2 wt% Zr-1.0 wt% Y were weighed2O3The composite powder is put into a graphite die with the diameter of 20mm, graphite pressure heads are put at two ends of the composite powder, after the powder is pre-pressed, the composite powder is put into a sintering furnace, and when the pressure in the furnace cavity is pumped to be below 20Pa, a sintering procedure is started: heating to 600 deg.C at a heating rate of 100 deg.C/min, and maintaining at 10MPa for 5 min; then raising the temperature to 900 ℃ at the heating rate of 100 ℃/min, preserving the heat for 5min, raising the pressure from 10MPa to 50MPa in the heating period, and quickly reducing the temperature to the room temperature after the heat preservation is finished;
4. homogenizing and annealing: the resulting Cu-0.75 wt% Cr-0.2 wt% Zr-1.0 wt% Y2O3Placing the alloy block in a high-temperature tube furnace, heating to 700 ℃ at the speed of 5 ℃/min, and preserving heat for 3 h; cooling to 500 deg.C at a rate of 5 deg.C/min, and cooling with the furnace while introducing argon gas at a flow rate of 300 ml/min;
cu-0.75 wt% Cr-0.2 wt% Zr-3.0 wt% Y after sintering2O3The Vickers hardness of the alloy block reaches 185.2HV0.1145.3HV higher than pure CuCrZr0.1The strength is improved to 378.3MPa, and the conductivity is improved84.3% IACS.
Example 2
Cu-0.75 wt% Cr-0.2 wt% Zr-2.0 wt% Y in this example2O3The copper alloy material is prepared by ball milling, wet chemical method, spark plasma sintering and final homogenizing annealing.
Cu-0.75 wt% Cr-0.2 wt% Zr-2.0 wt% Y in this example2O3The preparation method of the alloy block body comprises the following steps:
1. mechanical alloying: copper powder, chromium powder and zirconium powder are proportioned and weighed according to the proportion of Cu-0.75 wt% Cr-0.2 wt% Zr, the weighed materials are all poured into a ball milling tank, stainless steel grinding balls are placed into the ball milling tank according to the proportion of the ball material ratio of 10:1, air in the ball milling tank is replaced by argon in a glove box, the oxidation of the powder in the ball milling process is prevented, the ball milling tank is placed into a high-energy ball mill for ball milling after being packaged in the glove box, the ball milling specific parameters are ball milling for 40 hours at the rotating speed of 200rpm, and the evenly mixed Cu-0.75 wt% Cr-0.2 wt% Zr alloy powder can be obtained;
2. second phase particles Y2O3The doping of (2): taking the Cu-0.75 wt% Cr-0.2 wt% Zr alloy powder obtained in the step 1 and quantitative yttrium nitrate (Y (NO)3)3·6H2O) are dissolved in a beaker filled with 100ml of deionized water together, a glass rod is added with a polytetrafluoroethylene stirrer after being stirred uniformly, the beaker is placed in a magnetic stirrer, heated to 130 ℃ in an oil bath until the deionized water in the beaker is completely evaporated, the beaker is placed in a drying oven for drying for 16 hours at 130 ℃ to remove residual water, and the obtained CuCrZr-Y (NO) is obtained3)3And (3) putting the precursor powder into a high-temperature tube furnace for calcining and reducing: heating to 700 deg.C at a speed of 5 deg.C/min in hydrogen atmosphere at a flow rate of 500ml/min, maintaining for 2h, cooling to 500 deg.C at a speed of 5 deg.C/min, and furnace cooling to obtain Cu-0.75 wt% Cr-0.2 wt% Zr-2.0 wt% Y2O3Compounding powder;
3. and (3) sintering: 12g of Cu-0.75 wt% Cr-0.2 wt% Zr-2.0 wt% Y were weighed2O3Placing the composite powder into a graphite mold with a diameter of 20mm, placing graphite pressure heads at two ends, pre-pressing the powder, and placing the powderPutting the mixture into a sintering furnace, and starting a sintering procedure when the pressure in a furnace cavity is pumped to be below 20 Pa: heating to 600 deg.C at a heating rate of 100 deg.C/min, and maintaining at 10MPa for 5 min; then raising the temperature to 950 ℃ at the heating rate of 100 ℃/min, preserving the heat for 5min, raising the pressure from 10MPa to 60MPa during the heating period, and quickly reducing the temperature to room temperature after the heat preservation is finished;
4. homogenizing and annealing: the resulting Cu-0.75 wt% Cr-0.2 wt% Zr-2.0 wt% Y2O3Placing the alloy block in a high-temperature tube furnace, raising the temperature to 750 ℃ at the speed of 5 ℃/min, and preserving the heat for 3 h; then the temperature is reduced to 500 ℃ at the speed of 5 ℃/min, and finally the furnace is cooled, and argon with the flow rate of 400ml/min is introduced in the process.
Cu-0.75 wt% Cr-0.2 wt% Zr-2.0 wt% Y after sintering2O3The Vickers hardness of the alloy block reaches 253.2HV0.1145.3HV higher than pure CuCrZr0.1The strength was increased to 432.4MPa, and the conductivity was 78.4% IACS.
