CN113290229A - Method for preparing CuW/CuCr composite material by high-entropy alloy infiltration - Google Patents
Method for preparing CuW/CuCr composite material by high-entropy alloy infiltration Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 166
- 239000000956 alloy Substances 0.000 title claims abstract description 166
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000008595 infiltration Effects 0.000 title claims abstract description 23
- 238000001764 infiltration Methods 0.000 title claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 38
- 239000007790 solid phase Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 238000003825 pressing Methods 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000011651 chromium Substances 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000012459 cleaning agent Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- 229910000906 Bronze Inorganic materials 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004886 process control Methods 0.000 claims description 6
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 9
- 230000005501 phase interface Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 24
- 239000011572 manganese Substances 0.000 description 18
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D19/00—Casting in, on, or around objects which form part of the product
- B22D19/04—Casting in, on, or around objects which form part of the product for joining parts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/025—Composite material having copper as the basic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
- H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
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Abstract
The invention discloses a method for preparing a CuW/CuCr composite material by high-entropy alloy infiltration, which comprises the steps of weighing Mn, Fe, Cu, Cr and Co raw materials according to a certain atomic percentage, adding the raw materials into a mixer for mixing, then placing the mixture into a rigid die for pressing to obtain a high-entropy alloy blank, then sequentially stacking the CuW alloy, the high-entropy alloy blank and the CuCr alloy in a graphite crucible from top to bottom, and sequentially carrying out solid-phase sintering and liquid-phase connection in a sintering furnace to obtain the CuW/CuCr composite material. The invention realizes the connection between the dissimilar materials CuW and CuCr by introducing the high-entropy alloy of five components, improves the combination mode of a Cu/W phase interface, inhibits the formation of a brittle intermetallic compound phase at the interface and improves the interface combination strength.
Description
Technical Field
The invention belongs to the technical field of preparation of heterogeneous materials, and relates to a method for preparing a CuW/CuCr composite material by high-entropy alloy infiltration.
Background
With the comprehensive construction of the ultra-high voltage power grid in China, the power transmission and transformation equipment gradually changes to the ultra-high voltage application field. The CuW/CuCr composite material is widely applied to an electrical contact of a high-voltage capacitor bank switch, in an extra-high voltage alternating-current transmission project, the capacitor bank is switched on and off thousands of times per year, and the CuW/CuCr interface generates large stress concentration due to the high-frequency switching on and off, so that the interface generates cracks and further expands along a Cu/W phase interface, and finally the whole material is damaged along a joint surface to cause the CuW end to fall off. Therefore, how to improve the bonding strength and the high-temperature softening resistance of the CuW/CuCr dissimilar material interface becomes a key technology for prolonging the service life of the capacitor bank switch.
The CuW/CuCr interface, as analyzed microscopically, is composed primarily of a large number of Cu/W phase interfaces, i.e., a continuous copper phase common to both the CuW bond and a small number of side materials. And the Cu phase and the W phase are not mutually soluble, can not form firm metallurgical bonding and can only exist in the form of mechanical engaging force. Because the mechanical engaging force strength of heterogeneous material connection is far less than the metallurgical bonding force between atoms, the contribution of the Cu-Cu bonding couple to the CuW/CuCr interface bonding strength is large. Therefore, the key to improving the strength of the CuW/CuCr interface is how to improve the strength of the Cu/W phase interface. The intermediate high-entropy alloy interlayer is introduced into the interface of the heterogeneous material or the composite material, and is dissolved to diffuse towards the two sides of the interface, so that a metallurgical diffusion reaction is generated on the interface of the heterogeneous material, the mismatch phenomenon caused by large phase parameter difference can be improved, and the interface bonding strength of the heterogeneous material or the interface mechanical property of the composite material can be improved.
Disclosure of Invention
The invention aims to provide a method for preparing a CuW/CuCr composite material by high-entropy alloy infiltration, which solves the problem that the service life of a capacitor bank switch is short due to low interface bonding strength of the CuW/CuCr composite material under an extra-high voltage service condition in the prior art.
