CN117568687B - Nanometer second-phase reinforced superfine crystal tungsten copper composite material and preparation method thereof - Google Patents
Nanometer second-phase reinforced superfine crystal tungsten copper composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 128
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000013078 crystal Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000010949 copper Substances 0.000 claims abstract description 59
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000843 powder Substances 0.000 claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 38
- 239000010937 tungsten Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000005098 hot rolling Methods 0.000 claims abstract description 16
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 12
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 239000011651 chromium Substances 0.000 claims description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 33
- 239000010955 niobium Substances 0.000 claims description 26
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 25
- 238000000713 high-energy ball milling Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000005551 mechanical alloying Methods 0.000 claims description 16
- 238000004886 process control Methods 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 14
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 13
- 238000005275 alloying Methods 0.000 claims description 11
- 238000002490 spark plasma sintering Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 24
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 3
- 239000006104 solid solution Substances 0.000 description 6
- 238000002679 ablation Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910004525 TaCr Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007123 defense Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- 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
- C22C1/045—Alloys based on refractory metals
Abstract
The invention discloses a nano second phase reinforced superfine crystal tungsten copper composite material, which is characterized in that the nano second phase distribution in the composite material is Cr in the tungsten phase, ta or Nb in the copper phase and discontinuous Cr in the tungsten-copper interface 2 Ta or Cr 2 The invention also discloses a method for preparing the nano second-phase reinforced superfine crystal tungsten copper composite material, which comprises the steps of mixing Cu-Ta composite powder or Cu-Nb composite powder and W-Cr composite powder, ball milling, sintering and hot rolling to obtain the nano second-phase reinforced superfine crystal tungsten copper composite material. According to the invention, different nano second phases are not introduced into the tungsten matrix and the copper matrix respectively, meanwhile, a nano intermetallic compound is formed at the interface of the tungsten phase and the copper phase, and the introduction of the nano second phases remarkably enhances the strength of the matrix and the interface binding force between the tungsten phase and the copper phase, so that the high-temperature properties such as high-temperature strength, structural stability and the like of the material are remarkably improved.
Description
Technical Field
The invention belongs to the technical field of tungsten-copper composite materials, and particularly relates to a nano second-phase reinforced superfine crystal tungsten-copper composite material and a preparation method thereof.
Background
The tungsten-copper composite material has good electric conduction, heat conduction, high melting point, high electric breakdown strength, low contact resistance, high welding resistance, high heat resistance and other performances, and is widely applied to high-precision industries such as aerospace, national defense and military industry, power electronics, optical communication and the like. In recent years, along with the rapid development of the industries, the requirements on the quantity and the performance of tungsten-copper alloy are raised more and more, and particularly along with the development of new application of tungsten-copper composite materials in the field of military national defense, the application of high-temperature tungsten-copper composite materials is greatly growing. The tungsten-copper material used as high-tech and military national defense has high reliability, which puts higher demands on the high-temperature strength of the material, the ablation performance in high-temperature fuel gas and the like. The infiltration method is the most widely used method for preparing the tungsten-copper composite material, and the commercial tungsten-copper composite material is almost prepared by adopting the infiltration method at present. The tungsten-copper composite material prepared by the infiltration method has coarse grains and low material strength, and particularly, the material is seriously softened in a high-temperature environment and is difficult to meet the use requirement in the high-temperature environment. In order to further improve the comprehensive performance of the high-temperature tungsten copper composite material, the introduction of a strengthening phase and a nano structure into a tungsten copper matrix attracts wide attention of material researchers at home and abroad, and the two approaches are difficult to realize by an infiltration method.
Therefore, development of a new method suitable for mass production of nanocrystalline/ultrafine grain tungsten copper composite materials is urgently needed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the nano second-phase reinforced superfine crystal tungsten copper composite material aiming at the defects of the prior art. The tungsten-copper composite material introduces different nanometer second phases into the tungsten matrix and the copper matrix respectively, and simultaneously forms nanometer intermetallic compounds at interfaces of the tungsten phase and the copper phase, and the introduction of the nanometer second phases remarkably enhances the strength of the matrix and the interfacial binding force between the tungsten phase and the copper phase, so that the high-temperature properties of the material, such as high-temperature strength, structural stability and the like, are remarkably improved.
