CN113637865A - GO/TiCN-doped wear-resistant tungsten-copper composite material and preparation method thereof - Google Patents
GO/TiCN-doped wear-resistant tungsten-copper composite material and preparation method thereof Download PDFInfo
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- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 48
- 238000005245 sintering Methods 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000007747 plating Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- -1 2' -bipyridine Chemical compound 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 8
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 7
- 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 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 7
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 26
- 239000000463 material Substances 0.000 description 20
- 229910045601 alloy Inorganic materials 0.000 description 16
- 239000000956 alloy Substances 0.000 description 16
- 239000011159 matrix material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000002490 spark plasma sintering Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- YYFRJBKEQFXXIB-UHFFFAOYSA-N copper gold tungsten Chemical compound [W][Cu][Au] YYFRJBKEQFXXIB-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- 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
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
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- 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
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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Abstract
The invention provides a GO/TiCN doped wear-resistant tungsten-copper composite material and a preparation method thereof, wherein the traditional tungsten-copper alloy has poor wear resistance, the service life of the traditional tungsten-copper alloy used as a wear-resistant part is short, and the service condition of a contact part of the traditional tungsten-copper alloy is influenced.
Description
Technical Field
The invention belongs to the field of tungsten-copper composite materials, and particularly relates to a preparation method of a GO/TiCN-doped wear-resistant tungsten-copper composite material.
Background
The tungsten-copper composite material is an immiscible high-specific gravity pseudoalloy which is mainly W, Cu. Because of its outstanding properties of both W and Cu, such as: high temperature resistance, arc ablation resistance, easy cutting and processing, high strength, large specific gravity, good electric and thermal conductivity and sweating and cooling characteristics, and is widely used as an electric contact material, an electronic packaging material and a heat sink material. The method has wide application in the industries of metallurgy, military, aerospace and the like (guide rail materials of electromagnetic guns, nozzle nosecones of rocket engines and the like). In recent years, tungsten copper composites have also been increasingly used in other applications due to their special properties. Such as electrical materials on high-speed rails, guide materials, guide rails for television production lines, etc. The guide and guard part has a special working environment, and the working condition that the temperature reaches thousands of degrees puts a high requirement on the high-temperature resistance of the material. On the other hand, the guide and guard piece and the binding piece generate relative movement when working, so that the guide and guard material needs lower friction coefficient and higher wear resistance. However, most of the current research on tungsten-copper alloys focuses on mechanical properties.
In the existing traditional tungsten-copper alloy, due to the huge difference of melting points between the tungsten-copper alloy and the immiscibility of the tungsten-copper alloy and the tungsten-copper alloy, the general metal melting process is determined to be difficult to prepare the tungsten-copper based composite material with uniform components, high density, good hardness, wear resistance and the like, and the tungsten-copper based composite material has short service life when used as a wear-resistant part and influences the service condition of a contact part of the wear-resistant part. According to the national standard, the hardness of the W70Cu30 alloy is 170HV, and the density is 13.8g/cm3The density is 94.2%. If the defects of the tungsten-copper alloy can be compensated by adding other phases to improve the wear resistance of the tungsten-copper alloy, the tungsten-copper alloy is expected to be applied to the service in some extreme environments.
Due to the particularity of the structure of the tungsten-copper alloy, the strength of a tungsten matrix is obviously reduced along with the temperature rise, and the like, if the performance improvement effect is not obvious through the improvement of the preparation process, the addition of a third phase is a convenient and effective way.
In order to further improve the wear resistance of the tungsten-copper composite material, the invention introduces a preparation method of the tungsten-copper composite material with high wear resistance.
Disclosure of Invention
The invention aims to provide a preparation method of GO/TiCN doped wear-resistant tungsten-copper composite material, aiming at the problems that the tungsten-copper alloy in the prior art has poor wear resistance, so that the tungsten-copper alloy has short service life when used as a wear-resistant part and the service condition of a contact part of the tungsten-copper alloy is influenced.
In order to achieve the purpose, the invention adopts the following technical scheme:
copper-plated tungsten powder, nickel powder, copper powder and GO/TiCN-doped powder are adopted to prepare the tungsten-copper alloy through plasma sintering, and the sintered GO/TiCN hard particles are dispersed and distributed in the material to play a role of 'pinning', so that the densification and sintering of the composite material can be promoted, the strength of the material matrix can be enhanced, the wear resistance of the material can be improved, the friction coefficient can be reduced, and the service life of the material can be prolonged.
