CN117904478B - High-resistant Wen Guge alloy and preparation method thereof - Google Patents
High-resistant Wen Guge alloy and preparation method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 79
- 239000000956 alloy Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 83
- 238000010438 heat treatment Methods 0.000 claims abstract description 65
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000010941 cobalt Substances 0.000 claims abstract description 50
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 40
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical class [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000003723 Smelting Methods 0.000 claims abstract description 33
- 238000000265 homogenisation Methods 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000604 Ferrochrome Inorganic materials 0.000 claims abstract description 20
- 229910026551 ZrC Inorganic materials 0.000 claims abstract description 20
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 238000007747 plating Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000007943 implant Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000000788 chromium alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910001432 tin ion Inorganic materials 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000020084 Bone disease Diseases 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 206010060820 Joint injury Diseases 0.000 description 1
- 206010061363 Skeletal injury Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 molybdenum ion Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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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
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Powder Metallurgy (AREA)
Abstract
The application relates to the technical field of cobalt-chromium alloy preparation, and particularly discloses a high-strength Wen Guge alloy and a preparation method thereof. The preparation method of the high-temperature-resistant cobalt-chromium alloy comprises the following steps: mixing cobalt, iron, aluminum, zirconium carbide and boron to obtain a mixture, carrying out vacuum smelting on the mixture, casting an ingot, then carrying out homogenization treatment to obtain a blank, heating the blank, preserving heat, cooling, preserving heat, and cooling to room temperature to obtain pretreated cobalt; mixing pretreated cobalt, titanium powder and copper powder, vacuum smelting, adding micro-carbon ferrochromium powder, molybdenum powder, tungsten powder and chromium powder, heating and smelting, and casting ingots to obtain alloy ingots; homogenizing the alloy ingot to obtain a pretreated alloy ingot I; treating the pretreated alloy ingot I, and cooling to obtain a pretreated alloy ingot II; and performing heat treatment on the pretreated alloy ingot II to obtain the alloy ingot II. The cobalt-chromium alloy has better hardness, tensile strength and heat resistance.
Description
Technical Field
The application relates to the technical field of cobalt-chromium alloy preparation, in particular to a high-strength Wen Guge alloy and a preparation method thereof.
Background
In recent years, with the increase of the population aging problem and the increase of the patients suffering from bone diseases such as joint injury and bone injury, the market of medical implants is expanding. In order to meet the needs of patients, a great deal of research on implant materials and processing methods is conducted, and the aim is to prepare the medical implant with high precision, excellent mechanical properties and meeting biocompatibility.
Currently, commonly used implant materials include metallic materials, high molecular polymer materials, and ceramic materials. Among them, ceramic and polymer materials have good biocompatibility, but have poor mechanical strength, and cannot be applied to some bearing parts. In comparison, the cobalt-chromium alloy, titanium alloy, stainless steel and other metal materials not only meet the requirement of biocompatibility, but also have higher strength and fracture toughness, so that the cobalt-chromium alloy, titanium alloy, stainless steel and other metal materials are widely applied in the field of implants. Among them, cobalt-chromium alloy plays an important role for a long time due to its excellent biocompatibility and better mechanical properties.
The existing cobalt-chromium alloy is prepared by adopting an atomization method, and the obtained alloy has poor compactness and poor heat resistance.
Disclosure of Invention
In order to further improve the heat resistance and compactness of the cobalt-chromium alloy, the application provides a high-resistant Wen Guge alloy and a preparation method thereof.
