CN115896576A - High-strength tungsten alloy and preparation method thereof - Google Patents
High-strength tungsten alloy and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 239000000843 powder Substances 0.000 claims abstract description 36
- 150000003657 tungsten Chemical class 0.000 claims abstract description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 238000009713 electroplating Methods 0.000 claims abstract description 17
- -1 titanium hydride Chemical compound 0.000 claims abstract description 14
- 229910000048 titanium hydride Inorganic materials 0.000 claims abstract description 14
- 229910026551 ZrC Inorganic materials 0.000 claims abstract description 12
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 41
- 239000010962 carbon steel Substances 0.000 claims description 41
- 238000004070 electrodeposition Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000005498 polishing Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 11
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 11
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VKTHZHSHTVVWPN-UHFFFAOYSA-N [Na].[Na].[Na].[Na].[Na].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCN Chemical compound [Na].[Na].[Na].[Na].[Na].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCN VKTHZHSHTVVWPN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 abstract description 22
- 239000000956 alloy Substances 0.000 abstract description 17
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- 238000005245 sintering Methods 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 239000008139 complexing agent Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 229910052721 tungsten Inorganic materials 0.000 description 10
- 239000010937 tungsten Substances 0.000 description 10
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 7
- 238000002490 spark plasma sintering Methods 0.000 description 7
- 230000000536 complexating effect Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229960003330 pentetic acid Drugs 0.000 description 5
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- 230000008569 process Effects 0.000 description 3
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VZWGHDYJGOMEKT-UHFFFAOYSA-J sodium pyrophosphate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O VZWGHDYJGOMEKT-UHFFFAOYSA-J 0.000 description 2
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- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
The invention relates to a high-strength tungsten alloy and a preparation method thereof, belonging to the technical field of alloy preparation. The invention takes self-made electroplating modified tungsten alloy as a base material, and titanium powder, titanium hydride powder and zirconium carbide are added to the base material to carry out high-energy ball milling to prepare ball milling powder; and finally, performing discharge plasma sintering on ball-milling powder obtained by high-energy ball milling to finally prepare the high-strength tungsten alloy, and adding titanium element to construct a large number of crystal boundary and phase boundary radiation absorption defects in the electroplated modified tungsten nanocrystalline alloy, wherein titanium particles are partially aggregated at the crystal boundary to pin the interface, so that the size of alloy crystal grains is stabilized, dislocation and point defects in the crystal grains are reduced, and the hardness and compressive strength of the alloy material are improved.
Description
Technical Field
The invention relates to a high-strength tungsten alloy and a preparation method thereof, belonging to the technical field of alloy preparation.
Background
At present, tungsten and tungsten alloys have high density, high strength, low thermal expansion coefficient, excellent corrosion resistance, good processability and the like, and have been widely applied in many fields such as aerospace, electronics, chemical engineering and the like. Such as welding electrodes, cutting tools, feedstock for spraying, lamp filaments, tube electrodes, armor piercing bullets, and shaped charge liners. However, with the development of science and technology, the requirements of customers and the evolution of modern war, the hardness of the tungsten alloy is also required to be higher, and the hardness, the compressive strength and other properties of the conventional tungsten alloy can not meet the requirements of modern industry at present.
In view of the above-mentioned drawbacks, the present invention is to create a high strength tungsten alloy and a method for preparing the same, so that the high strength tungsten alloy has industrial utility value.
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a high strength tungsten alloy and a method for preparing the same.
The invention relates to a high-strength tungsten alloy which comprises the following raw materials in parts by weight:
70-80 parts of electroplating modified tungsten alloy;
20-30 parts of titanium powder;
10-15 parts of titanium hydride powder;
5-10 parts of zirconium carbide powder;
the electroplating modified tungsten alloy is prepared by electrodepositing carbon steel particles in an electrodeposition solution.
Further, the electrodeposition solution comprises the following raw materials in parts by weight:
30-40 parts of nickel sulfate;
60-70 parts of sodium tungstate;
80-90 parts of diethylenetriamine pentaacetic acid pentasodium;
30-40 parts of triethanolamine;
20-30 parts of ammonium dihydrogen phosphate;
30-40 parts of boric acid;
1000-1200 parts of deionized water.
