CN117884637A - Forming method of metal hydride and high-vacuum cooperative oxygen control integral contact and contact - Google Patents
Forming method of metal hydride and high-vacuum cooperative oxygen control integral contact and contact Download PDFInfo
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- CN117884637A CN117884637A CN202410275195.4A CN202410275195A CN117884637A CN 117884637 A CN117884637 A CN 117884637A CN 202410275195 A CN202410275195 A CN 202410275195A CN 117884637 A CN117884637 A CN 117884637A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 229910052987 metal hydride Inorganic materials 0.000 title claims abstract description 41
- 150000004681 metal hydrides Chemical class 0.000 title claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 23
- 239000001301 oxygen Substances 0.000 title claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 99
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 98
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 52
- 239000010439 graphite Substances 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 48
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 230000008595 infiltration Effects 0.000 claims abstract description 8
- 238000001764 infiltration Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 40
- 150000004678 hydrides Chemical class 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- -1 lanthanum hydride Chemical compound 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 4
- RSHAOIXHUHAZPM-UHFFFAOYSA-N magnesium hydride Chemical compound [MgH2] RSHAOIXHUHAZPM-UHFFFAOYSA-N 0.000 claims description 4
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000047 yttrium hydride Inorganic materials 0.000 claims description 4
- 230000002195 synergetic effect Effects 0.000 claims 2
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 abstract description 6
- 230000007812 deficiency Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229910000881 Cu alloy Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QZLJNVMRJXHARQ-UHFFFAOYSA-N [Zr].[Cr].[Cu] Chemical compound [Zr].[Cr].[Cu] QZLJNVMRJXHARQ-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Powder Metallurgy (AREA)
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Abstract
The invention discloses a method for forming an integral contact by combining metal hydride and high vacuum for controlling oxygen and the contact, which are implemented according to the following steps: step 1, ball milling, mixing and pressing W powder and Cu powder to obtain a pressed green body, and infiltrating and sintering the pressed green body to obtain a CuW alloy; step 2, placing the CuCrZr alloy, the CuW alloy and the metal hydride into a graphite mold; and 3, placing the graphite die in the step 2 in a furnace body, vacuumizing, heating to a set temperature, and preserving heat to obtain the CuW/CuCrZr integrated contact. The contact obtained by the method solves the problems of Cu 5 Zr phase deficiency and low alloy softening temperature caused by zirconium oxidation burning loss in a micro-area in the long-time infiltration molding process of the integral contact.
Description
Technical Field
The invention belongs to the technical field of electrical contacts, and particularly relates to a method for forming an integral contact by combining metal hydride and high-vacuum oxygen control, and also relates to a CuW/CuCrZr integral contact.
Background
The circuit breaker is a key device responsible for the connection and disconnection of a power grid, and the contact is a core component for opening and closing in the circuit breaker, is formed by connecting ablation-resistant copper-tungsten alloy and conductive copper alloy, and is also the best candidate material of the contact at present. With the continuous improvement of the installed capacity of the power grid, the breaking current of the high-voltage circuit breaker is continuously improved, particularly the commercial operation of an extra-high voltage power grid and the large-scale installation of the generator circuit breaker, the high-temperature softening deformation and the thermal stress effect of the copper alloy at the conductive end of the integral contact lead the bonding interface strength of the copper alloy and the copper alloy to be insufficient when the large current is broken, so that the key difficulty of restricting the normal open of the copper tungsten alloy (CuW alloy)/copper alloy integral contact directly influences the reliability and the service life of the safe operation of the contact product.
As a common high-strength high-conductivity copper alloy, the copper-chromium-zirconium (CuCrZr) alloy can be used for precipitating reinforced second-phase Cu 5 Zr particles in the material through solid solution, aging and other basic heat treatment processes, and the softening resistance of the CuCrZr alloy can be remarkably improved through the pinning effect of high-density Cu 5 Zr particles; at the same time, precipitation of the strengthening phase can reduce scattering effect of the matrix on electrons, and high strength and high conductivity are realized. The strength of the CuCrZr alloy after solution aging treatment is 3 times that of pure copper, the CuCrZr alloy has the conductivity of 80 percent IACS, and has good performances of no softening and the like under the high-temperature environment of 550 ℃, thus being a copper alloy material capable of simultaneously realizing high strength and high conductivity. However, in the long-time infiltration molding process of the integral contact, the problem of high-temperature oxidation of the CuCrZr alloy is remarkable, so that the prepared CuW/CuCrZr integral contact conductive end CuCrZr alloy is softened and deformed at high temperature, and the contact cannot be normally broken. Therefore, the technical problem that Cu 5 Zr phase is lost and the softening temperature of alloy is low due to zirconium oxidation burning loss in a micro-area in a long-time infiltration molding process is needed to be solved.