In order to solve the technical problems, the invention adopts the following technical scheme: a nano second phase reinforced superfine crystal tungsten copper composite material is characterized in that the nano second phase distribution in the composite material is characterized in that the nano second phase in the tungsten phase is Cr, the nano second phase in the copper phase is Ta or Nb, and the nano second phase at the tungsten-copper interface is discontinuous Cr 2 Ta or Cr 2 Nb。
According to the tungsten copper composite material, the nano second phase with higher density is introduced into the copper matrix and the tungsten matrix, the introduction of the nano second phase can prevent tungsten grains and copper grains from growing up in the sintering process, so that the final grain sizes of the tungsten grains and the copper grains are ultrafine grains, the structural characteristics of the nano second phase and the ultrafine grains enable the tungsten copper composite material to have higher high-temperature strength and high-temperature structural stability, the high-temperature performance of the composite material is obviously improved, and meanwhile, because Ta or Nb has no solid solubility in the copper matrix, the influence on the heat conductivity and the electric conductivity of the copper phase is smaller, and therefore, the tungsten copper composite material has higher high-temperature performance and conductivity.
The nano second phase reinforced superfine crystal tungsten copper composite material is characterized in that the sizes of tungsten grains and copper grains in the composite material are smaller than 1 mu m. The invention realizes ultra-fine grains by controlling the sizes of tungsten grains and copper grains, so that the strength, the hardness and the ablation resistance of the nano second phase reinforced ultra-fine grain tungsten-copper composite material are improved.
The nano second-phase reinforced superfine crystal tungsten copper composite material is characterized by comprising the following components in percentage by mass: 10% -50% of Cu, 0.5% -3% of Cr, 1% -6% of Ta or 1% -6% of Nb, and the balance of W and unavoidable impurities. The invention improves the traditional W-Cu composite material, which consists of tungsten phase and copper phase, respectively introduces different nanometer second phases into the tungsten phase and copper phase to prevent the growth of tungsten crystal grains and copper crystal grains in the sintering process, obviously improves the strength and ablation resistance of the tungsten-copper composite material, introduces Ta element or Nb element into the copper phase to form Ta or Nb nano-particles, introduces Cr element into the tungsten phase to form Cr nano-particles, and simultaneously, the interface of the tungsten phase and the copper phase can form Cr due to atomic diffusion reaction 2 Ta or Cr 2 Nb nanoparticles.
In addition, the invention provides a method for preparing the nano second phase reinforced ultra-fine grain tungsten copper composite material, which is characterized by comprising the following steps:
firstly, weighing copper powder and tantalum powder, or weighing copper powder and niobium powder, and then mechanically alloying to obtain Cu-Ta composite powder or Cu-Nb composite powder;
weighing tungsten powder and chromium powder, and then performing mechanical alloying to obtain W-Cr composite powder;
step three, mixing the Cu-Ta composite powder or the Cu-Nb composite powder obtained in the step one with the W-Cr composite powder obtained in the step two, and then performing low-energy ball milling to obtain mixed composite powder;
step four, sintering and molding the mixed composite powder obtained in the step three to obtain a composite green body;
and step five, hot rolling the composite blank obtained in the step four to obtain the nano second-phase reinforced superfine crystal tungsten copper composite material.