A preparation method of a high-strength tungsten alloy comprises the following specific preparation steps:
(1) Weighing 70-80 parts by weight of electroplating modified tungsten alloy, 20-30 parts by weight of titanium powder, 10-15 parts by weight of titanium hydride powder and 5-10 parts by weight of zirconium carbide powder, mixing to obtain mixed powder, putting the mixed powder into a high-energy planetary ball mill, and carrying out ball milling treatment for 20-24 hours at a ball-to-material ratio of 14;
(2) Pressing the ball-milling powder into a graphite mold with the inner diameter of 20mm, moving the graphite mold into an SPS chamber, firstly pressurizing to 40Mpa, heating to 1000 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, then pressurizing to 80Mpa, heating to 1200 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, finally heating to 1600 ℃ and keeping the temperature for 10min to finally obtain the high-strength tungsten alloy.
Further, the preparation method of the electroplating modified tungsten alloy comprises the following steps:
mixing the pretreated carbon steel particles and the electrodeposition solution according to the mass ratio of 1.
Further, the preparation steps of the pretreated carbon steel particles are as follows: selecting carbon steel particles with the particle size of 1-2 mm, grinding and polishing the carbon steel particles by using 600-mesh silicon carbide abrasive paper, immersing the carbon steel particles after grinding and polishing into a sodium hydroxide solution with the concentration of 40g/dm < 3 >, soaking and removing oil for 1-2 h, filtering, mixing filter residues and a dilute sulfuric acid solution with the mass fraction of 10% according to the mass ratio of 1.
Further, the preparation steps of the electrodeposition solution are as follows: weighing 30-40 parts of nickel sulfate, 60-70 parts of sodium tungstate, 80-90 parts of diethylenetriamine pentaacetic acid pentasodium, 30-40 parts of triethanolamine, 20-30 parts of ammonium dihydrogen phosphate, 30-40 parts of boric acid and 1000-1200 parts of deionized water, and mixing to obtain the electrodeposition solution.
By the scheme, the invention at least has the following advantages:
(1) Firstly, pretreating a carbon steel substrate in modes of sand paper polishing, alkaline leaching for oil removal and acid leaching activation to obtain pretreated carbon steel particles with surfaces suitable for deposition; then, taking nickel sulfate and sodium tungstate as main electrodeposition salts, taking diethylenetriaminepentaacetic acid pentasodium as a main complexing agent and triethanolamine as an auxiliary complexing agent to prepare an electrodeposition solution; the method comprises the steps of carrying out induction codeposition under the action of an electrodeposition solution, depositing nickel-tungsten alloy on the surface of carbon steel, and carrying out heat treatment on the carbon steel on which the nickel-tungsten alloy is deposited to finally prepare the electroplated modified tungsten alloy, wherein a main complexing agent used in the method is extremely strong in diethylenetriamine pentaacetic acid pentasodium complexing capacity, so that electrochemical polarization is increased in the electrodeposition process, the compactness of a coating is increased, the hardness and the mechanical strength of the electroplated modified tungsten alloy are improved, and triethanolamine serving as an auxiliary complexing agent can improve the complexity of a complexing network structure, so that deposited crystal nuclei are distributed radially, finally formed alloy structure crystal phases are dispersed and fused and wound with each other, so that a channel with dispersed internal stress is formed, the internal stress of the tungsten alloy is reduced, the crack resistance of the tungsten alloy is improved, and the subsequent heat treatment is carried out, because tungsten and nickel form a replacement type solid solution, and the tungsten atomic radius (1.37 zxft 3238) is larger than that of nickel (1.25 zxft 3262), the addition of tungsten causes the cell expansion of the nickel, the nickel has completely changed from the nickel to the amorphous state, so that the hardness of the electroplated modified tungsten alloy is further improved;
(2) Taking a self-made electroplating modified tungsten alloy as a base material, adding titanium powder, titanium hydride powder and zirconium carbide, and carrying out high-energy ball milling to obtain ball milling powder; and finally, performing discharge plasma sintering on ball-milling powder obtained by high-energy ball milling to finally prepare the high-strength tungsten alloy, and adding titanium element to construct a large number of crystal boundary and phase boundary radiation absorption defects in the electroplated modified tungsten nanocrystalline alloy, wherein titanium particles are partially aggregated at the crystal boundary to pin the interface, so that the size of alloy crystal grains is stabilized, dislocation and point defects in the crystal grains are reduced, and the hardness and compressive strength of the alloy material are improved.