Disclosure of Invention
The invention aims to provide a method for forming an integral contact by combining metal hydride and high-vacuum co-oxygen control, which solves the problems of Cu 5 Zr phase loss and low alloy softening temperature caused by zirconium oxidation burning loss in a micro-area in a long-time infiltration forming process of the integral contact.
It is another object of the present invention to provide a CuW/CuCrZr bulk contact obtained by the above molding method.
The technical scheme adopted by the invention is that the method for forming the integral contact by combining metal hydride and high vacuum for controlling oxygen is implemented according to the following steps:
Step 1, ball milling, mixing and pressing W powder and Cu powder to obtain a pressed green body, and infiltrating and sintering the pressed green body to obtain a CuW alloy;
Step 2, placing the CuCrZr alloy, the CuW alloy obtained in the step 1 and the metal hydride into a graphite mold;
And 3, placing the graphite die in the step 2 in a furnace body, vacuumizing, heating to a set temperature, and preserving heat to obtain the CuW/CuCrZr integrated contact.
The invention is also characterized in that in the step 1, the particle size of the W powder is 0.3-20 mu m, the particle size of the Cu powder is 20-100 mu m, and the addition amounts of the W powder and the Cu powder are respectively as follows: the weight percentage of the W powder is 95% -99%, the weight percentage of the Cu powder is 1% -5%, and the sum of the weight percentages is 100%.
Further, in step 1, the pressing process is as follows: and pressing the mixed powder on a four-column hydraulic press at the pressure of 340MPa, and maintaining the pressure for 30-120 s.
Further, in the step 1, the infiltration sintering process is as follows: and (3) placing the pressed green body and the T2 red copper block in a graphite crucible in sequence from bottom to top in an H 2 atmosphere sintering furnace, heating to 1300-1500 ℃, preserving heat for 30-120 min, and cooling along with the furnace.
Further, the metal hydride comprises a low-temperature reduction hydride and a high-temperature reduction hydride, the low-temperature reduction hydride is any one of magnesium hydride and calcium hydride, the high-temperature reduction hydride is any one of lanthanum hydride and yttrium hydride, the addition amount of the low-temperature reduction hydride is 1-3 times of the mass of Zr in the CuCrZr alloy, and the addition amount of the high-temperature reduction hydride is 3-5 times of the mass of Zr in the CuCrZr alloy.
Further, in the step 2, the graphite mold comprises a graphite crucible, a plurality of grooves are formed in the inner wall of the graphite crucible along the circumference of the graphite crucible, the grooves are sequentially distributed along the axial direction of the graphite crucible, and two adjacent grooves in the middle position are respectively arranged on two sides of the contact surface of the CuCrZr alloy and the CuW alloy;
each groove is internally provided with metal hydride, and the graphite crucible is internally provided with CuW alloy and CuCrZr alloy from bottom to top in sequence.
Further, a mixture of a low-temperature reducing hydride and a high-temperature reducing hydride is provided in each groove.
Further, the low-temperature reducing hydrides and the high-temperature reducing hydrides are alternately arranged in all the grooves.
Further, the specific process of the step 3 is as follows: and (3) placing the graphite die in the step (2) in a furnace body, sequentially adopting a mechanical pump, a Roots pump and a diffusion pump to perform three-stage vacuumizing treatment on the furnace body, so that the vacuum degree in the furnace body is not higher than 1.0X10 -2 Pa, heating to 400-600 ℃ at a heating rate of 15 ℃/min, preserving heat for 30-120 min, heating to 800-1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 30-120 min, and finally heating to 1200-1400 ℃ at a heating rate of 5 ℃/min for 1 h-4 h, and cooling along with the furnace to obtain the CuW/CuCrZr integral contact.
The other technical scheme adopted by the invention is that the CuW/CuCrZr integrated contact is obtained by adopting the forming method.