The invention provides a preparation method of a GO/TiCN-doped tungsten-copper composite material, which improves the wear resistance of a tungsten-copper alloy. The specific scheme is as follows:
(1) preparing copper-plated tungsten powder: quantitative weighing of CuSO4·5H2Preparing a plating solution by using O, sodium potassium tartrate tetrahydrate, ethylene diamine tetraacetic acid disodium, polyethylene glycol, 2' -bipyridyl, sodium hydroxide particles and formaldehyde. A fixed amount of tungsten powder was washed in 10wt.% NaOH solution and 20wt.% HCl solution for 15min and then added to the plating solution. And (3) keeping the temperature at 55 ℃ and magnetically stirring, continuously adding NaOH in the reaction process to maintain the pH value to be 11-13, washing the reacted powder to be neutral after the plating solution is changed from blue to colorless, and then putting the powder into a drying oven to keep the temperature at 50 ℃ for 6 hours for drying to obtain the copper-plated tungsten powder. Tungsten powder, CuSO4·5H2The mass ratio of the O, the potassium sodium tartrate tetrahydrate, the disodium ethylene diamine tetraacetate, the polyethylene glycol, the 2,2' -bipyridine, the sodium hydroxide particles and the formaldehyde is 20-30: 20-25: 1-10: 0.01-0.05: 10-20: 20-25.
(2) Weighing powder: copper powder, copper-plated tungsten powder, nickel powder, TiCN powder and GO powder are respectively weighed according to a certain proportion. The selected powder particle sizes were: 10-15 mu m of copper powder, 10-15 mu m of copper-plated tungsten powder, 10-15 mu m of nickel powder, 1-2 mu m of TiCN powder and 10-50 mu m of GO powder. The mass ratio of the copper powder, the copper-plated tungsten powder, the nickel powder, the TiCN powder and the GO powder is 9-10: 80-90: 0.5-3: 1-4: 0.1 to 1.
(3) Mechanical mixing: and (3) putting all the powder into a sealed tank, and mechanically mixing for 10-20 hours at a rotating speed of 100-150 r/min by using a planetary ball mill to obtain composite powder with uniform components.
(4) Plasma sintering: filling the composite powder into a graphite mold with an inner hole phi of 25mm, placing the graphite mold in a vacuum sintering furnace, sintering to prepare the tungsten-copper composite material, keeping the temperature at 1000-1100 ℃ for 5-7 min, keeping the pressure applied to the powder at 40Mpa for a heat preservation time period, and introducing hydrogen for protection in the heat preservation state during sintering to prevent excessive volatilization of Cu in the composite material in vacuum. And (4) taking out the die after the furnace temperature is reduced to room temperature, thus obtaining the GO/TiCN doped tungsten-copper composite material.
The invention has the advantages that:
(1) the tungsten-copper alloy has unobvious performance improvement effect through preparation process improvement due to factors such as the particularity of the structure of the tungsten-copper alloy, the strength of a tungsten matrix is obviously reduced along with the temperature rise, and the like. The invention adopts a way of adding a third phase to improve the performance of the tungsten-copper alloy. The traditional tungsten-copper alloy has poor wear resistance, and has short service life when used as a wear-resistant part, thereby influencing the service condition of a contact part of the wear-resistant part. The invention solves the problem of poor wear resistance under high temperature by adding GO/TiCN. By adding the particles with high hardness and high melting point, the effects of abrasion resistance and wear resistance can be achieved.
(2) According to the invention, copper-tungsten-plated powder is adopted in W70Cu30 alloy, and GO/TiCN powder with a proper proportion is added, so that the prepared composite material has compact structure, good uniformity and excellent performance, and is mainly applied to the field of high-temperature friction. According to the invention, copper-plated tungsten powder, nickel powder, copper powder, GO powder and TiCN powder are adopted, and spark plasma sintering is adopted to prepare the (SPS) tungsten-copper alloy, and the sintered GO powder and TiCN hard particles are dispersed and distributed in the material to play a role of pinning, so that the densification and sintering of the composite material can be promoted, the strength of the material matrix is enhanced, the wear resistance of the material is improved, the friction coefficient is reduced, and the service life of the material is prolonged.
