CN114086013B - High-strength high-conductivity ultrafine-grained tungsten-copper composite material and preparation method thereof - Google Patents
High-strength high-conductivity ultrafine-grained tungsten-copper composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000007747 plating Methods 0.000 claims abstract description 42
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005844 autocatalytic reaction Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000009423 ventilation Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000005253 cladding Methods 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract description 3
- 239000003870 refractory metal Substances 0.000 abstract description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 abstract description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract description 2
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 27
- 239000012071 phase Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 238000001000 micrograph Methods 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002490 spark plasma sintering Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000626 liquid-phase infiltration Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
Abstract
A high-strength high-conductivity ultra-fine grain tungsten-copper composite material and a preparation method thereof belong to the field of powder metallurgy technology and refractory metal materials. Preparing chemical plating solution by using copper sulfate, bipyridine, disodium ethylene diamine tetraacetate (EDTA-2 Na), sodium hydroxide and ethanol as raw materials; placing the ultra-fine tungsten powder into a plating solution, heating the solution to a specified temperature in a water bath, adding formaldehyde for plating, maintaining the pH stable, reducing the obtained composite powder in a hydrogen atmosphere, placing the composite powder into a mold, and sintering the composite powder at a high temperature for a short time by using discharge plasma sintering equipment to obtain the tungsten-copper composite material block. The realization of the ultra-fine grinding copper cladding structure and the maintenance of the ultra-fine grain structure ensure that the tungsten-copper composite material prepared by the invention has higher mechanical property and conductivity.
Description
Technical Field
The invention relates to a preparation method of an ultrafine grain tungsten-copper composite material, in particular to a method for preparing copper-coated ultrafine grain tungsten-copper composite powder by a chemical plating process and then sintering the copper-coated ultrafine grain tungsten-copper composite powder to prepare an ultrafine grain block material, belonging to the field of powder metallurgy technology and refractory metal materials.
Background
The tungsten-copper composite material integrates the advantages of refractory metal tungsten and nonferrous metal copper, has high hardness, high strength, low thermal expansion coefficient, good wear resistance, electric conduction and heat conduction performance and the like, and thus has wide application in the fields of aerospace, electronic and electrical engineering, nuclear industry, weaponry and the like. The traditional tungsten-copper composite material is mostly prepared by a melt infiltration method or a liquid phase sintering method, and both methods need to carry out long-time heat preservation on the material at high temperature, so that the obtained tissue structure is relatively thick, and the tungsten-copper composite material has relatively low mechanical property. With the rapid development of science and technology, the service environment of the tungsten-copper composite material becomes more severe, which puts higher demands on the performance of the tungsten-copper composite material.
According to related research reports, the performance of the tungsten-copper composite material is influenced by the structure and the components of the tungsten-copper composite material. In the aspect of component regulation, the sintering activity of the alloy element (such as iron, cobalt, nickel, zinc, zirconium, silver and the like) and the second phase (such as metal carbide, metal nitride, metal oxide and the like) can be improved by doping, and the hardness and the strength of the alloy element can be improved to a certain extent, but the electric and heat conductivity of the alloy element can be seriously deteriorated, so that the alloy element is not beneficial to the application of the alloy element in certain fields. In the aspect of structure regulation, research shows that the strength and the hardness of the tungsten-copper composite material are generally and continuously improved along with the refinement of the grain size, but the plasticity and the electric and heat conduction performance are also gradually reduced. Therefore, the nanocrystalline (grain size less than 100 nm) tungsten-copper composite material has the highest hardness and strength, but has poor electric and thermal conductivity and is also represented by brittle fracture. While the hardness of ultra-fine grain is slightly lower than that of nano-crystalline, but the conductivity and plasticity of ultra-fine grain (grain size 100-500 nm) are better than those of nano-crystalline, so that the ultra-fine grain has more excellent comprehensive performance. In addition, the connectivity of copper has a great influence on the conductivity of the tungsten-copper composite material, and the tungsten-copper composite material prepared by sintering the copper-coated tungsten powder has excellent conductivity due to higher copper connectivity, but the prepared tungsten-copper composite material has a thicker structure and general mechanical properties. Therefore, how to prepare the tungsten-copper composite material with excellent comprehensive performance through reasonable structure and component design is a research hotspot and technical challenge in the field.