The beneficial effects of the invention are as follows:
(1) According to the method for forming the integral contact by combining the metal hydride and the high-vacuum oxygen control, the oxygen content is controlled by utilizing the high-vacuum environment of the furnace body, so that oxidation is prevented; meanwhile, based on a metal oxidation-reduction principle, the oxidation burning loss rate of zirconium element in the CuCrZr alloy in the long-time infiltration process is effectively reduced, and the high-density precipitation of Cu 5 Zr phase is ensured;
(2) The CuCrZr alloy at the conductive end of the CuW/CuCrZr integrated contact, which is obtained by adopting the metal hydride and high-vacuum collaborative oxygen-control integrated contact molding method, has high softening temperature, and solves the serious problem that the contact cannot be normally closed due to high-temperature softening deformation of the copper alloy when large-capacity breaking occurs.
Drawings
FIG. 1 is a schematic diagram of the structure of a graphite mold in the method for forming an integral contact with metal hydride and high vacuum coordinated oxygen control according to the present invention;
FIG. 2 is a microstructure view of a CuCrZr alloy with a scale of 200nm in a CuW/CuCrZr integrated contact, which is obtained by the metal hydride and high vacuum collaborative oxygen control integrated contact molding method of the invention;
FIG. 3 is a microstructure view of a CuCrZr alloy with a scale of 10nm in a CuW/CuCrZr integrated contact obtained by the metal hydride and high vacuum collaborative oxygen control integrated contact molding method of the invention;
FIG. 4 is a microstructure view of a CuCrZr alloy with a scale of 10 1/nm of the inverted space in the CuW/CuCrZr integrated contact, which is obtained by the metal hydride and high vacuum collaborative oxygen control integrated contact molding method of the invention;
FIG. 5 is a microstructure of a CuCrZr alloy with a scale of 200nm in a CuW/CuCrZr bulk contact obtained in a comparative example;
FIG. 6 is a microstructure of a CuCrZr alloy with a scale of 10nm in a CuW/CuCrZr bulk contact obtained in a comparative example;
FIG. 7 is a microstructure view of the CuCrZr alloy with the scale of the inverted space of 51/nm in the CuW/CuCrZr integrated contactor obtained in the comparative example;
FIG. 8 is a graph showing the results of a test for the softening temperature of a CuCrZr alloy in a CuW/CuCrZr bulk contact obtained in example 3 of the present invention and a CuW/CuCrZr bulk contact obtained in comparative example.
In the figure, 1, a graphite crucible, 2, a groove, 3, a metal hydride, 4, a CuW alloy and 5, a CuCrZr alloy.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention relates to a method for forming an integral contact by combining metal hydride and high vacuum for controlling oxygen, which is implemented according to the following steps:
Step 1, mixing W powder with the particle size of 0.3-20 mu m and Cu powder with the particle size of 20-100 mu m at the rotating speed of 150-400 r/min for ball milling for 1-4 hours, pressing the mixed powder on a four-column hydraulic press at the pressure of 340MPa, maintaining the pressure for 30-120 s to obtain a pressed green body, sequentially placing the pressed green body and a T2 red copper block in a graphite crucible from bottom to top in an H 2 atmosphere sintering furnace, heating to 1300-1500 ℃ at the heating rate of 10 ℃/min, preserving heat for 30-120 min, and cooling along with a furnace to obtain a CuW alloy 4;
Wherein, the addition amounts of the W powder and the Cu powder are respectively as follows: the weight percentage of the W powder is 95% -99%, the weight percentage of the Cu powder is 1% -5%, and the sum of the weight percentages is 100%;
Step 2, placing the CuCrZr alloy 5, the CuW alloy 4 obtained in the step 1 and the metal hydride 3 in a graphite mold;