Drawings
FIG. 1 microstructure diagrams of doped and undoped GO/TiCN WolCu alloys, (a) undoped GO/TiCN, (b) doped TiCN, (c) doped GO, (d) doped GO/TiCN; note: the state during doping is GO, but the GO can be reduced into rGO in the high-temperature sintering process, so that the surface of the matrix is marked with the rGO;
FIG. 2 is a graph of wear scar morphology for gold tungsten-copper alloys with and without GO/TiCN, (a) with GO/TiCN, (b) with TiCN, (c) with GO, and (d) with GO/TiCN;
FIG. 3 effect of GO/TiCN doping on W70Cu30 alloy hardness;
FIG. 4 effect of GO/TiCN doping on the friction coefficient of W70Cu30 alloy;
FIG. 5 effect of GO/TiCN doping on wear rate of W70Cu30 alloy.
Detailed Description
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below. The method of the present invention is a method which is conventional in the art unless otherwise specified.
COMPARATIVE EXAMPLE 1 (preparation of W70Cu30 alloy undoped GO and TiCN)
According to tungsten powder, CuSO4·5H2Weighing and preparing O, potassium sodium tartrate tetrahydrate, disodium ethylene diamine tetraacetate, polyethylene glycol, 2' -bipyridine, sodium hydroxide particles and formaldehyde in a mass ratio of 25.6:25:24:23.5:4:0.02:15:20, washing tungsten powder in a 10wt.% NaOH solution and a 20wt.% HCl solution for 15min, and adding the tungsten powder into the plating solution. And (3) keeping the temperature at 55 ℃ and magnetically stirring, continuously adding NaOH in the reaction process to maintain the pH value to be 11-13, washing the reacted powder to be neutral after the plating solution turns from blue to colorless and is clear, and then putting the powder into a drying oven to be dried at 50 ℃ for 6 hours to obtain the copper-plated tungsten powder.
And 2, weighing the powder.
According to the mass ratio of copper powder to copper-plated tungsten powder to nickel powder of 11.5: the powder was weighed 87.5: 1. The selected powder particle sizes were: copper powder 10-15 μm, copper-plated tungsten powder 10-15 μm, and nickel powder 10-15 μm.
And 3, mechanically mixing the powder.
All the powders are put into a sealed tank and mixed for 10 hours by a planetary ball mill at the rotating speed of 150r/min to obtain evenly mixed composite powder.
And 4, sintering the sample.
Then 25g of the powder is put into a graphite die with an inner hole of phi 25mm and sintered in a vacuum sintering furnace. Sintering at 1050 deg.C under 40Mpa for 6min, and introducing hydrogen gas for protection. And (4) taking out the die after the furnace temperature is reduced to room temperature, thus obtaining the GO/TiCN-undoped tungsten-copper composite material.
Comparative example 2 (preparation of W70Cu30 alloy doped with 1.5wt% TiCN)
According to tungsten powder, CuSO4·5H2Weighing and preparing O, potassium sodium tartrate tetrahydrate, disodium ethylene diamine tetraacetate, polyethylene glycol, 2' -bipyridine, sodium hydroxide particles and formaldehyde in a mass ratio of 25.6:25:24:23.5:4:0.02:15:20, washing tungsten powder in a 10wt.% NaOH solution and a 20wt.% HCl solution for 15min, and adding the tungsten powder into the plating solution. And (3) keeping the temperature at 55 ℃ and magnetically stirring, continuously adding NaOH in the reaction process to maintain the pH value to be 11-13, washing the reacted powder to be neutral after the plating solution turns from blue to colorless and is clear, and then putting the powder into a drying oven to be dried at 50 ℃ for 6 hours to obtain the copper-plated tungsten powder.
And 2, weighing the powder.
According to the mass ratio of copper powder, copper-plated tungsten powder, nickel powder and TiCN powder of 10: 87.5:1: 1.5 weigh the powder. The selected powder particle sizes were: copper powder 10-15 μm, copper-plated tungsten powder 10-15 μm, nickel powder 10-15 μm, and TiCN powder 1-2 μm.
And 3, mechanically mixing the powder.
All the powders are put into a sealed tank and mixed for 10 hours by a planetary ball mill at the rotating speed of 150r/min to obtain evenly mixed composite powder.
And 4, sintering the sample.