The technical scheme adopted by the invention is that the method for preparing the CuW/CuCr composite material by high-entropy alloy infiltration is implemented according to the following steps:
step 1, weighing the following raw materials in atomic percentage:
5-25% of Mn, 5-20% of Fe, 5-25% of Cu, 5-35% of Cr and 5-25% of Co, wherein the sum of atomic percentages of the elements is 100%;
step 2, adding the raw materials and the process control agent weighed in the step 1 into a mixer for mixing, uniformly mixing to obtain a mixture, and placing the mixture into a rigid die for pressing to obtain a high-entropy alloy blank;
step 3, processing and flattening the pre-bonded end of the CuW alloy, cleaning the pre-bonded end, drying for later use, cutting out a chromium bronze alloy bar, selecting the cut machined surface as a pre-bonded surface of the CuCr alloy, and drying for later use after cleaning;
step 4, stacking the high-entropy alloy blank, the CuW alloy and the CuCr alloy obtained in the step 2 and the step 3 in a crucible from top to bottom in sequence according to the sequence of the CuW alloy, the high-entropy alloy blank and the CuCr alloy;
and 5, heating the crucible in a sintering furnace, performing solid-phase sintering on the high-entropy alloy, performing liquid-phase connection on the heterogeneous material after the solid-phase sintering is finished, and cooling to obtain the CuW/CuCr composite material.
The invention is also characterized in that:
in the step 1, the granularity of Cu, Cr, Co, Fe and Mn is 50-400 meshes, and the purity is 99.9%.
In the step 2, the process control agent is absolute ethyl alcohol, glycerol, butanediol or stearic acid.
The ratio of the balls to the materials mixed in the step 2 is 10-40:1, and the mixing time is 8-12 h.
The pressing pressure in the step 2 is 100-400Mpa, the pressure maintaining time is 30-60s, and the height of the high-entropy alloy blank is 0.5-3 mm.
And 3, arranging a groove matched with the high-entropy alloy blank at the pre-bonding end part of the CuW alloy.
And 3, cleaning the CuW alloy and the CuCr alloy by using a KQ-50DE type numerical control ultrasonic cleaner at the cleaning temperature of 15-25 ℃, firstly cleaning for 15-30 minutes by using an acetone cleaning agent, and then cleaning for 15-30 minutes by using an alcohol cleaning agent.
In the step 5, the heating rate of the solid phase sintering is 5-30 ℃/min, the temperature of the solid phase sintering is 600-1000 ℃, and the heat preservation time is 1-4 h.
And (5) after the solid phase sintering is finished, heating at a heating rate of 5-30 ℃/min, performing liquid phase connection at the temperature of 1100-1400 ℃, keeping the temperature for 0.5-4h, cooling to 800-1000 ℃ at a cooling rate of 5-30 ℃/min, and then cooling to room temperature along with the furnace.
The invention has the beneficial effects that: according to the method for preparing the CuW/CuCr composite material by high-entropy alloy infiltration, the connection between the CuW and the CuCr of the heterogeneous material is realized by introducing the high-entropy alloy with five components, the high-entropy effect of the high-entropy alloy can inhibit the formation of a brittle intermetallic compound phase at an interface, the formation of a simple body-centered cubic or face-centered cubic solid solution at the interface is promoted, and the interface bonding strength is improved. The hardness and the conductivity of the CuCr side of the CuW/CuCr composite material prepared by the method at a position 4mm away from the interface reach 95HB and 64IACS respectively, and meanwhile, the high-entropy alloy has wide component range, good connection adaptability to CuW alloys of different grades, simple process and low cost, and is suitable for mass production.