The foregoing is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clear and clear, and to implement the technical solutions according to the content of the description, the following is a description of preferred embodiments of the present invention.
Detailed Description
The following examples are given to further illustrate embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
(1) Selecting carbon steel particles with the particle size of 1-2 mm, grinding and polishing the carbon steel particles by using 600-mesh silicon carbide abrasive paper, and immersing the carbon steel particles with the grinding and polishing concentration of 40g/dm 3 Soaking the mixture in a sodium hydroxide solution for degreasing for 1-2 h, filtering, mixing the filter residue with a 10% dilute sulfuric acid solution according to a mass ratio of 1; firstly, pretreating a carbon steel substrate in modes of sanding, alkaline leaching for oil removal and acid leaching activation to obtain pretreated carbon steel particles with surfaces suitable for deposition;
(2) Weighing 30-40 parts of nickel sulfate, 60-70 parts of sodium tungstate, 80-90 parts of diethylenetriamine pentaacetic acid pentasodium, 30-40 parts of triethanolamine, 20-30 parts of ammonium dihydrogen phosphate, 30-40 parts of boric acid and 1000-1200 parts of deionized water, and mixing to obtain an electrodeposition solution; then, preparing an electrodeposition solution by taking nickel sulfate and sodium tungstate as main electrodeposition salt, diethylene triamine penta-acetic acid pentasodium as a main complexing agent and triethanolamine as an auxiliary complexing agent;
(3) Mixing the pretreated carbon steel particles and the electrodeposition solution according to the mass ratio of 1 2 Carrying out electrodeposition treatment for 2-4 h, filtering and separating to obtain a filter cake after the electrodeposition treatment is finished, putting the filter cake into a muffle furnace, carrying out heat treatment for 2h at 500-600 ℃, and discharging to obtain the electroplated modified tungsten alloy; inducing codeposition under the action of the electrodeposition solution to deposit nickel-tungsten alloy on the surface of the carbon steel, and then carrying out heat treatment on the carbon steel on which the nickel-tungsten alloy is deposited to finally prepare the electroplating modified tungsten alloyThe complexing agent diethylene triamine penta acetic acid pentasodium has extremely strong complexing ability, electrochemical polarization is increased in the process of electrodeposition, so that the density of a plating layer is increased, the hardness and mechanical strength of the electroplated modified tungsten alloy are improved, the complexity of a complexing network structure can be improved by an auxiliary complexing agent triethanolamine, the deposition crystal nuclei are distributed in a radial manner, the finally formed alloy structure crystal phases are dispersed and fused and wound with each other, so that a channel with dispersed internal stress is formed, the internal stress of the tungsten alloy is reduced, the crack resistance of the tungsten alloy is improved, and the subsequent heat treatment is carried out, because tungsten and nickel form a displacement type solid solution, the tungsten atomic radius (1.37 nm) is larger than the nickel atomic radius (1.25 nm), the addition of tungsten enables the crystal cells of nickel to expand, the nickel-tungsten alloy completely generates amorphous-crystalline state conversion, the hardness is further increased, and the hardness of the electroplated modified tungsten alloy is improved;
(4) Weighing 70-80 parts by weight of electroplating modified tungsten alloy, 20-30 parts by weight of titanium powder, 10-15 parts by weight of titanium hydride powder and 5-10 parts by weight of zirconium carbide powder, mixing to obtain mixed powder, putting the mixed powder into a high-energy planetary ball mill, and carrying out ball milling treatment for 20-24 hours at a ball-to-material ratio of 14; taking a self-made electroplating modified tungsten alloy as a base material, adding titanium powder, titanium hydride powder and zirconium carbide, and carrying out high-energy ball milling to obtain ball milling powder;
(5) Pressing the ball-milling powder into a graphite mold with the inner diameter of 20mm, moving the graphite mold into an SPS chamber, pressurizing to 40Mpa, heating to 1000 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, pressurizing to 80Mpa, heating to 1200 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, heating to 1600 ℃ and keeping the temperature for 10min to finally obtain the high-strength tungsten alloy. And finally, performing discharge plasma sintering on ball-milling powder obtained by high-energy ball milling to finally prepare the high-strength tungsten alloy, and adding titanium element to construct a large number of crystal boundary and phase boundary radiation absorption defects in the electroplated modified tungsten nanocrystalline alloy, wherein titanium particles are partially aggregated at the crystal boundary to pin the interface, so that the size of alloy crystal grains is stabilized, dislocation and point defects in the crystal grains are reduced, and the hardness and compressive strength of the alloy material are improved.