Then 25g of the powder is put into a graphite die with an inner hole of phi 25mm and sintered in a vacuum sintering furnace. Sintering at 1050 deg.C under 40Mpa for 6min, and introducing hydrogen gas for protection. And taking out the mold after the furnace temperature is reduced to the room temperature to obtain the TiCN-doped tungsten-copper composite material.
COMPARATIVE EXAMPLE 3 (preparation of W70Cu30 alloy doped with 0.3wt% GO)
According to tungsten powder, CuSO4·5H2Weighing and preparing O, potassium sodium tartrate tetrahydrate, disodium ethylene diamine tetraacetate, polyethylene glycol, 2' -bipyridine, sodium hydroxide particles and formaldehyde in a mass ratio of 25.6:25:24:23.5:4:0.02:15:20, washing tungsten powder in a 10wt.% NaOH solution and a 20wt.% HCl solution for 15min, and adding the tungsten powder into the plating solution. And (3) keeping the temperature at 55 ℃ and magnetically stirring, continuously adding NaOH in the reaction process to maintain the pH value to be 11-13, washing the reacted powder to be neutral after the plating solution turns from blue to colorless and is clear, and then putting the powder into a drying oven to be dried at 50 ℃ for 6 hours to obtain the copper-plated tungsten powder.
And 2, weighing the powder.
According to the mass ratio of copper powder, copper-plated tungsten powder, nickel powder and GO powder being 11.2: 87.5:1: 0.3 weigh the powder. The selected powder particle sizes were: copper powder 10-15 μm, copper-plated tungsten powder 10-15 μm, nickel powder 10-15 μm, and GO powder 10-50 μm.
And 3, mechanically mixing the powder.
All the powders are put into a sealed tank and mixed for 10 hours by a planetary ball mill at the rotating speed of 150r/min to obtain evenly mixed composite powder.
And 4, sintering the sample.
Then 25g of the powder is put into a graphite die with an inner hole of phi 25mm and sintered in a vacuum sintering furnace. Sintering at 1050 deg.C under 40Mpa for 6min, and introducing hydrogen gas for protection. And (4) taking out the die after the furnace temperature is reduced to room temperature, and obtaining the GO-doped tungsten-copper composite material.
Example 1 (preparation of W70Cu30 alloy doped with 0.3wt% GO and 1.5wt% TiCN)
According to tungsten powder, CuSO4·5H2Weighing and preparing O, potassium sodium tartrate tetrahydrate, disodium ethylene diamine tetraacetate, polyethylene glycol, 2' -bipyridine, sodium hydroxide particles and formaldehyde in a mass ratio of 25.6:25:24:23.5:4:0.02:15:20, washing tungsten powder in a 10wt.% NaOH solution and a 20wt.% HCl solution for 15min, and adding the tungsten powder into the plating solution. And (3) keeping the temperature at 55 ℃ and magnetically stirring, continuously adding NaOH in the reaction process to maintain the pH value to be 11-13, washing the reacted powder to be neutral after the plating solution turns from blue to colorless and is clear, and then putting the powder into a drying oven to be dried at 50 ℃ for 6 hours to obtain the copper-plated tungsten powder.
And 2, weighing the powder.
According to the mass ratio of copper powder, copper-plated tungsten powder, nickel powder, TiCN powder and GO powder of 9.7: 87.5:1: 1.5: 0.3 weigh the powder. The selected powder particle sizes were: 10-15 mu m of copper powder, 10-15 mu m of copper-plated tungsten powder, 10-15 mu m of nickel powder, 1-2 mu m of TiCN powder and 10-50 mu m of GO powder.
And 3, mechanically mixing the powder.
All the powders are put into a sealed tank and mixed for 10 hours by a planetary ball mill at the rotating speed of 150r/min to obtain evenly mixed composite powder.
And 4, sintering the sample.
Then 25g of the powder is put into a graphite die with an inner hole of phi 25mm and sintered in a vacuum sintering furnace. Sintering at 1050 deg.C under 40Mpa for 6min, and introducing hydrogen gas for protection. And (4) taking out the die after the furnace temperature is reduced to room temperature, thus obtaining the GO/TiCN doped tungsten-copper composite material.
The traditional tungsten-copper alloy has poor wear resistance, and has short service life when used as a wear-resistant part, thereby influencing the service condition of a contact part of the wear-resistant part. The GO/TiCN doped tungsten-copper alloy prepared by the method disclosed by the invention has the advantages that the wear resistance of the tungsten-copper alloy is improved, and the friction coefficient is reduced.