Drawings
FIG. 1 is a flow chart of a method for preparing a CuW/CuCr composite material by high-entropy alloy infiltration according to the invention;
FIG. 2 shows the hardness of the CuCr composite material with different manganese contents at a position 4mm away from the interface on the CuCr side in the method for preparing the CuW/CuCr composite material by high-entropy alloy infiltration;
FIG. 3 is an SEM image of the joint surface of the CuW/CuCr composite material prepared in example 2 of the present invention;
FIG. 4 is a line scan of the CuW/CuCr composite bonding interface prepared in example 4 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention discloses a method for preparing a CuW/CuCr composite material by high-entropy alloy infiltration, which is implemented according to the following steps as shown in figure 1:
step 1, weighing the following raw materials in atomic percentage:
5-25% of Mn, 5-20% of Fe, 5-25% of Cu, 5-35% of Cr and 5-25% of Co, wherein the sum of atomic percentages of the elements is 100%;
wherein the granularity of Cu, Cr, Co, Fe and Mn is 50-400 meshes, and the purity is 99.9%;
step 2, adding the raw materials and the process control agent weighed in the step 1 into a mixer for mixing, wherein the ball-material ratio for mixing is 10-40:1, the mixing time is 8-12h, the mixture is obtained after uniform mixing, the mixture is placed into a rigid die for pressing to obtain a high-entropy alloy blank, the pressing pressure is 100-400MPa, the pressure maintaining time is 30-60s, and the height of the high-entropy alloy blank is 0.5-3 mm;
the process control agent is absolute ethyl alcohol, glycerol, butanediol or stearic acid;
step 3, processing and flattening the pre-bonded end of the CuW alloy, cleaning the pre-bonded end, drying for later use, cutting out a chromium bronze alloy bar, selecting the cut-out processing surface as a pre-bonded surface of the CuCr alloy, and drying for later use after cleaning;
the pre-combination end part of the CuW alloy is provided with a groove matched with the high-entropy alloy blank;
cleaning CuW alloy and CuCr alloy by using a KQ-50DE type numerical control ultrasonic cleaner at 15-25 ℃, firstly cleaning for 15-30 minutes by using an acetone cleaning agent, and then cleaning for 15-30 minutes by using an alcohol cleaning agent;
step 4, stacking the high-entropy alloy blank, the CuW alloy and the CuCr alloy obtained in the step 2 and the step 3 in a crucible from top to bottom in sequence according to the sequence of the CuW alloy, the high-entropy alloy blank and the CuCr alloy, and embedding the high-entropy alloy blank into a groove at the pre-combined end part of the CuW alloy;
and step 5, placing the crucible in a sintering furnace for heating at a heating rate of 5-30 ℃/min, performing solid-phase sintering on the high-entropy alloy, wherein the temperature of the solid-phase sintering is 600-fold glass-ceramic composite material, the heat preservation time is 1-4h, after the solid-phase sintering is finished, heating at a heating rate of 5-30 ℃/min, performing liquid-phase connection at a temperature of 1100-fold glass-ceramic composite material.
The invention realizes the connection between the heterogeneous materials CuW and CuCr by introducing the multi-component high-entropy alloy, the high-entropy effect of the high-entropy alloy can inhibit the formation of brittle intermetallic compound phases at the interface, promote the interface to form simple body-centered cubic or face-centered cubic solid solution, improve the interface bonding strength, and simultaneously the high-temperature softening resistance of the high-entropy alloy can also prevent the interface from softening at high temperature under the influence of larger arc heat.
The selected alloy elements Fe, Mn, Cu, Cr and Co are the main original two points of the composition of the high-entropy alloy: the five elements of Fe, Mn, Cu, Cr and Co are in the subgroup of the fourth period in the periodic table, and the five elements are adjacent in position, close in atomic radius and very similar in performance. Secondly, the five elements have certain solid solubility in W and Cu, so that firm metallurgical bonding can be formed; the multi-principal-element characteristic of the high-entropy alloy can avoid excessive erosion caused by adding of a single element to a W framework to reduce interface bonding strength, and the high-entropy effect can inhibit an interface from generating a hard and brittle intermetallic compound due to adding of an alloy element, so that the interface is formed in the form of W, Cu two-phase solid solution, the interface bonding mode of the whole material prepared by the conventional method is changed, and the synergistic effect of multiple elements is fully exerted.