In a first aspect, the application provides a preparation method of a high Wen Guge-resistant alloy, which adopts the following technical scheme:
a preparation method of a high Wen Guge-resistant alloy comprises the following steps:
(1) Mixing cobalt, iron, aluminum, zirconium carbide and boron to obtain a mixture, carrying out vacuum smelting on the mixture, casting an ingot, carrying out homogenization treatment to obtain a blank, heating the blank to 1100-1120 ℃, preserving heat for 8-9h, cooling to 850-870 ℃ and preserving heat for 15-16h, finally cooling to room temperature, and grinding to obtain pretreated cobalt;
(2) Mixing the pretreated cobalt, titanium powder and copper powder obtained in the step (1), vacuum smelting at 1300-1500 ℃, then adding micro-carbon ferrochrome powder, molybdenum powder, tungsten powder and chromium powder, heating to 1800-2000 ℃, smelting, and casting ingots to obtain alloy ingots;
(3) Homogenizing the alloy ingot obtained in the step (2) for 4-5 times to obtain a pretreated alloy ingot I; the temperature of each homogenization treatment is 1000-1100 ℃, and the treatment time is 30-35h;
(4) Sequentially treating the pretreated alloy ingot I obtained in the step (3) at 1100-1200 ℃ for 1-2h, then treating at 700-800 ℃ for 2-3h, and cooling to obtain a pretreated alloy ingot II;
(5) And (3) carrying out heat treatment on the pretreated alloy ingot II obtained in the step (4) to obtain the alloy.
By adopting the technical scheme, the cobalt-chromium alloy has better strength and hardness, the cobalt element is treated, and cobalt is mixed with iron, aluminum, zirconium carbide and boron, so that the brittleness of the cobalt element is improved, and meanwhile, the segregation condition in the cobalt-chromium alloy synthesis process is reduced; the cobalt element is converted into a gamma-phase matrix in the heating process, and then a large amount of chromium atoms are dissolved in the matrix to replace lattice atoms to generate lattice distortion, so that the solid solution strengthening effect is achieved; in addition, raw materials such as molybdenum powder, tungsten powder and the like are introduced in the preparation process of the cobalt-chromium alloy, the bonding force among molybdenum and tungsten atoms is strong and is not easy to diffuse, the dissolving capacity in a gamma-phase matrix is limited, and insoluble phases with strong bonding force are formed and distributed among grain boundaries; with the improvement of the solid solution capacity of the gamma-cobalt matrix, part of molybdenum and tungsten are dissolved into the matrix, and as the radius of molybdenum and tungsten atoms is large, the molybdenum and tungsten atoms are dissolved into the gamma-cobalt matrix to cause lattice distortion, so that the movement of cobalt atoms is blocked, and the effect of solid solution strengthening is achieved; after aging treatment, the cobalt-chromium alloy may be converted into a mechanical mixed structure with staggered layers, so that the prepared alloy has better performance; the micro-carbon ferrochrome and zirconium carbide are introduced into the cobalt-chromium alloy, so that crystal grains and crystal boundaries of the prepared alloy are conveniently reinforced, second-phase particles such as the micro-carbon ferrochrome and the zirconium carbide are dispersed and distributed in a cobalt matrix, the migration of the crystal boundaries is conveniently reduced, the crystal grains are further refined, the finer the crystal grains are, the weaker the catalysis caused by impurities is, and therefore the prepared alloy has better performance.
Preferably, the cooling in the step (4) is liquid nitrogen cooling, and the cooling comprises the following stages: s1, cooling from 700-800 ℃ to 15-20 ℃ at a cooling rate of 10-12 ℃/S; s2, maintaining the temperature at 15-20 ℃ for 200-250S.
By adopting the technical scheme, the cooling rate is high during cooling, the energy fluctuation is large, the nucleation driving force is large, the nucleation is facilitated, the diffusion migration and aggregation of atoms are reduced, the energy transmission is also greatly limited, the solidification time is short, the grains are not grown and solidified, the obtained grains are fine, and the prepared alloy has better performance.
Preferably, the heat treatment in the step (5) includes the following stages: step one, raising the temperature from room temperature to 300-350 ℃ at a heating rate of 15-18 ℃/h; step two, preserving heat for 8 to 10 hours at the temperature of 300 to 350 ℃; step three, heating from 300-350 ℃ to 400-500 ℃ at a heating rate of 15-18 ℃/h; step four, preserving heat for 15-20h at 400-500 ℃; step five, cooling from 400-500 ℃ to 300-350 ℃ at a cooling rate of 8-10 ℃/h; step six, preserving heat for 5 to 8 hours at the temperature of 300 to 350 ℃; step seven, heating from 300-350 ℃ to 450-480 ℃ at a heating rate of 15-18 ℃/h; step eight, preserving heat for 8-12h at 450-480 ℃; step nine, cooling from 450-480 ℃ to 250-270 ℃ at a cooling rate of 8-10 ℃/h; and step ten, cooling from 250-270 ℃ to room temperature, wherein the cooling rate is 15-20 ℃/min.