Fig. 1 is a microstructure photograph of a W70Cu30 alloy before and after a tungsten copper composite material is doped with GO/TiCN, and after the tungsten copper composite material is doped with GO and TiCN, it can be seen that large-scale W phase aggregation appears on the surface of a substrate before the tungsten copper composite material is doped (a in fig. 1), after the tungsten copper composite material is doped with TiCN alone (b in fig. 1), and after the GO is doped alone (c in fig. 1), grains of the composite material are significantly refined, because graphene oxide prevents the growth of the grains in a sintering process in the substrate, and at the same time, TiCN particles can play a role in "pinning", prevent the aggregation of the substrate particles in the sintering process, and make the structure of the composite material more compact and uniform. FIG. 2 is a frictional wear topography of W70Cu30 alloy before and after a tungsten copper composite material is doped with GO/TiCN and after GO and TiCN are doped separately, under the conditions of a load of 10N, a motor frequency of 10Hz and a frictional wear test time of 30min, it can be seen that a grinding trace area (a in FIG. 2) before doping has a lot of material peeling phenomena and a micro-crack phenomenon is obvious, and the wear mechanism of the tungsten copper composite material is mainly abrasive wear and fatigue wear according to the frictional wear topography; the wear mark area (b in figure 2) after doping TiCN has more cracks and furrows, the wear mechanism can be judged to be mainly abrasive wear and fatigue wear, the wear mark area (c in figure 2) after doping GO has the material surface layer falling phenomenon and the pit appearance, the wear mechanism is mainly abrasive wear and adhesive wear, and the wear mark area (d in figure 2) after doping GO/TiCN has cracks and furrows, and the wear mechanism is mainly abrasive wear and fatigue wear. Hardness and room temperature frictional wear performance of the W70Cu30 alloy before and after GO/TiCN doping are shown in FIGS. 3, 4 and 5.
Referring to fig. 3, 4 and 5, table 1 is obtained, and the properties of the W70Cu30 alloy before and after doping GO/TiCN are compared, so that it can be seen that after doping GO/TiCN, the hardness of the W70Cu30 alloy is improved by 27.4%, the friction coefficient is reduced by 50.4%, the wear rate is reduced by 81.6%, and the wear resistance and the antifriction are both obviously improved.
This is because:
(1) the TiCN particles are uniformly dispersed in the matrix as a hard phase, so that the hardness of the matrix can be enhanced, and the wear rate is reduced; in addition, TiCN particles can be distributed between the tungsten-copper phase and GO to guide element diffusion, so that the tungsten-copper phase and GO are connected more tightly, and the hardness and the density of the composite material are improved.
(2) The TiCN hard particles can effectively enhance the bonding strength of a W-Cu/GO interface, can effectively resist shear stress and prevent graphene oxide on the surface of a matrix from being stripped in a friction process; due to the pinning effect of TiCN particles, under the action of normal load, graphene oxide is easier to shear and peel between layers, and is continuously spread on a wear contact surface to form a graphene lubricating film, so that the friction coefficient is reduced.
(3) When the composite material is subjected to external load, the graphene oxide can transfer and bear partial load so as to prevent cracks at an interface from expanding; the material has a synergistic effect with the bonding strength of the TiCN particle reinforced material interface, and can better reduce the friction coefficient and the wear rate of the material.