The high-entropy alloy is embedded in the CuW pre-combination end groove which is matched with the high-entropy alloy, so that the loss of the high-entropy alloy pressed compact in the liquid phase connection process can be reduced, and the contact reaction between the high-entropy alloy pressed compact and a crucible in the liquid phase connection process is prevented.
The CuCr alloy is a chromium bronze bar with low Cr content, so that the whole material has good conductivity.
According to the invention, solid-phase sintering of the high-entropy alloy blank is carried out in the same sintering furnace according to a time sequence, and then heterogeneous materials are connected. In addition, the solid-phase sintering is beneficial to improving the compactness of the high-entropy alloy blank and reducing the probability of generating defects such as holes. On the other hand, the solid phase sintering process is also a heterogeneous material liquid phase connection preheating process, which is beneficial to improving the production efficiency and saving the production cost.
Example 1
A method for preparing a CuW/CuCr composite material by high-entropy alloy infiltration is implemented according to the following steps:
step 1, weighing the following raw materials in atomic percentage:
25% of Mn, 20% of Fe, 20% of Cu, 10% of Cr and 25% of Co, wherein the sum of atomic percentages of the above elements is 100%;
wherein the granularity of Cu, Cr, Co, Fe and Mn is 300 meshes, and the purity is 99.9%;
step 2, adding the raw materials weighed in the step 1 and absolute ethyl alcohol into a mixer for mixing, wherein the ball-material ratio for mixing is 10:1, the mixing time is 8 hours, the mixture is obtained after uniform mixing, the mixture is placed into a rigid die for pressing to obtain a high-entropy alloy blank, the pressing pressure is 400MPa, the pressure maintaining time is 30s, and the height of the high-entropy alloy blank is 2 mm;
step 3, processing and flattening the pre-bonded end of the CuW alloy, cleaning the pre-bonded end, drying for later use, cutting out a chromium bronze alloy bar, selecting the cut machined surface as a pre-bonded surface of the CuCr alloy, and drying for later use after cleaning;
the pre-combination end part of the CuW alloy is provided with a groove matched with the high-entropy alloy blank;
cleaning the CuW alloy and the CuCr alloy by using a KQ-50DE type numerical control ultrasonic cleaner at the cleaning temperature of 15 ℃, firstly cleaning for 15 minutes by using an acetone cleaning agent, and then cleaning for 15 minutes by using an alcohol cleaning agent;
step 4, stacking the high-entropy alloy blank, the CuW alloy and the CuCr alloy obtained in the step 2 and the step 3 in a crucible from top to bottom in sequence according to the sequence of the CuW alloy, the high-entropy alloy blank and the CuCr alloy, and embedding the high-entropy alloy blank into a groove at the pre-combined end part of the CuW alloy;
and 5, placing the crucible in a sintering furnace for heating at a heating rate of 30 ℃/min, performing solid-phase sintering on the high-entropy alloy, wherein the temperature of the solid-phase sintering is 1000 ℃, the heat preservation time is 2h, after the solid-phase sintering is finished, heating at a heating rate of 30 ℃/min, performing liquid-phase connection at 1400 ℃, the heat preservation time is 0.5h, then cooling to 1000 ℃ at a cooling rate of 30 ℃/min, and then cooling to room temperature along with the furnace, thus obtaining the CuW/CuCr composite material.