Example 1
(1) Selecting carbon steel particles with the particle size of 1mm, grinding and polishing the carbon steel particles by using 600-mesh silicon carbide abrasive paper, immersing the carbon steel particles after grinding and polishing into a sodium hydroxide solution with the concentration of 40g/dm < 3 >, soaking and deoiling for 1h, filtering, mixing filter residues with a dilute sulfuric acid solution with the mass fraction of 10% according to the mass ratio of 1;
(2) Weighing 30 parts of nickel sulfate, 60 parts of sodium tungstate, 80 parts of diethylenetriamine pentaacetic acid pentasodium, 30 parts of triethanolamine, 20 parts of ammonium dihydrogen phosphate, 30 parts of boric acid and 1000 parts of deionized water, and mixing to obtain an electrodeposition solution;
(3) Mixing the pretreated carbon steel particles and the electrodeposition solution according to a mass ratio of 1;
(4) Weighing 70 parts of electroplating modified tungsten alloy, 20 parts of titanium powder, 10 parts of titanium hydride powder and 5 parts of zirconium carbide powder, mixing to obtain mixed powder, putting the mixed powder into a high-energy planetary ball mill, and carrying out ball milling treatment for 20 hours at a ball-to-material ratio of 14;
(5) Pressing the ball-milling powder into a graphite mold with the inner diameter of 20mm, moving the graphite mold into an SPS chamber, pressurizing to 40Mpa, heating to 1000 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, pressurizing to 80Mpa, heating to 1200 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, heating to 1600 ℃ and keeping the temperature for 10min to finally obtain the high-strength tungsten alloy.
Example 2
(1) Selecting carbon steel particles with the particle size of 2mm, grinding and polishing the carbon steel particles by using 600-mesh silicon carbide abrasive paper, immersing the carbon steel particles after grinding and polishing into a sodium hydroxide solution with the concentration of 40g/dm < 3 >, soaking and deoiling for 2 hours, filtering, mixing filter residues with a dilute sulfuric acid solution with the mass fraction of 10% according to the mass ratio of 1;
(2) Weighing 35 parts of nickel sulfate, 65 parts of sodium tungstate, 85 parts of diethylenetriaminepentaacetic acid pentasodium, 35 parts of triethanolamine, 25 parts of ammonium dihydrogen phosphate, 35 parts of boric acid and 1100 parts of deionized water, and mixing to obtain an electrodeposition solution;
(3) Mixing the pretreated carbon steel particles and the electrodeposition solution according to a mass ratio of 1;
(4) Weighing 75 parts of electroplating modified tungsten alloy, 25 parts of titanium powder, 13 parts of titanium hydride powder and 8 parts of zirconium carbide powder, mixing to obtain mixed powder, putting the mixed powder into a high-energy planetary ball mill, and carrying out ball milling treatment for 22 hours at a ball-to-material ratio of 14;
(5) Pressing the ball-milling powder into a graphite mold with the inner diameter of 20mm, moving the graphite mold into an SPS chamber, firstly pressurizing to 40Mpa, heating to 1000 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, then pressurizing to 80Mpa, heating to 1200 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, finally heating to 1600 ℃ and keeping the temperature for 10min to finally obtain the high-strength tungsten alloy.