The metal hydride comprises a hydride for low-temperature reduction and a hydride for high-temperature reduction, wherein the hydride for low-temperature reduction is any one of magnesium hydride and calcium hydride, the addition amount of the hydride for low-temperature reduction is 1-3 times of the Zr mass in the CuCrZr alloy 5, the hydride for high-temperature reduction is any one of lanthanum hydride and yttrium hydride, and the addition amount of the hydride for high-temperature reduction is 3-5 times of the Zr mass in the CuCrZr alloy 5;
the structure of the graphite mold is shown in fig. 1, and the graphite mold comprises a graphite crucible 1, wherein a plurality of grooves 2 are formed in the inner wall of the graphite crucible 1 along the circumference of the inner wall of the graphite crucible 1, the grooves 2 are sequentially distributed along the axial direction of the graphite crucible 1, and two adjacent grooves 2 positioned in the middle position are respectively arranged on two sides of the contact surface of a CuCrZr alloy 5 and a CuW alloy 4; the specific placement positions of the CuCrZr alloy 5, the CuW alloy 4 obtained in the step 1 and the metal hydride 3 in the graphite mold are as follows: the metal hydride 3 is arranged in each groove 2, the CuW alloy 4 and the CuCrZr alloy 5 are sequentially arranged in the graphite crucible 1 from bottom to top, and the height of the groove 2 positioned at the top is not higher than the top of the CuCrZr alloy 5;
Specifically, a mixture of a low-temperature reducing hydride and a high-temperature reducing hydride is provided in each of the grooves 2, or a mixture of a low-temperature reducing hydride and a high-temperature reducing hydride is alternately provided in all of the grooves 2;
Based on the metal oxidation-reduction principle, the invention takes metal hydrides as a sacrificial agent in a micro-area by means of a graphite die, utilizes magnesium hydride, calcium hydride and other metal hydrides to decompose at a low temperature of 400-600 ℃ and lanthanum hydride, yttrium hydride and other metal hydrides at a high temperature of 800-1000 ℃ to produce hydrogen and oxygen-philic elementary metal which are preferentially combined with zirconium and oxygen to play a reduction role, thereby effectively reducing the oxidation burning loss of zirconium element in the CuCrZr alloy 5 in a long-time infiltration process and ensuring the high-density precipitation of Cu 5 Zr phase;
And 3, placing the graphite die in the step 2 in a furnace body, sequentially adopting a mechanical pump, a Roots pump and a diffusion pump to perform three-stage vacuumizing treatment on the furnace body, enabling the vacuum degree in the furnace body to be not higher than 1.0X10 -2 Pa, heating to 400-600 ℃ at a heating rate of 15 ℃/min, preserving heat for 30-120 min, heating to 800-1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 30-120 min, and finally heating to 1200-1400 ℃ at a heating rate of 5 ℃/min, preserving heat for 1 h-4 h, and then cooling along with the furnace to obtain the CuW/CuCrZr integral contact.
Firstly, the method adopts a three-stage vacuumizing design of a mechanical pump, a Roots pump and a diffusion pump, so that the air entering in the reaction process is greatly reduced, the oxidation problem caused by no air and other gas impurities in the furnace body is ensured, and the oxidation of the CuCrZr alloy is avoided; secondly, the method of the invention uses metal hydride for low-temperature reduction and metal hydride for high-temperature reduction to decompose in a low-temperature zone and a high-temperature zone respectively, so that oxygen generated in gas exhausted from a graphite crucible used in the process of reducing and heating due to the complex structure of the whole contact is further ensured to oxidize the CuCrZr alloy in a micro-zone; in conclusion, the method adopts the two schemes and the three-stage cooperative oxygen control technology to ensure the oxidation burning loss of Zr element in the CuCrZr alloy, thereby ensuring the high-density precipitation of Cu 5 Zr precipitation phase and leading the alloy to have higher softening temperature.
The CuW/CuCrZr integrated contact is obtained by adopting the metal hydride and high-vacuum collaborative oxygen control integrated contact molding method.