Example 3
Cu-0.75 wt% Cr-0.2 wt% Zr-3.0 wt% Y in this example2O3The copper alloy material is prepared by ball milling, wet chemical method, spark plasma sintering and final homogenizing annealing.
Cu-0.75 wt% Cr-0.2 wt% Zr-3.0 wt% Y in this example2O3The preparation method of the alloy block body comprises the following steps:
1. mechanical alloying: copper powder, chromium powder and zirconium powder are proportioned and weighed according to the proportion of Cu-0.75 wt% Cr-0.2 wt% Zr, the weighed materials are all poured into a ball milling tank, stainless steel grinding balls are placed into the ball milling tank according to the proportion of ball material ratio of 15:1, air in the ball milling tank is replaced by argon in a glove box, the oxidation of the powder in the ball milling process is prevented, the ball milling tank is placed into a high-energy ball mill for ball milling after being packaged in the glove box, the ball milling specific parameters are ball milling for 20 hours at the rotating speed of 400rpm, and the Cu-0.75 wt% Cr-0.2 wt% Zr alloy powder which is uniformly mixed can be obtained;
2. second phase particles Y2O3The doping of (2): taking the Cu-0.75 wt% Cr-0.2 wt% Zr alloy powder obtained in the step 1 and quantitative yttrium nitrate (Y (NO)3)3·6H2O)Dissolving the raw materials in a beaker filled with 100ml of deionized water, adding a polytetrafluoroethylene stirrer into the beaker after a glass rod is uniformly stirred, putting the beaker in a magnetic stirrer, heating the beaker to 140 ℃ in an oil bath until the deionized water in the beaker is completely evaporated, putting the beaker in a drying oven, drying for 24 hours at 120 ℃ to remove residual water, and obtaining the CuCrZr-Y (NO)3)3And (3) putting the precursor powder into a high-temperature tube furnace for calcining and reducing: heating to 800 deg.C at a speed of 5 deg.C/min in hydrogen atmosphere at a flow rate of 500ml/min, maintaining for 2h, cooling to 500 deg.C at a speed of 5 deg.C/min, and furnace cooling to obtain Cu-0.75 wt% Cr-0.2 wt% Zr-3.0 wt% Y2O3Compounding powder;
3. and (3) sintering: 12g of Cu-0.75 wt% Cr-0.2 wt% Zr-3.0 wt% Y were weighed2O3The composite powder is put into a graphite die with the diameter of 20mm, graphite pressure heads are put at two ends of the composite powder, after the powder is pre-pressed, the composite powder is put into a sintering furnace, and when the pressure in the furnace cavity is pumped to be below 20Pa, a sintering procedure is started: heating to 600 deg.C at a heating rate of 100 deg.C/min, and maintaining at 10MPa for 5 min; then raising the temperature to 1000 ℃ at the heating rate of 100 ℃/min, preserving the heat for 5min, raising the pressure from 10MPa to 70MPa during the heating period, and quickly reducing the temperature to the room temperature after the heat preservation is finished;
4. homogenizing and annealing: the resulting Cu-0.75 wt% Cr-0.2 wt% Zr-3.0 wt% Y2O3Placing the alloy block in a high-temperature tube furnace, heating to 800 ℃ at the speed of 5 ℃/min, and preserving heat for 3 h; then the temperature is reduced to 500 ℃ at the speed of 5 ℃/min, and finally the furnace is cooled, and argon with the flow rate of 500ml/min is introduced in the process.
Cu-0.75 wt% Cr-0.2 wt% Zr-3.0 wt% Y after sintering2O3The Vickers hardness of the alloy block reaches 272.3HV0.1145.3HV higher than pure CuCrZr0.1The strength was increased to 460.6MPa, and the conductivity was slightly decreased to 74.9% IACS.
TABLE 1 Cu-0.75 wt% Cr-0.2 wt% Zr-Y2O3Mechanical properties of block
As can be seen from FIG. 1, the morphology of the powder is changed from spherical to cake-shaped, and the elements Cr and Zr in the ball-milled CuCrZr powder are uniformly distributed. The invention realizes the combination of three alloys of Cu, Cr and Zr at atomic level by a ball milling mode. Cu, Cr and Zr powder is subjected to long-time violent impact and collision between powder particles and grinding balls in a high-energy ball mill, so that the powder particles are repeatedly subjected to cold welding and fracture, atoms in the powder particles are diffused, and CuCrZr alloying powder is obtained.
From FIG. 2 it can be seen that the powder surface presents a number of fine protruding particles with a composition of yttria illustrating the wet chemical process to obtain Y2O3Dispersedly distributed CuCrZr-Y2O3And (3) compounding the powder.
It can be seen from FIG. 3 that the fracture is mainly composed of individual dimples, illustrating that the fracture mode of the test specimen is ductile fracture.