Example 3
(1) Selecting carbon steel particles with the particle size of 2mm, grinding and polishing the carbon steel particles by using 600-mesh silicon carbide abrasive paper, then soaking the carbon steel particles after grinding and polishing into a sodium hydroxide solution with the concentration of 40g/dm < 3 >, removing oil for 2h, then filtering, mixing filter residues and a dilute sulfuric acid solution with the mass fraction of 10% according to the mass ratio of 1, soaking and activating for 40min, and then discharging to obtain pretreated carbon steel particles;
(2) Weighing 40 parts of nickel sulfate, 70 parts of sodium tungstate, 90 parts of pentasodium diethylenetriaminepentaacetate, 40 parts of triethanolamine, 30 parts of ammonium dihydrogen phosphate, 40 parts of boric acid and 1200 parts of deionized water, and mixing to obtain an electrodeposition solution;
(3) Mixing the pretreated carbon steel particles and the electrodeposition solution according to a mass ratio of 1;
(4) Weighing 80 parts by weight of electroplating modified tungsten alloy, 30 parts by weight of titanium powder, 15 parts by weight of titanium hydride powder and 10 parts by weight of zirconium carbide powder, mixing to obtain mixed powder, putting the mixed powder into a high-energy planetary ball mill, and carrying out ball milling treatment for 24 hours at a ball-to-material ratio of 14;
(5) Pressing the ball-milling powder into a graphite mold with the inner diameter of 20mm, moving the graphite mold into an SPS chamber, firstly pressurizing to 40Mpa, heating to 1000 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, then pressurizing to 80Mpa, heating to 1200 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, finally heating to 1600 ℃ and keeping the temperature for 10min to finally obtain the high-strength tungsten alloy.
Comparative example
Comparative example 1:
the preparation method of comparative example 1 is substantially the same as that of example 1 of the present invention except that a high-strength tungsten alloy was similarly prepared by using sodium pyrophosphate decahydrate as a complexing agent instead of pentasodium diethylenetriaminepentaacetate as a main complexing agent;
comparative example 2:
the preparation method of comparative example 2 is substantially the same as that of example 1 of the present invention except that triethanolamine, which is an auxiliary complexing agent, is not added, and a high-strength tungsten alloy is also prepared;
comparative example 3:
the comparative example 3 was prepared in substantially the same manner as in example 1 of the present invention, except that high-energy ball milling and spark plasma sintering were carried out without adding titanium powder and titanium hydride powder, and a high-strength tungsten alloy was also prepared;
the performance of examples 1 to 3 of the present invention and comparative examples 1 to 3 were measured, respectively, and the results are shown in table 1:
TABLE 1 Performance test results
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Density (%) | 98.1 | 98.8 | 98.1 | 90.3 | 95.3 | 92.1 |
| Hardness (HV) | 763 | 769 | 762 | 743 | 752 | 748 |
| Compressive strength (Mpa) | 2293 | 2301 | 2295 | 2206 | 2256 | 2239 |
As can be seen from the detection data in the table above, the tungsten alloy prepared in the embodiments 1-3 of the invention has high density, strong hardness and high compressive strength, and the technical scheme of the invention has high feasibility;
in contrast example 1, sodium pyrophosphate decahydrate, which is a complexing agent, was used instead of pentasodium diethylenetriaminepentaacetate, which is a complexing agent of the present invention, as a main complexing agent, and a high-strength tungsten alloy was also prepared; in comparative example 2, the high-strength tungsten alloy was prepared in the same manner without adding triethanolamine as an auxiliary complexing agent; finally, the density, hardness and compressive strength of the final tungsten alloy are obviously reduced, so that the method can be proved that the carbon steel substrate is pretreated by sanding, alkaline leaching for oil removal and acid leaching activation to obtain pretreated carbon steel particles with surfaces suitable for deposition; then, taking nickel sulfate and sodium tungstate as main electrodeposition salts, taking diethylenetriaminepentaacetic acid pentasodium as a main complexing agent and triethanolamine as an auxiliary complexing agent to prepare an electrodeposition solution; the method comprises the steps of carrying out induction codeposition under the action of an electrodeposition solution, depositing nickel-tungsten alloy on the surface of carbon steel, and carrying out heat treatment on the carbon steel on which the nickel-tungsten alloy is deposited to finally prepare the electroplated modified tungsten alloy, wherein a main complexing agent used in the method is extremely strong in diethylenetriamine pentaacetic acid pentasodium complexing capacity, so that electrochemical polarization is increased in the