At present, the preparation method of the ultra-fine grain tungsten-copper composite material mainly comprises a mechanical ball milling method and a chemical synthesis method. The chemical synthesis method is to prepare the tungsten-copper composite material by taking tungsten and copper salts as raw materials and adopting the processes of powder making, reduction, sintering and the like. The mechanical ball milling method is to perform ball milling and mixing by using coarse tungsten powder and copper powder, and the method can only obtain a composite material with a uniform structure and low connectivity, and has complex operation and low efficiency. Meanwhile, the tungsten phase in the tungsten-copper composite material prepared by the mechanical ball milling method has larger size, and the uniform dispersion of tungsten crystal grains is difficult to realize. According to literature research, research has been conducted on the preparation of copper-clad tungsten composite powder by coating micron-sized tungsten powder by using chemical plating and electroplating processes, and then the preparation of tungsten-copper composite material by using methods such as liquid phase sintering and the like. However, because the ultra-fine tungsten powder is easy to agglomerate, no report is available for coating the ultra-fine tungsten powder by using a plating process. How to efficiently prepare the ultra-fine grain tungsten-copper composite material with high copper connectivity is also a difficulty.
Based on the background, the invention realizes the preparation of the ultra-fine grain tungsten-copper composite powder with a copper cladding structure by utilizing an improved chemical plating process, and simultaneously prepares the ultra-fine grain tungsten-copper composite material block with adjustable and controllable components, uniform macroscopic structure and excellent comprehensive performance by combining a spark plasma sintering process.
Disclosure of Invention
The invention provides a preparation method of a high-strength high-conductivity ultrafine grain tungsten-copper composite material with controllable components, aiming at the problem of high-efficiency preparation of a high-performance tungsten-copper composite material.
The method comprises the following process flows and principles: copper sulfate, bipyridine, disodium ethylene diamine tetraacetate (EDTA-2 Na), sodium hydroxide and ethanol are used as raw materials to prepare the chemical plating solution; putting the ultra-fine tungsten powder into a plating solution, heating the solution to a specified temperature in a water bath, adding formaldehyde for plating, continuously dropwise adding a sodium hydroxide solution to maintain stable pH, and continuously carrying out ultrasonic stirring treatment on the plating solution in the plating process; after a certain time, the plating process is finished, and the obtained composite powder is filtered, repeatedly washed for three times and dried; reducing the dried powder in a hydrogen atmosphere to remove a small amount of oxygen in the washing process; and finally, filling the reduced powder into a die, and sintering at high temperature for a short time by using discharge plasma sintering equipment to obtain the tungsten-copper composite material block. In the process, the introduction of ethanol in the plating solution is beneficial to improving the wettability of the tungsten powder and the plating solution, thereby promoting the nucleation of copper nanoparticles on the surface of the ultra-fine tungsten powder and improving the coating effect of the ultra-fine powder; the continuous stirring and ultrasound in the plating process are beneficial to the dispersion of the superfine tungsten powder, and the plating uniformity is improved; the rapidity of spark plasma sintering effectively inhibits the growth of crystal grains and ensures the maintenance of an ultra-fine crystal structure. In conclusion, the realization of the ultra-fine grinding copper cladding structure and the maintenance of the ultra-fine grain structure ensure that the tungsten-copper composite material prepared by the invention has higher mechanical property and conductivity.