Example 2
A method for preparing a CuW/CuCr composite material by high-entropy alloy infiltration is implemented according to the following steps:
step 1, weighing the following raw materials in atomic percentage:
20% of Mn, 20% of Fe, 20% of Cu, 20% of Cr and 20% of Co, wherein the sum of atomic percentages of the above elements is 100%;
wherein the granularity of Cu, Cr, Co, Fe and Mn is 300 meshes, and the purity is 99.9%;
step 2, adding the raw materials weighed in the step 1 and absolute ethyl alcohol into a mixer for mixing, wherein the ball-material ratio for mixing is 30:1, the mixing time is 12 hours, the mixture is obtained after uniform mixing, the mixture is placed into a rigid die for pressing to obtain a high-entropy alloy blank, the pressing pressure is 400MPa, the pressure maintaining time is 30s, and the height of the high-entropy alloy blank is 0.5 mm;
step 3, processing and flattening the pre-bonded end of the CuW alloy, cleaning the pre-bonded end, drying for later use, cutting out a chromium bronze alloy bar, selecting the cut machined surface as a pre-bonded surface of the CuCr alloy, and drying for later use after cleaning;
the pre-bonding end part of the CuW alloy is provided with a groove matched with the high-entropy alloy blank;
cleaning the CuW alloy and the CuCr alloy by using a KQ-50DE type numerical control ultrasonic cleaner at the cleaning temperature of 17 ℃, firstly cleaning for 20 minutes by using an acetone cleaning agent, and then cleaning for 20 minutes by using an alcohol cleaning agent; step 4, stacking the high-entropy alloy blank, the CuW alloy and the CuCr alloy obtained in the step 2 and the step 3 in a crucible from top to bottom in sequence according to the sequence of the CuW alloy, the high-entropy alloy blank and the CuCr alloy, and embedding the high-entropy alloy blank into a groove at the pre-combined end part of the CuW alloy;
and 5, placing the crucible in a sintering furnace for heating at a heating rate of 20 ℃/min, performing solid-phase sintering on the high-entropy alloy, wherein the temperature of the solid-phase sintering is 950 ℃, the heat preservation time is 1.5h, after the solid-phase sintering is finished, heating at a heating rate of 20 ℃/min, performing liquid-phase connection at 1200 ℃, the heat preservation time is 2h, then cooling to 950 ℃ at a cooling rate of 20 ℃/min, and then cooling to room temperature along with the furnace, thus obtaining the CuW/CuCr composite material.
Example 3
A method for preparing a CuW/CuCr composite material by high-entropy alloy infiltration is implemented according to the following steps
Step 1, weighing the following raw materials in atomic percentage:
15 percent of Mn, 15 percent of Fe, 5 to 25 percent of Cu, 25 percent of Cr and 25 percent of Co, wherein the sum of the atomic percentages of the above elements is 100 percent;
wherein the granularity of Cu, Cr, Co, Fe and Mn is 200 meshes, and the purity is 99.9%;
step 2, adding the raw materials weighed in the step 1 and glycerol into a mixer for mixing, wherein the ball-material ratio for mixing is 20:1, the mixing time is 8 hours, the mixture is obtained after uniform mixing, the mixture is placed into a rigid die for pressing to obtain a high-entropy alloy blank, the pressing pressure is 100Mpa, the pressure maintaining time is 60s, and the height of the high-entropy alloy blank is 2 mm;
step 3, processing and flattening the pre-bonded end of the CuW alloy, cleaning the pre-bonded end, drying for later use, cutting out a chromium bronze alloy bar, selecting the cut machined surface as a pre-bonded surface of the CuCr alloy, and drying for later use after cleaning;
the pre-bonding end part of the CuW alloy is provided with a groove matched with the high-entropy alloy blank;
cleaning the CuW alloy and the CuCr alloy by using a KQ-50DE type numerical control ultrasonic cleaner at the cleaning temperature of 20 ℃, firstly cleaning for 25 minutes by using an acetone cleaning agent, and then cleaning for 25 minutes by using an alcohol cleaning agent;
step 4, stacking the high-entropy alloy blank, the CuW alloy and the CuCr alloy obtained in the step 2 and the step 3 in a crucible from top to bottom in sequence according to the sequence of the CuW alloy, the high-entropy alloy blank and the CuCr alloy, and embedding the high-entropy alloy blank into a groove at the pre-combined end part of the CuW alloy;
and 5, placing the crucible in a sintering furnace for heating at a heating rate of 5 ℃/min, performing solid-phase sintering on the high-entropy alloy, wherein the temperature of the solid-phase sintering is 600 ℃, the heat preservation time is 3h, after the solid-phase sintering is finished, heating at a heating rate of 5 ℃/min, performing liquid-phase connection at 1100 ℃, the heat preservation time is 3h, then cooling to 800 ℃ at a cooling rate of 5 ℃/min, and then cooling to room temperature along with the furnace, thus obtaining the CuW/CuCr composite material.