The invention is to weighCopper powder and tantalum powder or copper powder and niobium powder are respectively prepared, cu-Ta composite powder or Cu-Nb composite powder is respectively prepared, different nanometer second phase reinforced superfine tungsten copper composite materials are obtained, different use requirements are met, by mechanically alloying copper powder and tantalum powder or copper powder and niobium powder, in order to form Cu-Ta or Cu-Nb supersaturated solid solution, ta and Nb have no solid solubility in Cu, ta and Nb can be separated out of a Cu matrix to form a second phase in the subsequent sintering and processing processes, tungsten powder and chromium powder are mechanically alloyed to have the same effect to form a W-Cr supersaturated solid solution, cr can be separated out of the W matrix to form a separation phase in the subsequent forming process, the uniform distribution of the tungsten matrix and the copper matrix is realized by low-energy ball milling in order to uniformly mix the copper composite powder and the tungsten composite powder, on the one hand, the composite powder is made into a block body by sintering and forming the Cu matrix, ta or Nb nano second phase can be separated out in the W phase, and TaCr phase can be separated out at the W phase and Cu phase interface in the sintering and forming process 2 Or NbCr 2 The formation of the precipitated phase can prevent W crystal grains and Cu crystal grains from growing up in a high-temperature environment so as to keep an ultra-fine crystal structure, the composite material is further densified through hot rolling, and the density of the nano second-phase reinforced ultra-fine crystal tungsten-copper composite material is improved.
The method is characterized in that the particle size of the copper powder in the first step is 0.5-45 mu m, the particle size of the tantalum powder is 0.05-3 mu m, and the particle size of the niobium powder is 0.05-3 mu m; in the second step, the particle size of the tungsten powder is 0.1-45 mu m, and the particle size of the chromium powder is 0.1-5 mu m. The invention ensures that the prepared nano second phase reinforced ultra-fine grain tungsten copper composite material is compounded with ultra-fine grains by limiting the grain size of the raw materials.
The method is characterized in that the mechanical alloying in the first step is performed by high-energy ball milling, the rotating speed of the high-energy ball milling is 350 rpm-600 rpm, the ball-material ratio is 10-15:1, the atmosphere is argon, the time is 30-60 h, and the process control agent is ethanol, n-heptane or acetone. The invention ensures that copper powder and tantalum powder or copper powder and niobium powder are fully mechanically alloyed by controlling the parameters of mechanical alloying to form a Cu-Ta or Cu-Nb supersaturated solid solution.
The method is characterized in that the mechanical alloying in the second step is performed by high-energy ball milling, the rotating speed of the high-energy ball milling is 450-650 rpm, the ball-material ratio is 12-15:1, the atmosphere is argon, the time is 35-65 h, and the process control agent is ethanol, n-heptane or acetone. The invention ensures that tungsten powder and chromium powder are fully mechanically alloyed by controlling the parameters of mechanical alloying, so as to form W-Cr supersaturated solid solution.
The method is characterized in that the rotating speed of the low-energy ball milling in the third step is 150-250 rpm, the ball-material ratio is 5-10:1, the atmosphere is high-purity argon, and the time is 5-20 hours. The invention ensures that the copper composite powder and the tungsten composite powder are fully and uniformly mixed by controlling the parameters of low-energy ball milling, and realizes uniform distribution of the tungsten matrix and the copper matrix.
The method is characterized in that the sintering and forming in the fourth step is hot-press sintering or spark plasma sintering, the temperature of the hot-press sintering is 850-1000 ℃, the pressure is 30-50 MPa, the heat preservation time is 2h, the temperature of the spark plasma sintering is 800-1000 ℃, the pressure is 40-50 MPa, and the heat preservation time is 5min. The method ensures that Ta or Nb nano second phase can be separated out in the Cu matrix, cr nano separation phase can be separated out in the W phase, and TaCr can be formed at the interface of the W phase and the Cu phase by controlling parameters of hot-press sintering and spark plasma sintering 2 Or NbCr 2 The formation of the nano precipitated phase can prevent W grains and Cu grains from growing up in a high-temperature environment so as to maintain an ultrafine grain structure.
The method is characterized in that the temperature of the hot rolling in the fifth step is 800-950 ℃ and the deformation is 20-60%. According to the invention, by controlling the parameters of hot rolling, the composite blank is further densified, and the density of the nano second-phase reinforced superfine crystal tungsten copper composite material is improved.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, different nano second phases are respectively introduced into the tungsten matrix and the copper matrix, meanwhile, a nano intermetallic compound is formed at the interface of the tungsten phase and the copper phase, and the introduction of the nano second phases remarkably enhances the strength of the matrix and the interface binding force between the tungsten phase and the copper phase, so that the high-temperature properties of the material, such as high-temperature strength, structural stability and the like, are remarkably improved.