The invention provides a preparation method of a component-controllable, high-strength and high-conductivity ultrafine-grained tungsten-copper composite material. The method is characterized by comprising the following steps:
(1) Copper plating with superfine tungsten powder; firstly, copper sulfate, bipyridine, EDTA-2Na, sodium hydroxide and ethanol are used as raw materials to prepare a plating solution, wherein the concentration of the copper sulfate is 5-24g/L, the concentration of the bipyridine is 0.02-0.2g/L, the concentration of the EDTA-2Na is 15-50g/L, the concentration of the ethanol is 100-500ml/L, and the addition amount of the sodium hydroxide is required to ensure that the pH value of the solution is 11-12; then mixing the plating solution and the tungsten powder according to a certain stoichiometric ratio, putting the mixture in a water bath device, continuously stirring and ultrasonically heating the mixture to 60-90 ℃, dropwise adding sufficient formaldehyde into the plating solution for plating, and continuously adding a sodium hydroxide solution to maintain the pH value between 11 and 12; continuously depositing copper on the surface of the superfine tungsten powder under the autocatalysis of the tungsten powder to prepare copper-coated superfine tungsten powder;
(2) Filtering and collecting the copper-coated superfine tungsten powder obtained in the step (1), repeatedly washing with deionized water, finally washing with ethanol and drying at room temperature under a ventilation condition; then placing the dried copper-coated superfine tungsten powder into a tube furnace, and preserving the heat for 30-120 minutes at 750-900 ℃ in a hydrogen atmosphere to remove oxygen elements introduced in the preparation process to obtain high-purity superfine tungsten-copper composite powder;
(3) Filling the superfine tungsten-copper composite powder obtained in the step (2) into a graphite die, and then performing discharge plasma sintering under vacuum to obtain a superfine crystal tungsten-copper composite material block; the heating rate is 50-200 deg.C/min, the holding temperature is 950-1020 deg.C, the holding time is 2-20min, and the pressure is 20-200MPa. The cooling mode is furnace cooling.
In the step (1), the control of the copper plating content can be realized according to the proportion of the plating solution and the added tungsten powder and the plating conditions. The step (2) can realize the micro-regulation and control of the grain size of the composite material according to the initial grain size and sintering parameters of the ultrafine powder. The method can theoretically regulate and control the copper content in a large range to prepare the ultra-fine grain tungsten-copper composite material with different components.
The features and advantages of the invention are as follows:
the existing plating technology can only realize plating on the surface of micron-sized tungsten powder, the prepared coarse-grain tungsten-copper composite material has lower mechanical property, and the invention realizes plating on the surface of superfine tungsten powder by improving the formula of plating solution and the plating process. Secondly, the existing preparation method of the ultra-fine grain tungsten-copper composite material has the problems of low efficiency, uneven tissue structure and the like, and the high copper connectivity is difficult to realize, the invention can realize the macroscopic uniformity of the tissue by combining the improved plating process and the discharge plasma sintering technology, and the high-efficiency preparation of the tungsten-copper ultra-fine grain composite material with the high copper connectivity, and the grain sizes of the tungsten phase and the copper phase in the prepared ultra-fine grain tungsten-copper composite material are both between 100 and 500 nanometers. Meanwhile, due to the special structure of the ultra-fine grain tungsten-copper composite material prepared by the invention, the ultra-fine grain tungsten-copper composite material has better mechanical-electrical property matching property compared with other existing tungsten-copper composite materials. Finally, because the initial superfine tungsten powder has certain self-connectivity, a certain amount of bag-shaped structures exist in the superfine crystal tungsten-copper composite material prepared by the invention, and the bag-shaped structures can be used as characteristic marks of the superfine crystal tungsten-copper composite material prepared by the invention.