Example 4
The invention discloses a method for preparing a CuW/CuCr composite material by high-entropy alloy infiltration, which is implemented according to the following steps as shown in figure 1:
step 1, weighing the following raw materials in atomic percentage:
20% of Mn, 20% of Fe, 20% of Cu, 20% of Cr and 20% of Co, wherein the sum of atomic percentages of the elements is 100%;
wherein the granularity of Cu, Cr, Co, Fe and Mn is 300 meshes, and the purity is 99.9%;
step 2, adding the raw materials weighed in the step 1 and butanediol into a mixer for mixing, wherein the ball-material ratio for mixing is 40:1, the mixing time is 12 hours, uniformly mixing to obtain a mixture, placing the mixture into a rigid die for pressing to obtain a high-entropy alloy blank, the pressing pressure is 400Mpa, the pressure maintaining time is 60s, and the height of the high-entropy alloy blank is 1 mm;
step 3, processing and flattening the pre-bonded end of the CuW alloy, cleaning the pre-bonded end, drying for later use, cutting out a chromium bronze alloy bar, selecting the cut machined surface as a pre-bonded surface of the CuCr alloy, and drying for later use after cleaning;
the pre-bonding end part of the CuW alloy is provided with a groove matched with the high-entropy alloy blank;
cleaning the CuW alloy and the CuCr alloy by using a KQ-50DE type numerical control ultrasonic cleaner at the cleaning temperature of 25 ℃, firstly cleaning for 30 minutes by using an acetone cleaning agent, and then cleaning for 30 minutes by using an alcohol cleaning agent;
step 4, stacking the high-entropy alloy blank, the CuW alloy and the CuCr alloy obtained in the step 2 and the step 3 in a crucible from top to bottom in sequence according to the sequence of the CuW alloy, the high-entropy alloy blank and the CuCr alloy, and embedding the high-entropy alloy blank into a groove at the pre-combined end part of the CuW alloy;
and 5, placing the crucible in a sintering furnace for heating at a heating rate of 15 ℃/min, performing solid-phase sintering on the high-entropy alloy, wherein the temperature of the solid-phase sintering is 850 ℃, the heat preservation time is 1h, after the solid-phase sintering is finished, heating at a heating rate of 15 ℃/min, performing liquid-phase connection at 1300 ℃, the heat preservation time is 1h, then cooling to 850 ℃ at a cooling rate of 15 ℃/min, and then cooling to room temperature along with the furnace, thus obtaining the CuW/CuCr composite material.
FIG. 2 is a graph of the hardness of the composite material of the present invention with different manganese contents at a distance of 4mm from the CuCr side to the interface; as can be seen from FIG. 2, with the increase of Mn content in the high-entropy alloy, the hardness of the CuCr side 4mm away from the interface is reduced, so that the proper Mn content is beneficial to connecting the whole material; FIG. 3 is an SEM image of a joint surface of the CuW/CuCr composite material prepared in example 2 of the invention, and it can be seen from FIG. 3 that the CuW/CuCr composite material containing the CuCrCoFeMn high-entropy alloy interlayer in the joint surface region has good interface bonding and no hole cracks or other defects affecting the interface bonding strength; fig. 4 is a line scan diagram of the bonding interface of the CuW/CuCr composite material prepared in example 4 of the present invention, and it can be seen from fig. 4 that both the high-entropy alloy interlayers can be fully dissolved and diffused into the heterogeneous materials on both sides of the interface, the high-entropy alloy interlayers have good fusion property with the heterogeneous materials on both sides of the interface, no unmelted material remains on the interface, and metallurgical diffusion and dissolution occur on the CuW/CuCr interface, so that the two phases of Cu and W that are originally immiscible with each other generate metallurgical bonding at the Cu/W phase interface.