TABLE 1 comparison of W70Cu30 alloy properties before and after GO/TiCN doping
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A preparation method of a GO/TiCN doped tungsten-copper composite material is characterized by comprising the following steps:
(1) preparing copper-plated tungsten powder: quantitative weighing of CuSO4·5H2Preparing a plating solution from O, potassium sodium tartrate tetrahydrate, disodium ethylene diamine tetraacetate, polyethylene glycol, 2' -bipyridine, sodium hydroxide particles and formaldehyde, washing quantitative tungsten powder in NaOH solution and HCl solution respectively, adding the washed tungsten powder into the plating solution, keeping the temperature at 55 ℃ and magnetically stirring, continuously adding NaOH to maintain the pH value to be 11-13 in the reaction process, washing the reacted powder to be neutral after the plating solution turns to be colorless from blue, and then putting the washed powder into a drying box to keep the temperature at 50 ℃ for 6 hours for drying to obtain copper-plated tungsten powder;
(2) weighing powder: respectively weighing copper powder, copper-plated tungsten powder, nickel powder, TiCN powder and GO powder according to a certain proportion;
(3) mechanical mixing: putting all the powder into a sealed tank, and mixing for 10-20 hours by using a planetary ball mill to obtain composite powder with uniform components;
(4) plasma sintering: filling the composite powder into a graphite mold, placing the graphite mold in a vacuum sintering furnace for sintering to prepare the tungsten-copper composite material, wherein the heat preservation temperature is 1000-1100 ℃, the heat preservation time is 5-7 min, the heat preservation time period is 40Mpa of pressure applied to the composite powder, during sintering, hydrogen needs to be introduced for protection in the heat preservation state, excessive volatilization of Cu in the composite material in vacuum is prevented, and the mold is taken out after the furnace temperature is reduced to the room temperature, so that the GO/TiCN doped tungsten-copper composite material is obtained.
2. The method according to claim 1, wherein the concentration of the NaOH solution in step (1) is 10wt.%, and the concentration of the HCl solution is 20 wt.%.
3. The method according to claim 1, wherein the tungsten powder in step (1) is washed in the NaOH solution and the HCl solution for 15 min.
4. The method according to claim 1, wherein the tungsten powder and CuSO are used in the step (1)4·5H2The mass ratio of O, potassium sodium tartrate tetrahydrate, disodium ethylene diamine tetraacetate, polyethylene glycol, 2' -bipyridine, sodium hydroxide particles and formaldehyde is 20-30: 20-25: 1-10: 0.01-0.05: 10-20: 20-25.
5. The preparation method according to claim 1, wherein the mass ratio of the copper powder, the copper-plated tungsten powder, the nickel powder, the TiCN powder and the GO powder in the step (2) is 9-10: 80-90: 0.5-3: 1-4: 0.1 to 1.
6. The method of claim 1, wherein the particle size of the powder selected in step (2) is: 10-15 mu m of copper powder, 10-15 mu m of copper-plated tungsten powder, 10-15 mu m of nickel powder, 1-2 mu m of TiCN powder and 10-50 mu m of GO powder.
7. The preparation method according to claim 1, wherein the rotation speed of the planetary ball mill in the step (3) is 100 to 150 r/min.
8. The method according to claim 1, wherein the inner bore of the graphite mold in the step (4) is phi 25 mm.
9. GO/TiCN doped tungsten copper composites made by the method of any of claims 1-8.
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| JP2003328055A (en) * | 2002-05-15 | 2003-11-19 | Nikko Materials Co Ltd | COPPER PLATED SiC COMPOSITE POWDER, METHOD FOR MANUFACTURING THE COMPOSITE METALLIC POWDER, COPPER PLATED SiC COMPOSITE POWDER SINTERED BODY, AND METHOD FOR MANUFACTURING THE SINTERED BODY |
| CN101537491A (en) * | 2009-04-30 | 2009-09-23 | 北京科技大学 | Preparation method of copper-coated tungsten composite powder |
| CN108950279A (en) * | 2018-07-27 | 2018-12-07 | 西北有色金属研究院 | A method of collaboration improves CuW contact material arc erosion performance |
| CN109234597A (en) * | 2018-11-22 | 2019-01-18 | 江苏经纬阀业有限公司 | A kind of tungsten-copper alloy and preparation method thereof |
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| JP2003328055A (en) * | 2002-05-15 | 2003-11-19 | Nikko Materials Co Ltd | COPPER PLATED SiC COMPOSITE POWDER, METHOD FOR MANUFACTURING THE COMPOSITE METALLIC POWDER, COPPER PLATED SiC COMPOSITE POWDER SINTERED BODY, AND METHOD FOR MANUFACTURING THE SINTERED BODY |
| CN101537491A (en) * | 2009-04-30 | 2009-09-23 | 北京科技大学 | Preparation method of copper-coated tungsten composite powder |
| CN108950279A (en) * | 2018-07-27 | 2018-12-07 | 西北有色金属研究院 | A method of collaboration improves CuW contact material arc erosion performance |
| CN109234597A (en) * | 2018-11-22 | 2019-01-18 | 江苏经纬阀业有限公司 | A kind of tungsten-copper alloy and preparation method thereof |
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