Drawings
FIG. 1: a phase analysis spectrum (X-ray diffraction spectrum) of the W20Cu ultra-fine grained tungsten copper composite material prepared in example 1, i.e., the composite material block in step (3);
FIG. 2: a micro-topography (scanning electron microscope image) of the W20Cu ultra-fine grained tungsten copper composite material prepared in example 1;
FIG. 3: a microscopic morphology (transmission electron microscope image) of the W20Cu ultrafine grained tungsten copper composite material prepared in example 1;
FIG. 4: a microscopic morphology (scanning electron microscope image) of the W30Cu ultra-fine grained tungsten copper composite powder prepared in example 2;
FIG. 5: a phase analysis spectrum (X-ray diffraction spectrum) of the W30Cu ultra-fine grained tungsten copper composite material prepared in example 2, i.e., the composite material block in step (3);
FIG. 6: a micro-topography (scanning electron microscope image) of the W30Cu ultra-fine grained tungsten copper composite material prepared in example 2;
FIG. 7: a microscopic morphology (transmission electron microscope image) of the W30Cu ultrafine grained tungsten copper composite material prepared in example 2;
FIG. 8: a micro-topography (scanning electron microscope image) of the W40Cu ultra-fine grained tungsten-copper composite material prepared in example 3;
FIG. 9: the compressive stress strain curve of the W40Cu ultra-fine grained tungsten copper composite material prepared in example 3;
Detailed Description
The following detailed description is merely exemplary in nature and is intended to provide the person skilled in the art with a better understanding of the present patent, and is not intended to limit the scope of the patent; any equivalent alterations or modifications made according to the spirit of the disclosure of this patent are intended to be included in the scope of this patent.
Example 1
Firstly weighing 6.72g of copper sulfate pentahydrate, 0.2g of bipyridine and 16g of EDTA-2Na in 300ml of water, stirring to form emulsion, adding sodium hydroxide to regulate the pH value to be about 12, and adding 100ml of ethanol. Then adding 7.4g of superfine tungsten powder into the plating solution, heating the solution to 80 ℃ in a water bath under the condition of stirring and ultrasound, then adding 20ml of formaldehyde for plating, continuously adding sodium hydroxide solution to maintain the pH value between 11 and 12, and filtering, washing and drying the plated powder after 20 min. The powder obtained was subsequently reduced at 800 degrees celsius for 1h under a hydrogen atmosphere. And finally, sintering the sample by using discharge plasma sintering, wherein the pressure is 100MPa, the heating rate is 100 ℃/min, the heat preservation temperature is 1000 ℃, and the heat preservation time is 5 minutes, so that the tungsten-copper ultrafine crystal composite material with the copper content of 20wt.% is finally prepared. Wherein the grain sizes of the tungsten phase and the copper phase are both between 100 and 500 nanometers, the compactness is about 94 percent, the average compressive strength can reach 1600MPa, the hardness reaches 500HV, and the electric conductivity is about 38 percent IACS. The phase analysis result of the ultra-fine grain tungsten-copper composite material prepared in this example is shown in fig. 1, and the microscopic morphology is shown in fig. 2 and 3.
Example 2
Firstly, 3.36g of copper sulfate pentahydrate, 0.2g of bipyridine and 10g of EDTA-2Na are weighed and dissolved in 200ml of water, stirred until emulsion is formed, then sodium hydroxide is added to regulate the pH value to be about 12, and 80ml of ethanol is added. Then adding 2.4g of superfine tungsten powder into the plating solution, heating the solution to 80 ℃ in a water bath under the condition of stirring and ultrasound, then adding 10ml of formaldehyde for plating, continuously adding sodium hydroxide solution to maintain the pH value between 11 and 12, and filtering, washing and drying the plated powder after 20 min. The powder obtained was subsequently reduced at 800 degrees celsius for 1h under a hydrogen atmosphere. And finally, sintering the sample by utilizing discharge plasma sintering, wherein the pressure is 100MPa, the heating rate is 100 ℃/min, the heat preservation temperature is 1000 ℃, and the heat preservation time is 5 minutes, so that the tungsten-copper ultrafine crystal composite material with the copper content of 30wt.% is finally prepared. Wherein the grain sizes of the tungsten phase and the copper phase are both between 100 and 500 nanometers, the compactness is about 94 percent, the average compressive strength can reach 1200MPa, the hardness reaches 360HV, and the electric conductivity is about 48 percent IACS. The morphology of the ultra-fine grained tungsten-copper composite powder prepared in this example is shown in fig. 4, the phase analysis result of the composite block is shown in fig. 5, and the micro-morphology is shown in fig. 6 and 7.