Claims (9)
1. A method for preparing a CuW/CuCr composite material by high-entropy alloy infiltration is characterized by comprising the following steps:
step 1, weighing the following raw materials in atomic percentage:
5-25% of Mn, 5-20% of Fe, 5-25% of Cu, 5-35% of Cr and 5-25% of Co, wherein the sum of atomic percentages of the elements is 100%;
step 2, adding the raw materials and the process control agent weighed in the step 1 into a mixer for mixing, uniformly mixing to obtain a mixture, and placing the mixture into a rigid die for pressing to obtain a high-entropy alloy blank;
step 3, processing and flattening the pre-bonded end of the CuW alloy, cleaning the pre-bonded end, drying for later use, cutting out a chromium bronze alloy bar, selecting the cut machined surface as a pre-bonded surface of the CuCr alloy, and drying for later use after cleaning;
step 4, stacking the high-entropy alloy blank, the CuW alloy and the CuCr alloy obtained in the step 2 and the step 3 in a crucible from top to bottom in sequence according to the sequence of the CuW alloy, the high-entropy alloy blank and the CuCr alloy;
and 5, heating the crucible in a sintering furnace, performing solid-phase sintering on the high-entropy alloy, performing liquid-phase connection on the heterogeneous material after the solid-phase sintering is finished, and cooling to obtain the CuW/CuCr composite material.
2. The method for preparing the CuW/CuCr composite material through high-entropy alloy infiltration according to claim 1, wherein the particle sizes of Cu, Cr, Co, Fe and Mn in the step 1 are all 50-400 meshes, and the purity is 99.9%.
3. A method for preparing CuW/CuCr composite material by high-entropy alloy infiltration according to claim 1, wherein the process control agent in the step 2 is absolute ethyl alcohol, glycerol, butanediol or stearic acid.
4. The method for preparing the CuW/CuCr composite material through high-entropy alloy infiltration according to claim 1, wherein the ball-to-material ratio of mixing in the step 2 is 10-40:1, and the mixing time is 8-12 h.
5. The method for preparing the CuW/CuCr composite material by high-entropy alloy infiltration according to claim 1, wherein the pressing pressure in the step 2 is 100-400MPa, the dwell time is 30-60s, and the height of the high-entropy alloy blank is 0.5-3 mm.
6. The method for preparing the CuW/CuCr composite material through high-entropy alloy infiltration according to claim 1, wherein the pre-bonding end part of the CuW alloy in the step 3 is provided with a groove matched with the high-entropy alloy blank.
7. The method for preparing the CuW/CuCr composite material through high-entropy alloy infiltration according to claim 1, wherein a KQ-50DE type numerical control ultrasonic cleaner is used for cleaning the CuW alloy and the CuCr alloy in the step 3, the cleaning temperature is 15-25 ℃, an acetone cleaning agent is used for cleaning for 15-30 minutes, and an alcohol cleaning agent is used for cleaning for 15-30 minutes.
8. The method for preparing CuW/CuCr composite material by high-entropy alloy infiltration according to claim 1, wherein the heating rate of solid-phase sintering in the step 5 is 5-30 ℃/min, the temperature of solid-phase sintering is 600-1000 ℃, and the holding time is 1-4 h.
9. The method for preparing CuW/CuCr composite material through high-entropy alloy infiltration according to claim 1, wherein after the solid-phase sintering in the step 5 is completed, the CuW/CuCr composite material is heated at a heating rate of 5-30 ℃/min, liquid-phase connection is performed at 1100-1400 ℃, the heat preservation time is 0.5-4h, and then the CuW/CuCr composite material is cooled to 800-1000 ℃ at a cooling rate of 5-30 ℃/min, and then the CuW/CuCr composite material is cooled to room temperature along with a furnace.
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