Example 1
Step 1, ball milling W powder with the average particle size of 0.3 mu m and Cu powder with the particle size of 20 mu m for 1H at the rotation speed of 400r/min, pressing the mixed powder on a four-column hydraulic press at the pressure of 340MPa, maintaining the pressure for 30s to obtain a pressed green body, sequentially placing the pressed green body and a T2 red copper block in a graphite crucible from bottom to top in an H 2 atmosphere sintering furnace, heating to 1300 ℃ at the heating rate of 10 ℃/min, preserving heat for 120min, and cooling along with the furnace to obtain CuW alloy 4;
Wherein, the addition amounts of the W powder and the Cu powder are respectively as follows: the weight percentage of the W powder is 95 percent, and the weight percentage of the Cu powder is 5 percent;
Step 2, processing the CuCrZr alloy 5 and the CuW alloy 4 obtained in the step 1 into designed sizes, respectively performing ultrasonic cleaning in acetone or alcohol to remove oil stains and impurities adhered to the surface, and placing the CuCrZr alloy 5, the CuW alloy 4 obtained in the step 1 and the metal hydride 3 in a graphite mold, wherein the specific placing positions are as follows: the inside of each groove 2 is provided with a mixture of low-temperature reduction hydride magnesium hydride and high-temperature reduction hydride lanthanum hydride, the inside of the graphite crucible 1 is sequentially provided with a CuW alloy 4 and a CuCrZr alloy 5 from bottom to top, and the height of the groove 2 positioned at the top is not higher than the top of the CuCrZr alloy 5;
Wherein the addition amount of the hydride for low-temperature reduction is 1 time of the Zr mass in the CuCrZr alloy 5, and the addition amount of the hydride for high-temperature reduction is 5 times of the Zr mass in the CuCrZr alloy 5;
And 3, placing the graphite die in the step 2 in a furnace body, sequentially adopting a mechanical pump, a Roots pump and a diffusion pump to perform three-stage vacuumizing treatment on the furnace body, so that the vacuum degree in the furnace body is not higher than 1.0X10 -2 Pa, heating to 400 ℃ at a heating rate of 15 ℃/min, preserving heat for 120min, heating to 1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 30min, heating to 1200 ℃ at a heating rate of 5 ℃/min, preserving heat for 4h, and cooling with the furnace to obtain the CuW/CuCrZr integrated contact.
Example 2
Step 1, ball milling W powder with the average particle size of 20 mu m and Cu powder with the particle size of 100 mu m for 4 hours at the rotating speed of 150r/min, pressing the mixed powder on a four-column hydraulic press at the pressure of 340MPa, maintaining the pressure for 120 seconds to obtain a pressed green body, sequentially placing the pressed green body and a T2 red copper block in a graphite crucible from bottom to top in an H 2 atmosphere sintering furnace, heating to 1500 ℃ at the heating rate of 10 ℃/min, preserving heat for 30 minutes, and cooling along with the furnace to obtain CuW alloy 4;
wherein, the addition amounts of the W powder and the Cu powder are respectively as follows: the weight percentage of the W powder is 99 percent, and the weight percentage of the Cu powder is 1 percent;
Step 2, processing the CuCrZr alloy 5 and the CuW alloy 4 obtained in the step 1 into designed sizes, respectively performing ultrasonic cleaning in acetone or alcohol to remove oil stains and impurities adhered to the surface, and placing the CuCrZr alloy 5, the CuW alloy 4 obtained in the step 1 and the metal hydride 3 in a graphite mold, wherein the specific placing positions are as follows: the inside of each groove 2 is provided with a mixture of low-temperature reduction hydride calcium hydride and high-temperature reduction hydride yttrium hydride, the inside of the graphite crucible 1 is sequentially provided with a CuW alloy 4 and a CuCrZr alloy 5 from bottom to top, and the height of the groove 2 positioned at the top is not higher than the top of the CuCrZr alloy 5;
Wherein the addition amount of the hydride for low-temperature reduction is 3 times of the Zr mass in the CuCrZr alloy 5, and the addition amount of the hydride for high-temperature reduction is 3 times of the Zr mass in the CuCrZr alloy 5;
And 3, placing the graphite die in the step 2 in a furnace body, sequentially adopting a mechanical pump, a Roots pump and a diffusion pump to perform three-stage vacuumizing treatment on the furnace body, so that the vacuum degree in the furnace body is not higher than 1.0X10 -2 Pa, heating to 600 ℃ at a heating rate of 15 ℃/min for 30min, heating to 800 ℃ at a heating rate of 10 ℃/min for 120min, heating to 1400 ℃ at a heating rate of 5 ℃/min for 1h, and cooling with the furnace to obtain the CuW/CuCrZr integrated contact.