Example 3
Firstly weighing 6.72g of copper sulfate pentahydrate, 0.2g of bipyridine and 20g of EDTA-2Na, dissolving in 300ml of water, stirring to form emulsion, adding sodium hydroxide to regulate the pH value to be about 12, and adding 100ml of ethanol. Then adding 3.6g of superfine tungsten powder into the plating solution, heating the superfine tungsten powder to 80 ℃ in a water bath under the stirring ultrasonic condition, then adding 20ml of formaldehyde for plating, continuously adding sodium hydroxide solution to maintain the pH value between 11 and 12, and filtering, washing and drying the plated powder after 20 min. The obtained powder was subsequently reduced at 800 degrees celsius for 30min under hydrogen atmosphere. And finally, sintering the sample by utilizing discharge plasma sintering, wherein the heating rate is 100 ℃/min, the pressure is 100MPa, the heat preservation temperature is 1000 ℃, and the heat preservation time is 10 minutes, so that the tungsten-copper ultrafine crystal composite material with the copper content of 40wt.% is finally prepared. Wherein the grain sizes of the tungsten phase and the copper phase are both between 100 and 500 nanometers, the compactness is about 94 percent, the average compressive strength can reach 900MPa, the hardness reaches 240HV, and the electric conductivity is about 58 percent IACS. The phase microscopic morphology of the ultra-fine grain tungsten-copper composite material prepared in this example is shown in fig. 8, and the compressive stress strain curve thereof is shown in fig. 9.
Claims (1)
1. A preparation method of a high-strength high-conductivity ultrafine grain tungsten-copper composite material is characterized by comprising the following steps:
(1) Copper plating with superfine tungsten powder; firstly, copper sulfate, bipyridine, EDTA-2Na, sodium hydroxide and ethanol are used as raw materials to prepare a plating solution, wherein the concentration of the copper sulfate is 5-24g/L, the concentration of the bipyridine is 0.02-0.2g/L, the concentration of the EDTA-2Na is 15-50g/L, the concentration of the ethanol is 100-500ml/L, and the addition amount of the sodium hydroxide is required to ensure that the pH value of the solution is 11-12; then mixing the plating solution and the tungsten powder, adding continuous stirring and ultrasound in a water bath device, heating to 80 ℃, dropwise adding sufficient formaldehyde into the plating solution for plating, and continuously adding sodium hydroxide solution to maintain the pH value between 11 and 12; continuously depositing copper on the surface of the superfine tungsten powder under the autocatalysis of the tungsten powder to prepare copper-coated superfine tungsten powder;
(2) Filtering and collecting the copper-coated superfine tungsten powder obtained in the step (1), repeatedly washing with deionized water, finally washing with ethanol and drying at room temperature under a ventilation condition; then placing the dried copper-coated superfine tungsten powder into a tube furnace, and preserving the heat for 30-60 minutes at 750-900 ℃ in a hydrogen atmosphere to remove oxygen elements introduced in the preparation process to obtain high-purity superfine tungsten-copper composite powder;
(3) Filling the superfine tungsten-copper composite powder obtained in the step (2) into a graphite die, and then performing discharge plasma sintering under vacuum to obtain a superfine crystal tungsten-copper composite material block; the heating rate is 100-200 ℃/min, the heat preservation temperature is 950-1020 ℃, the heat preservation time is 2-20min, and the pressure is 100-200MPa; the cooling mode is furnace cooling;
the copper content in the final product ultra-fine grain tungsten-copper composite material is 20wt.%, 30wt.% or 40wt.%;
the grain sizes of the tungsten phase and the copper phase in the prepared ultra-fine grain tungsten-copper composite material are both between 100 and 500 nanometers.
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| CN102433480A (en) * | 2011-12-01 | 2012-05-02 | 北京理工大学 | Tungsten-copper alloy with low skeleton connectivity and preparation method thereof |
| CN106435319A (en) * | 2016-12-15 | 2017-02-22 | 四川恒珲新材料科技有限公司 | Tungsten-copper alloy and production method thereof |
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