As can be seen from Table 1, the spark plasma sintering can obtain a block with a density close to 100%, which follows Y2O3The content is increased, and the hardness and the strength are respectively increased to 185.2-272.3 HV0.1And 378.3-460.6 MPa, and the conductivity is maintained at a higher level of 84.3-74.9% IACS, so that the strength and hardness of the traditional CuCrZr alloy are improved while the conductivity is ensured.
The above examples merely illustrate specific embodiments of the present disclosure, but embodiments of the present disclosure are not limited by the above. Any changes, modifications, substitutions, combinations, and simplifications which do not materially depart from the spirit and principles of the inventive concepts disclosed herein are intended to be equivalent permutations and to be included within the scope of the invention as defined by the following claims.
Claims (7)
1. Doped Y2O3The preparation method of the reinforced CuCrZr alloy is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: mechanical alloying
Putting a certain amount of copper powder, chromium powder and zirconium powder into a ball milling tank, replacing air in the ball milling tank with argon in a glove box to prevent oxidation of the powder in the ball milling process, putting stainless steel grinding balls into the ball milling tank according to the ball-to-material ratio of 10: 1-15: 1, sealing the ball milling tank in the glove box, and then putting the ball milling tank into a high-energy ball mill for ball milling to obtain CuCrZr alloy powder;
step two: second phase particles Y2O3Incorporation of
Taking the CuCrZr alloy powder obtained in the step one and Y (NO)3)3·6H2Dissolving O in a beaker filled with 100-300 ml of deionized water, adding a polytetrafluoroethylene stirrer into the beaker after a glass rod is uniformly stirred, putting the beaker in a magnetic stirrer, heating the beaker to 120-140 ℃ in an oil bath, drying the beaker for 12-24 hours at 120-140 ℃ after deionized water in the beaker is completely evaporated, removing residual water, and obtaining the CuCrZr-Y (NO)3)3The precursor powder is placed in a high-temperature tube furnace for calcination and reduction to finally obtain the CuCrZr-Y2O3Composite powder;
step three: spark plasma sintering
Weighing 10-15 g of CuCrZr-Y prepared in the second step2O3Placing the composite powder into a graphite mold with the diameter of 20mm, placing graphite pressure heads at two ends of the composite powder, prepressing the powder, placing the powder into a sintering furnace, starting sintering when the pressure in the furnace cavity is pumped to be below 20Pa, and quickly cooling to room temperature after heat preservation is finished to obtain compact CuCrZr-Y2O3An alloy block;
step four: homogenizing annealing
The CuCrZr-Y obtained in the third step2O3Placing the alloy block in a high-temperature tube furnace, heating to 700-800 ℃ at the speed of 5 ℃/min, and preserving heat for 3 h; cooling to 500 ℃ at a speed of 5 ℃/min, and finally cooling along with the furnace, wherein argon gas with a flow rate of 300-500 ml/min is introduced in the process.
2. Doping Y as set forth in claim 12O3Preparation of reinforced CuCrZr alloyThe preparation method is characterized by comprising the following steps: in the first step, the ball milling speed is 200-400 rpm, and the ball milling time is 20-40 h.
3. Doping Y as set forth in claim 12O3The preparation method of the reinforced CuCrZr alloy is characterized by comprising the following steps: in the first step, the copper powder, the chromium powder and the zirconium powder are mixed according to the proportion of Cu- (0.6-0.8) wt% of Cr- (0.1-0.3) wt% of Zr, and the copper powder, the chromium powder and the zirconium powder are all spherical particles with the granularity of 1-5 mu m.
4. Doping Y as set forth in claim 12O3The preparation method of the reinforced CuCrZr alloy is characterized by comprising the following steps: in the second step, CuCrZr powder and Y (NO)3)3·6H2The content of O is in accordance with CuCrZr-1 wt% Y2O3，CuCrZr-2wt％Y2O3，CuCrZr-3wt％Y2O3And (4) proportioning.
5. Doping Y as set forth in claim 12O3The preparation method of the reinforced CuCrZr alloy is characterized by comprising the following steps: in the second step, CuCrZr-Y (NO)3)3The calcination and reduction of the precursor powder in the high-temperature tube furnace have the following specific parameters: in a hydrogen atmosphere with a flow rate of 300-500 ml/min, raising the temperature to 600-800 ℃ at a speed of 5 ℃/min, preserving the heat for 2h, then lowering the temperature to 500 ℃ at a speed of 5 ℃/min, and finally cooling along with the furnace.
6. Doping Y as set forth in claim 12O3The preparation method of the reinforced CuCrZr alloy is characterized by comprising the following steps: and in the third step, the pre-pressure of the powder is 3 MPa.
7. Doping Y as set forth in claim 12O3The preparation method of the reinforced CuCrZr alloy is characterized by comprising the following steps: the sintering procedure in the third step is as follows: raising the temperature to 600 ℃ at the heating rate of 100 ℃/min, preserving the heat for 3-5 min, then raising the temperature to 900-1000 ℃ at the heating rate of 100 ℃/min, preserving the heat for 3-5 min, and raising the pressure from 0-10 MPa to 50-70 MPa during the heating.
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