Example 3
Step 1, ball milling W powder with the average particle size of 6 mu m and Cu powder with the particle size of 60 mu m at the rotating speed of 200r/min for 2 hours, pressing the mixed powder on a four-column hydraulic press at the pressure of 340MPa, maintaining the pressure for 60 seconds to obtain a pressed green body, sequentially placing the pressed green body and a T2 red copper block in a graphite crucible from bottom to top in an H 2 atmosphere sintering furnace, heating to 1350 ℃ at the heating rate of 10 ℃/min, preserving heat for 60 minutes, and cooling along with the furnace to obtain CuW alloy 4;
wherein, the addition amounts of the W powder and the Cu powder are respectively as follows: the mass percentage of the W powder is 97%, and the mass percentage of the Cu powder is 3%;
Step 2, processing the CuCrZr alloy 5 and the CuW alloy 4 obtained in the step 1 into designed sizes, respectively performing ultrasonic cleaning in acetone or alcohol to remove oil stains and impurities adhered to the surface, and placing the CuCrZr alloy 5, the CuW alloy 4 obtained in the step 1 and the metal hydride 3 in a graphite mold, wherein the specific placing positions are as follows: the method comprises the steps that hydride magnesium hydride for low-temperature reduction and hydride yttrium hydride for high-temperature reduction are alternately arranged in all grooves 2, a CuW alloy 4 and a CuCrZr alloy 5 are sequentially arranged in a graphite crucible 1 from bottom to top, and the height of the groove 2 at the top is not higher than that of the CuCrZr alloy 5;
Wherein the addition amount of the hydride for low-temperature reduction is 2 times of the Zr mass in the CuCrZr alloy 5, and the addition amount of the hydride for high-temperature reduction is 3 times of the Zr mass in the CuCrZr alloy 5;
And 3, placing the graphite die in the step 2 in a furnace body, sequentially adopting a mechanical pump, a Roots pump and a diffusion pump to perform three-stage vacuumizing treatment on the furnace body, so that the vacuum degree in the furnace body is not higher than 1.0X10 -2 Pa, heating to 500 ℃ at a heating rate of 15 ℃/min for 60min, heating to 900 ℃ at a heating rate of 10 ℃/min for 60min, heating to 1300 ℃ at a heating rate of 5 ℃/min for 2h, and cooling with the furnace to obtain the CuW/CuCrZr integrated contact.
Comparative example
Step 1, ball milling W powder with the average particle size of 6 mu m and Cu powder with the particle size of 60 mu m at the rotating speed of 200r/min for 2 hours, pressing the mixed powder on a four-column hydraulic press at the pressure of 340MPa, maintaining the pressure for 60 seconds to obtain a pressed green body, sequentially placing the pressed green body and a T2 red copper block in a graphite crucible from bottom to top in an H 2 atmosphere sintering furnace, heating to 1350 ℃ at the heating rate of 10 ℃/min, preserving heat for 60 minutes, and cooling along with the furnace to obtain a CuW alloy;
wherein, the addition amounts of the W powder and the Cu powder are respectively as follows: the mass percentage of the W powder is 97%, and the mass percentage of the Cu powder is 3%;
Step 2, processing the CuCrZr alloy and the CuW alloy obtained in the step 1 into designed sizes, respectively performing ultrasonic cleaning in acetone or alcohol to remove oil stains and impurities adhered to the surface, and sequentially placing the CuCrZr alloy and the CuW alloy obtained in the step 1 into a graphite crucible from top to bottom;
And 3, placing the graphite crucible in the step 2 in a furnace body, sequentially adopting a mechanical pump, a Roots pump and a diffusion pump to perform three-stage vacuumizing treatment on the furnace body, so that the vacuum degree in the furnace body is not higher than 1.0X10 -2 Pa, heating to 500 ℃ at a heating rate of 15 ℃/min for 60min, heating to 900 ℃ at a heating rate of 10 ℃/min for 60min, heating to 1300 ℃ at a heating rate of 5 ℃/min for 2h, and cooling with the furnace to obtain the CuW/CuCrZr integrated contact.
Observing the CuW/CuCrZr integral contact obtained by the method under a transmission electron microscope, and as can be seen from figures 2, 3 and 4, the CuCrZr alloy prepared by adopting the collaborative oxygen control technology not only can be separated out by Cr particles, but also can be separated out by high-density Cu 5 Zr; the CuW/CuCrZr integrated contact obtained in the comparative example is observed under a transmission electron microscope, and as can be seen from fig. 5, 6 and 7, after the calibration analysis of the transmission electron microscope, the precipitated phase in the alloy is mainly Cr particles, and the Zr element is difficult to detect the Cu 5 Zr precipitated phase because of oxidation burning loss in the sintering process.
The conductivity of the CuCrZr alloy in the CuW/CuCrZr integrated contacts obtained in the embodiments 1-3 is more than or equal to 84% IACS, the softening temperature is higher than 500 ℃, the interface bonding strength is still higher than 300MPa at 500 ℃, and the service requirements of large-current on-off on the breaker contacts can be met, wherein the softening temperature of the embodiment 3 is highest; as shown in FIG. 8, the CuCrZr in the CuW/CuCrZr bulk contact obtained in example 3 of the present invention
The softening temperature of the alloy was raised to 570 ℃.