2. The tungsten phase and the copper phase of the tungsten-copper composite material prepared by the invention have ultrafine grain structures, and the introduction of the nano second phase inhibits the growth of tungsten grains and copper grains in the sintering process, so that the ultrafine grain structure is reserved, the ultrafine grain has high-density grain boundaries, and the existence of the interfaces can further improve the high-temperature ablation resistance of the material.
3. According to the invention, copper powder and tantalum powder or copper powder and niobium powder are weighed, and Cu-Ta composite powder or Cu-Nb composite powder is prepared respectively, so that different nanometer second phase reinforced superfine crystal tungsten copper composite materials are obtained, and different use requirements are met.
4. According to the invention, copper powder and tantalum powder or copper powder and niobium powder are mechanically alloyed, in order to form a Cu-Ta or Cu-Nb supersaturated solid solution, ta and Nb have no solid solubility in Cu, ta and Nb are separated out of a Cu matrix to form a second phase in the subsequent sintering and processing processes, tungsten powder and chromium powder are mechanically alloyed to play the same role to form a W-Cr supersaturated solid solution, cr is separated out of a W matrix to form a separated phase in the subsequent forming process, and the purpose of uniformly mixing copper composite powder and tungsten composite powder is realized by low-energy ball milling.
5. The invention is to make the composite powder into a block by sintering and forming, meanwhile, ta or Nb nano second phase can be separated out in the Cu matrix during the sintering and forming process, cr nano separation phase can be separated out in the W phase, and TaCr can be formed at the interface of the W phase and the Cu phase 2 Or NbCr 2 The formation of the precipitated phase can prevent W crystal grains and Cu crystal grains from growing up in a high-temperature environment so as to keep an ultra-fine crystal structure, the composite material is further densified through hot rolling, and the density of the nano second-phase reinforced ultra-fine crystal tungsten-copper composite material is improved.
The technical scheme of the invention is further described in detail by examples.
Detailed Description
Example 1
The embodiment comprises the following steps:
firstly, weighing copper powder and tantalum powder, and then mechanically alloying the copper powder and the tantalum powder to obtain Cu-Ta composite powder; the grain diameter of the copper powder is 0.5 mu m, and the grain diameter of the tantalum powder is 0.05 mu m; the mechanical alloying is high-energy ball milling, the rotating speed of the high-energy ball milling is 350rpm, the ball-material ratio is 15:1, the atmosphere is argon, the time is 60 hours, and the adopted process control agent is ethanol;
weighing tungsten powder and chromium powder, and then mechanically alloying the tungsten powder and the chromium powder to obtain W-Cr composite powder; the particle size of the tungsten powder is 0.1 mu m, and the particle size of the chromium powder is 0.1 mu m; the mechanical alloying is high-energy ball milling, the rotating speed of the high-energy ball milling is 450rpm, the ball-material ratio is 15:1, the atmosphere is argon, the time is 65h, and the adopted process control agent is ethanol;
step three, mixing the Cu-Ta composite powder obtained in the step one with the W-Cr composite powder obtained in the step two, and performing low-energy ball milling to obtain mixed composite powder; the rotating speed of the low-energy ball milling is 200rpm, the ball-material ratio is 5:1, the atmosphere is argon, and the time is 5 hours;
step four, carrying out hot-pressing sintering on the mixed composite powder obtained in the step three to obtain a composite green body; the hot-pressed sintering temperature is 850 ℃, the pressure is 50MPa, and the heat preservation time is 2 hours;
step five, hot rolling the composite blank obtained in the step four to obtain a nano second-phase reinforced superfine crystal tungsten copper composite material; the temperature of the hot rolling is 800 ℃, and the rolling deformation is 20%.