electrodeposition process, the compactness of a coating is increased, the hardness and the mechanical strength of the electroplated modified tungsten alloy are improved, and triethanolamine serving as an auxiliary complexing agent can improve the complexity of a complexing network structure, so that deposited crystal nuclei are distributed radially, finally formed alloy structure crystal phases are dispersed and fused and wound with each other, so that a channel with dispersed internal stress is formed, the internal stress of the tungsten alloy is reduced, the crack resistance of the tungsten alloy is improved, and the subsequent heat treatment is carried out, because tungsten and nickel form a replacement type solid solution, and the tungsten atomic radius (1.37 zxft 3238) is larger than that of nickel (1.25 zxft 3262), the addition of tungsten causes the cell expansion of the nickel, the nickel has completely changed from the nickel to the amorphous state, so that the hardness of the electroplated modified tungsten alloy is further improved;
comparative example 3 high-strength tungsten alloy was also obtained by high-energy ball milling and spark plasma sintering without adding titanium powder and titanium hydride powder; the hardness, the density and the compressive strength of the final tungsten alloy are reduced, so that the fact that the self-made electroplating modified tungsten alloy is used as a base material, titanium powder, titanium hydride powder and zirconium carbide are added, and high-energy ball milling is carried out to prepare ball milling powder; and finally, performing discharge plasma sintering on ball-milling powder obtained by high-energy ball milling to finally prepare the high-strength tungsten alloy, and adding titanium element to construct a large number of crystal boundary and phase boundary radiation absorption defects in the electroplated modified tungsten nanocrystalline alloy, wherein titanium particles are partially aggregated at the crystal boundary to pin the interface, so that the size of alloy crystal grains is stabilized, dislocation and point defects in the crystal grains are reduced, and the hardness and compressive strength of the alloy material are improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (6)
1. The high-strength tungsten alloy is characterized by comprising the following raw materials in parts by weight:
70-80 parts of electroplating modified tungsten alloy;
20-30 parts of titanium powder;
10-15 parts of titanium hydride powder;
5-10 parts of zirconium carbide powder;
the electroplating modified tungsten alloy is prepared by electrodepositing carbon steel particles in an electrodeposition solution.
2. The high-strength tungsten alloy according to claim 1, wherein the electrodeposition solution comprises the following raw materials in parts by weight:
30-40 parts of nickel sulfate;
60-70 parts of sodium tungstate;
80-90 parts of diethylene triamine pentaacetic acid pentasodium salt;
30-40 parts of triethanolamine;
20-30 parts of ammonium dihydrogen phosphate;
30-40 parts of boric acid;
1000-1200 parts of deionized water.
3. The method for preparing a high-strength tungsten alloy according to claim 2, which is characterized by comprising the following specific preparation steps:
(1) Weighing 70-80 parts by weight of electroplating modified tungsten alloy, 20-30 parts by weight of titanium powder, 10-15 parts by weight of titanium hydride powder and 5-10 parts by weight of zirconium carbide powder, mixing to obtain mixed powder, putting the mixed powder into a high-energy planetary ball mill, and carrying out ball milling treatment for 20-24 hours at a ball-to-material ratio of 14;
(2) Pressing the ball-milling powder into a graphite mold with the inner diameter of 20mm, moving the graphite mold into an SPS chamber, firstly pressurizing to 40Mpa, heating to 1000 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, then pressurizing to 80Mpa, heating to 1200 ℃ at the speed of 100 ℃/min, keeping the temperature for 30min, finally heating to 1600 ℃ and keeping the temperature for 10min to finally obtain the high-strength tungsten alloy.
4. The method for preparing the high-strength tungsten alloy according to claim 3, wherein the method for preparing the electroplating modified tungsten alloy comprises the following steps:
mixing the pretreated carbon steel particles and the electrodeposition solution according to a mass ratio of 1.
5. The method for preparing the high-strength tungsten alloy according to claim 4, wherein the preparation steps of the pretreated carbon steel particles are as follows: selecting carbon steel particles with the particle size of 1-2 mm, grinding and polishing the carbon steel particles by using 600-mesh silicon carbide abrasive paper, immersing the carbon steel particles after grinding and polishing into a sodium hydroxide solution with the concentration of 40g/dm < 3 >, soaking and deoiling for 1-2 h, filtering, mixing filter residues and a dilute sulfuric acid solution with the mass fraction of 10% according to the mass ratio of 1.