By adopting the technical scheme, the pretreated alloy ingot II is subjected to heat treatment in the following manner, so that chromium powder and micro-carbon ferrochrome are better dispersed in a cobalt powder matrix, the compactness of the cobalt-chromium alloy is better improved, and the hardness and strength of the prepared cobalt-chromium alloy are further improved.
Preferably, in the step (1), the mass ratio of cobalt, iron, aluminum, zirconium carbide and boron is (25-30): (8-10): (2-3): (2-3): (1-2).
By adopting the technical scheme, the proportion of the five components of cobalt, iron, aluminum, zirconium carbide and boron is adjusted, so that the proportion of the five components is optimal, and the boron, the iron and the zirconium carbide are mutually matched, thereby further promoting solid solution strengthening and fine grain strengthening, being convenient for improving the strength of the alloy, improving the brittleness of cobalt element and being convenient for obtaining cobalt with better performance, and further enabling the prepared cobalt-chromium alloy to have good heat resistance and good mechanical property.
Preferably, the homogenization treatment in the step (1) is carried out at a temperature of 700-800 ℃, the heat preservation time is 20-30h, and the temperature change rate is 15-20 ℃/min.
By adopting the technical scheme, after the pretreated cobalt powder is subjected to homogenization treatment, the internal compactness is better, and the iron, aluminum, zirconium carbide and boron elements are more uniformly mixed with the cobalt powder, so that the brittleness of the cobalt powder is improved conveniently and better, the performance of the prepared cobalt-chromium alloy is reduced, the content of internal cracks is reduced, and the hardness and heat resistance of the cobalt-chromium alloy are further improved.
Preferably, the mass ratio of the pretreated cobalt, titanium powder, copper powder, micro-carbon ferrochrome powder, molybdenum powder, tungsten powder and chromium powder in the step (2) is (40-50): (2-3): (0.1-0.5): (8-10): (5-6): (4-5): (2-3).
By adopting the technical scheme, the proportions of the seven components of the pretreated cobalt, titanium powder, copper powder, micro-carbon chromium iron powder, molybdenum powder, tungsten powder and chromium powder are adjusted, so that the proportions of the seven components are optimal, the high temperature resistance and mechanical properties of the prepared alloy ingot are improved better, and then the alloy ingot is subjected to homogenization, solution aging treatment and heat treatment, so that the prepared alloy has smaller pores, higher hardness and better heat resistance.
Preferably, before smelting in the step (2), the furnace body is vacuumized, and when the vacuum degree in the furnace is less than or equal to 0.65Pa, inert gas is filled in the furnace, and the pressurizing force is 0.05-0.06MPa.
By adopting the technical scheme, the vacuum degree and the filled gas in the furnace are controlled before alloy smelting, which is beneficial to further improving the performance of the prepared alloy ingot.
Preferably, the inert gas in the step (2) is any one of nitrogen and argon.
By adopting the technical scheme, nitrogen or argon is adopted as filling gas in the furnace, so that the condition that the alloy is oxidized in the smelting process is reduced, and the mechanical property of the prepared alloy is improved.
Preferably, the mixing in the step (1) is carried out in a V-shaped mixer, the rotating speed is 50-60r/min, and the mixing time is 30-40h.
Through adopting above-mentioned technical scheme, when carrying out the preliminary treatment to cobalt powder, mix in V type blendor for cobalt, iron, aluminium, zirconium carbide, boron mix more evenly, help further improving the performance of the cobalt powder after the preliminary treatment, be convenient for further improving the mechanical properties of the alloy of making, segregation and defect in the alloy preparation process are reduced.