According to detection, the nano second-phase reinforced ultra-fine grain tungsten copper composite material prepared by the embodiment comprises the following components: 10% of Cu, 0.5% of Cr, 1% of Ta and the balance of W and unavoidable impurities, wherein the distribution characteristic of the nanometer second phase is that the nanometer second phase in the tungsten phase is Cr, the nanometer second phase in the copper phase is Ta, and the nanometer second phase at the tungsten-copper interface is discontinuous Cr 2 Ta, and the sizes of tungsten grains and copper grains are smaller than 1 mu m; the heat-resistant temperature of the nano second-phase reinforced superfine crystal tungsten copper composite material prepared by the embodiment reaches 700 ℃, the thermal conductivity reaches 160W/mK, and the thermal expansion coefficient is 6.3 multiplied by 10 -6 /K。
The process control agent in this example may be replaced with n-heptane or acetone, and the tantalum powder may be replaced with niobium powder having the same mass percentage and the same particle size.
Example 2
The embodiment comprises the following steps:
firstly, weighing copper powder and tantalum powder, and then mechanically alloying the copper powder and the tantalum powder to obtain Cu-Ta composite powder; the grain diameter of the copper powder is 3 mu m, and the grain diameter of the tantalum powder is 0.1 mu m; the mechanical alloying is high-energy ball milling, the rotating speed of the high-energy ball milling is 450rpm, the ball-material ratio is 12:1, the atmosphere is argon, the time is 45h, and the adopted process control agent is n-heptane;
weighing tungsten powder and chromium powder, and then mechanically alloying the tungsten powder and the chromium powder to obtain W-Cr composite powder; the particle size of the tungsten powder is 0.5 mu m, and the particle size of the chromium powder is 1 mu m; the mechanical alloying is high-energy ball milling, the rotating speed of the high-energy ball milling is 500rpm, the ball-material ratio is 15:1, the atmosphere is argon, the time is 50h, and the adopted process control agent is n-heptane;
step three, mixing the Cu-Ta composite powder obtained in the step one with the W-Cr composite powder obtained in the step two, and performing low-energy ball milling to obtain mixed composite powder; the rotating speed of the low-energy ball milling is 250rpm, the ball-material ratio is 5:1, the atmosphere is argon, and the time is 10 hours;
step four, carrying out hot-pressing sintering on the mixed composite powder obtained in the step three to obtain a composite green body; the hot-pressed sintering temperature is 1000 ℃, the pressure is 30MPa, and the heat preservation time is 2 hours;
step five, hot rolling the composite blank obtained in the step four to obtain a nano second-phase reinforced superfine crystal tungsten copper composite material; the temperature of the hot rolling is 850 ℃, and the rolling deformation is 30%.
According to detection, the nano second-phase reinforced ultra-fine grain tungsten copper composite material prepared by the embodiment comprises the following components: cu 20%, cr 1%, ta 2%, and the balance W and unavoidable impurities, the distribution of the nano second phase is characterized in that the nano second phase in the tungsten phase is Cr, the nano second phase in the copper phase is Ta, and the nano second phase at the tungsten-copper interfaceIs discontinuous Cr 2 Ta, and the sizes of tungsten grains and copper grains are smaller than 1 mu m; the heat-resistant temperature of the nano second-phase reinforced superfine crystal tungsten copper composite material prepared by the embodiment reaches 800 ℃, the thermal conductivity reaches 192W/mK, and the thermal expansion coefficient is 7.8x10 -6 /K。
It should be noted that the process control agent in this embodiment may be replaced by ethanol or acetone, and the tantalum powder may be replaced by niobium powder having the same mass percentage and the same particle size.