6. The method for preparing a high-strength tungsten alloy according to claim 4, wherein the electrodeposition solution is prepared by the steps of: weighing 30-40 parts of nickel sulfate, 60-70 parts of sodium tungstate, 80-90 parts of diethylenetriamine pentaacetic acid pentasodium, 30-40 parts of triethanolamine, 20-30 parts of ammonium dihydrogen phosphate, 30-40 parts of boric acid and 1000-1200 parts of deionized water, and mixing to obtain the electrodeposition solution.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5160534A (en) * | 1990-06-15 | 1992-11-03 | Hitachi Metals Ltd. | Titanium-tungsten target material for sputtering and manufacturing method therefor |
| WO2001077418A1 (en) * | 2000-04-07 | 2001-10-18 | Hui Gao | The method for electrodepositing rare-earth and transition metal alloys |
| WO2003066936A2 (en) * | 2002-02-06 | 2003-08-14 | Liqun Feng | Commercial process for electroplating nickel-phosphorus coatings |
| KR20050028449A (en) * | 2003-09-18 | 2005-03-23 | 한국원자력연구소 | Method for electroplating ni-p-b alloy and its plating solution |
| JP2006104574A (en) * | 2004-09-13 | 2006-04-20 | Kogane Mekki Kojo:Kk | Nickel-tungsten alloy plating liquid and method for forming nickel-tungsten alloy plated film |
| US20100140098A1 (en) * | 2008-05-15 | 2010-06-10 | Solopower, Inc. | Selenium containing electrodeposition solution and methods |
| CN104611599A (en) * | 2015-01-13 | 2015-05-13 | 西安理工大学 | Preparation method of aplitic tungsten-titanium alloy |
| CN105296777A (en) * | 2015-10-30 | 2016-02-03 | 西安理工大学 | Preparation method for low rich titanium-phase tungsten titanium alloy |
| CN112226662A (en) * | 2020-10-21 | 2021-01-15 | 广州大学 | Double-nanostructure tungsten alloy with good high-temperature stability and preparation method and application thereof |
| CN112359298A (en) * | 2020-10-30 | 2021-02-12 | 江苏盖特钨业科技有限公司 | High-toughness coarse-grain hard alloy and preparation method thereof |
| CN113186473A (en) * | 2021-04-14 | 2021-07-30 | 江苏盖特钨业科技有限公司 | Tungsten carbide cobalt hard alloy and preparation method thereof |
| US20220162764A1 (en) * | 2019-08-09 | 2022-05-26 | Changzhou University | Preparation method of copper-based graphene composite with high thermal conductivity |
-
2022
- 2022-12-23 CN CN202211661511.9A patent/CN115896576B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5160534A (en) * | 1990-06-15 | 1992-11-03 | Hitachi Metals Ltd. | Titanium-tungsten target material for sputtering and manufacturing method therefor |
| WO2001077418A1 (en) * | 2000-04-07 | 2001-10-18 | Hui Gao | The method for electrodepositing rare-earth and transition metal alloys |
| WO2003066936A2 (en) * | 2002-02-06 | 2003-08-14 | Liqun Feng | Commercial process for electroplating nickel-phosphorus coatings |
| KR20050028449A (en) * | 2003-09-18 | 2005-03-23 | 한국원자력연구소 | Method for electroplating ni-p-b alloy and its plating solution |
| JP2006104574A (en) * | 2004-09-13 | 2006-04-20 | Kogane Mekki Kojo:Kk | Nickel-tungsten alloy plating liquid and method for forming nickel-tungsten alloy plated film |
| US20100140098A1 (en) * | 2008-05-15 | 2010-06-10 | Solopower, Inc. | Selenium containing electrodeposition solution and methods |
| CN104611599A (en) * | 2015-01-13 | 2015-05-13 | 西安理工大学 | Preparation method of aplitic tungsten-titanium alloy |
| CN105296777A (en) * | 2015-10-30 | 2016-02-03 | 西安理工大学 | Preparation method for low rich titanium-phase tungsten titanium alloy |
| US20220162764A1 (en) * | 2019-08-09 | 2022-05-26 | Changzhou University | Preparation method of copper-based graphene composite with high thermal conductivity |
| CN112226662A (en) * | 2020-10-21 | 2021-01-15 | 广州大学 | Double-nanostructure tungsten alloy with good high-temperature stability and preparation method and application thereof |
| CN112359298A (en) * | 2020-10-30 | 2021-02-12 | 江苏盖特钨业科技有限公司 | High-toughness coarse-grain hard alloy and preparation method thereof |
| CN113186473A (en) * | 2021-04-14 | 2021-07-30 | 江苏盖特钨业科技有限公司 | Tungsten carbide cobalt hard alloy and preparation method thereof |
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