Claims (8)
1. The integral contact forming method for the metal hydride and the high vacuum cooperative oxygen control is characterized by comprising the following steps of:
Step 1, ball milling, mixing and pressing W powder and Cu powder to obtain a pressed green body, and infiltrating and sintering the pressed green body to obtain a CuW alloy (4);
step2, placing the CuCrZr alloy (5), the CuW alloy (4) obtained in the step 1 and the metal hydride (3) in a graphite mold;
the graphite mold comprises a graphite crucible (1), wherein a plurality of grooves (2) are formed in the inner wall of the graphite crucible (1) along the circumference of the inner wall of the graphite crucible, the grooves (2) are sequentially distributed along the axial direction of the graphite crucible (1), and two adjacent grooves (2) positioned at the middle position are respectively arranged at two sides of the contact surface of the CuCrZr alloy (5) and the CuW alloy (4);
Each groove (2) is internally provided with a metal hydride (3), and the graphite crucible (1) is internally provided with a CuW alloy (4) and a CuCrZr alloy (5) from bottom to top in sequence;
step 3, placing the graphite die in the step 2 in a furnace body, vacuumizing, heating to a set temperature, and preserving heat to obtain a CuW/CuCrZr integrated contact;
The specific process of the step 3 is as follows: and (3) placing the graphite die in the step (2) in a furnace body, sequentially adopting a mechanical pump, a Roots pump and a diffusion pump to perform three-stage vacuumizing treatment on the furnace body, so that the vacuum degree in the furnace body is not higher than 1.0X10 -2 Pa, heating to 400-600 ℃ at a heating rate of 15 ℃/min, preserving heat for 30-120 min, heating to 800-1000 ℃ at a heating rate of 10 ℃/min, preserving heat for 30-120 min, and finally heating to 1200-1400 ℃ at a heating rate of 5 ℃/min for 1 h-4 h, and cooling along with the furnace to obtain the CuW/CuCrZr integral contact.
2. The method for forming the metal hydride and high-vacuum synergistic oxygen-controlling integrated contact according to claim 1, wherein in the step 1, the particle size of the W powder is 0.3-20 μm, the particle size of the Cu powder is 20-100 μm, and the addition amounts of the W powder and the Cu powder are respectively as follows: the weight percentage of the W powder is 95% -99%, the weight percentage of the Cu powder is 1% -5%, and the sum of the weight percentages is 100%.
3. The method for forming the metal hydride and high vacuum co-oxygen controlled integrated contact according to claim 1, wherein in step 1, the pressing process is as follows: and pressing the mixed powder on a four-column hydraulic press at the pressure of 340MPa, and maintaining the pressure for 30-120 s.
4. The method for forming a monolithic contact with co-oxygen control under high vacuum and metal hydride as set forth in claim 1, wherein in step 1, the infiltration sintering process is as follows: and (3) placing the pressed green body and the T2 red copper block in a graphite crucible in sequence from bottom to top in an H 2 atmosphere sintering furnace, heating to 1300-1500 ℃, preserving heat for 30-120 min, and cooling along with the furnace.
5. The method for forming the metal hydride and the high-vacuum synergistic oxygen-controlling integrated contact according to claim 1, wherein in the step 2, the metal hydride comprises a low-temperature reduction hydride and a high-temperature reduction hydride, the low-temperature reduction hydride is any one of magnesium hydride and calcium hydride, the high-temperature reduction hydride is any one of lanthanum hydride and yttrium hydride, the addition amount of the low-temperature reduction hydride is 1-3 times of the mass of Zr in the CuCrZr alloy (5), and the addition amount of the high-temperature reduction hydride is 3-5 times of the mass of Zr in the CuCrZr alloy (5).
6. The method for forming a monolithic contact with co-operating high vacuum oxygen control with metal hydride according to claim 5, wherein said mixture of low temperature reducing hydride and high temperature reducing hydride is disposed in each of said grooves (2).
7. The method for forming the integrated contact with the metal hydride and the high-vacuum cooperative oxygen control according to claim 5, wherein the hydride for low-temperature reduction and the hydride for high-temperature reduction are alternately arranged in all grooves (2).
A cuw/CuCrZr monolithic contact, characterized in that it is obtained by a molding method according to any one of claims 1 to 7.
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