Example 3
The embodiment comprises the following steps:
firstly, weighing copper powder and tantalum powder, and then mechanically alloying the copper powder and the tantalum powder to obtain Cu-Ta composite powder; the grain size of the copper powder is 15 mu m, and the grain size of the tantalum powder is 1 mu m; the mechanical alloying is high-energy ball milling, the rotating speed of the high-energy ball milling is 500rpm, the ball-material ratio is 12:1, the atmosphere is argon, the time is 40 hours, and the adopted process control agent is n-heptane;
weighing tungsten powder and chromium powder, and then mechanically alloying the tungsten powder and the chromium powder to obtain W-Cr composite powder; the particle size of the tungsten powder is 3 mu m, and the particle size of the chromium powder is 3 mu m; the mechanical alloying is high-energy ball milling, the rotating speed of the high-energy ball milling is 600rpm, the ball-material ratio is 12:1, the atmosphere is argon, the time is 60 hours, and the adopted process control agent is n-heptane;
step three, mixing the Cu-Ta composite powder obtained in the step one with the W-Cr composite powder obtained in the step two, and performing low-energy ball milling to obtain mixed composite powder; the rotating speed of the low-energy ball milling is 150rpm, the ball-material ratio is 10:1, the atmosphere is argon, and the time is 20 hours;
step four, carrying out spark plasma sintering on the mixed composite powder obtained in the step three to obtain a composite green body; the temperature of the spark plasma sintering is 800 ℃, the pressure is 50MPa, and the heat preservation time is 5min;
step five, hot rolling the composite blank obtained in the step four to obtain a nano second-phase reinforced superfine crystal tungsten copper composite material; the temperature of the hot rolling is 900 ℃, and the rolling deformation is 50%.
According to detection, the nano second-phase reinforced ultra-fine grain tungsten copper composite material prepared by the embodiment comprises the following components: 30% of Cu, 2% of Cr, 4% of Ta and the balance of W and unavoidable impurities, wherein the distribution characteristic of the nanometer second phase is that the nanometer second phase in the tungsten phase is Cr, the nanometer second phase in the copper phase is Ta, and the nanometer second phase at the tungsten-copper interface is discontinuous Cr 2 Ta, and the sizes of tungsten grains and copper grains are smaller than 1 mu m; the heat-resistant temperature of the nano second-phase reinforced superfine crystal tungsten copper composite material prepared by the embodiment reaches 900 ℃, the thermal conductivity reaches 230W/mK, and the thermal expansion coefficient is 8.9x10 -6 /K。
It should be noted that the process control agent in this embodiment may be replaced by ethanol or acetone, and the tantalum powder may be replaced by niobium powder having the same mass percentage and the same particle size.
Example 4
The embodiment comprises the following steps:
firstly, weighing copper powder and tantalum powder, and then mechanically alloying the copper powder and the tantalum powder to obtain Cu-Ta composite powder; the grain diameter of the copper powder is 45 mu m, and the grain diameter of the tantalum powder is 3 mu m; the mechanical alloying is high-energy ball milling, the rotating speed of the high-energy ball milling is 600rpm, the ball-material ratio is 10:1, the atmosphere is argon, the time is 30 hours, and the adopted process control agent is n-heptane;
weighing tungsten powder and chromium powder, and then mechanically alloying the tungsten powder and the chromium powder to obtain W-Cr composite powder; the particle size of the tungsten powder is 45 mu m, and the particle size of the chromium powder is 5 mu m; the mechanical alloying is high-energy ball milling, the rotating speed of the high-energy ball milling is 650rpm, the ball-material ratio is 12:1, the atmosphere is argon, the time is 35h, and the adopted process control agent is n-heptane;
step three, mixing the Cu-Ta composite powder obtained in the step one with the W-Cr composite powder obtained in the step two, and performing low-energy ball milling to obtain mixed composite powder; the rotating speed of the low-energy ball milling is 250rpm, the ball-material ratio is 7:1, the atmosphere is argon, and the time is 10 hours;
step four, carrying out spark plasma sintering on the mixed composite powder obtained in the step three to obtain a composite green body; the temperature of the spark plasma sintering is 1000 ℃, the pressure is 40MPa, and the heat preservation time is 5min;
step five, hot rolling the composite blank obtained in the step four to obtain a nano second-phase reinforced superfine crystal tungsten copper composite material; the temperature of the hot rolling is 950 ℃, and the rolling deformation is 60%.
According to detection, the nano second-phase reinforced ultra-fine grain tungsten copper composite material prepared by the embodiment comprises the following components: 50% of Cu, 3% of Cr, 6% of Ta and the balance of W and unavoidable impurities, wherein the distribution characteristic of the nanometer second phase is that the nanometer second phase in the tungsten phase is Cr, the nanometer second phase in the copper phase is Ta, and the nanometer second phase at the tungsten-copper interface is discontinuous Cr 2 Ta, and the sizes of tungsten grains and copper grains are smaller than 1 mu m; the heat-resistant temperature of the nano second-phase reinforced superfine crystal tungsten copper composite material prepared by the embodiment reaches 900 ℃, the thermal conductivity reaches 260W/mK, and the thermal expansion coefficient is 1.5x10 -5 /K。
It should be noted that the process control agent in this embodiment may be replaced by ethanol or acetone, and the tantalum powder may be replaced by niobium powder having the same mass percentage and the same particle size.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (9)
1. A nano second phase reinforced superfine crystal tungsten copper composite material is characterized in that the nano second phase distribution in the composite material is characterized in that the nano second phase in the tungsten phase is Cr, the nano second phase in the copper phase is Ta or Nb, and the nano second phase at the tungsten-copper interface is discontinuous Cr 2 Ta or Cr 2 Nb; the composite material comprises the following components in percentage by mass: 10% -50% of Cu, 0.5% -3% of Cr, 1% -6% of Ta or 1% -6% of Nb, and the balance of W and unavoidable impurities.
2. The nano second phase reinforced ultra-fine grain tungsten copper composite of claim 1, wherein the size of both tungsten grains and copper grains in the composite is less than 1 μm.
3. A method of preparing a nano second phase reinforced ultra-fine grain tungsten copper composite as claimed in claim 1 or 2, comprising the steps of:
firstly, weighing copper powder and tantalum powder, or weighing copper powder and niobium powder, and then mechanically alloying to obtain Cu-Ta composite powder or Cu-Nb composite powder;
weighing tungsten powder and chromium powder, and then performing mechanical alloying to obtain W-Cr composite powder;
step three, mixing the Cu-Ta composite powder or the Cu-Nb composite powder obtained in the step one with the W-Cr composite powder obtained in the step two, and then performing low-energy ball milling to obtain mixed composite powder;
step four, sintering and molding the mixed composite powder obtained in the step three to obtain a composite green body;
and step five, hot rolling the composite blank obtained in the step four to obtain the nano second-phase reinforced superfine crystal tungsten copper composite material.
4. A method according to claim 3, wherein in step one the copper powder has a particle size of 0.5 μm to 45 μm, the tantalum powder has a particle size of 0.05 μm to 3 μm, and the niobium powder has a particle size of 0.05 μm to 3 μm; in the second step, the particle size of the tungsten powder is 0.1-45 mu m, and the particle size of the chromium powder is 0.1-5 mu m.
5. The method according to claim 3, wherein the mechanical alloying in the first step is performed by high-energy ball milling, the rotational speed of the high-energy ball milling is 350 rpm-600 rpm, the ball-to-material ratio is 10-15:1, the atmosphere is argon, the time is 30-60 h, and the process control agent is ethanol, n-heptane or acetone.
6. The method according to claim 3, wherein the mechanical alloying in the second step is performed by high-energy ball milling, the rotational speed of the high-energy ball milling is 450-650 rpm, the ball-to-material ratio is 12-15:1, the atmosphere is argon, the time is 35-65 h, and the process control agent is ethanol, n-heptane or acetone.
7. The method according to claim 3, wherein in the third step, the rotation speed of the low-energy ball milling is 150-250 rpm, the ball-material ratio is 5-10:1, the atmosphere is high-purity argon, and the time is 5-20 h.
8. The method according to claim 3, wherein the sintering and forming is hot press sintering or spark plasma sintering, the temperature of the hot press sintering is 850 ℃ to 1000 ℃, the pressure is 30mpa to 50mpa, the heat preservation time is 2 hours, the temperature of the spark plasma sintering is 800 ℃ to 1000 ℃, the pressure is 40mpa to 50mpa, and the heat preservation time is 5 minutes.
9. A method according to claim 3, wherein the hot rolling in step five is carried out at a temperature of 800 ℃ to 950 ℃ and a deformation of 20% to 60%.
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