Preferably, the molybdenum powder is modified molybdenum powder, and the preparation method of the modified molybdenum powder comprises the following steps: mixing alumina with sodium hydroxide solution, magnetically stirring, filtering and drying to obtain pretreated alumina I; mixing the pretreated alumina I with dilute hydrochloric acid, filtering and drying to obtain pretreated alumina II; mixing the pretreated aluminum oxide II and the tin chloride solution, magnetically stirring, filtering and drying to obtain pretreated aluminum oxide III; mixing the pretreated alumina III and the palladium chloride solution, magnetically stirring, filtering and drying to obtain pretreated alumina IV; adjusting the pH value of the plating solution to be alkaline by adopting a sodium hydroxide solution, placing pretreated aluminum oxide four into the plating solution for plating, heating in a water bath, centrifuging, cleaning and drying to obtain the plating solution, wherein each liter of the plating solution is mainly prepared from the following raw materials in parts by weight: 30-31 parts of molybdenum sulfate, 30-31 parts of hydrazine hydrate, 5-8 parts of ethylenediamine tetraacetic acid, 10-12 parts of tartaric acid and the balance of water.
Through adopting above-mentioned technical scheme, mix aluminium oxide and sodium hydroxide solution and be convenient for reduce the oil stain on aluminium oxide surface, dilute hydrochloric acid is convenient for increase aluminium oxide surface's roughness, so that later stage sensitize and activate aluminium oxide, bivalent tin ion adheres to the surface of aluminium oxide, in palladium chloride solution, bivalent tin ion is oxidized into tetravalent tin ion, palladium ion is reduced and adheres to on the active site on aluminium oxide surface, be convenient for improve aluminium oxide's activity, molybdenum ion in the plating solution is reduced into the molybdenum simple substance through oxidation reduction, the parcel is on aluminium oxide surface, be convenient for further improve molybdenum's hardness, and then improve the performance of the cobalt chromium alloy of making.
In a second aspect, the application provides a high Wen Guge resistant alloy, which adopts the following technical scheme:
a high-temperature resistant Wen Guge alloy is prepared by the preparation method of the high-temperature resistant cobalt-chromium alloy.
By adopting the technical scheme, the cobalt-chromium alloy prepared by adopting the method has good hardness and good performance.
In summary, the application has the following beneficial effects:
1. according to the preparation method of the high-temperature-resistant cobalt-chromium alloy, cobalt powder is pretreated, and cobalt, iron, aluminum, zirconium carbide and boron are mixed, so that the brittleness of cobalt element is improved, and the performance of the prepared cobalt-chromium alloy is improved.
2. According to the preparation method of the high-temperature-resistant cobalt-chromium alloy, the micro-carbon ferrochrome and zirconium carbide are introduced, so that crystal grains and crystal boundaries of the prepared alloy are conveniently reinforced, second-phase particles such as the micro-carbon ferrochrome and the zirconium carbide are dispersed and distributed in a cobalt matrix, the migration of the crystal boundaries is conveniently reduced, the crystal grains are further refined, the finer the crystal grains are, the catalysis caused by impurities is weakened, and therefore the prepared alloy has better performance.
Detailed Description
The present application will be described in further detail with reference to examples.
The present application will be described more fully hereinafter in order to facilitate an understanding of the present application. This application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The raw materials of the examples and comparative examples of the present application are commercially available in general except for the specific descriptions.
The manufacturer of the micro-carbon ferrochrome powder is Dou Jinchun metal material Co.
Examples
Example 1
The preparation method of the high-temperature-resistant cobalt-chromium alloy comprises the following steps:
(1) Mixing cobalt, iron, aluminum, zirconium carbide and boron according to a mass ratio of 25:8:2:2:1 to obtain a mixture, carrying out vacuum smelting on the mixture, casting an ingot at 1700 ℃, carrying out homogenization treatment to obtain a blank, heating the blank to 1100 ℃, preserving heat for 8 hours, cooling to 850 ℃ at 10 ℃/min, preserving heat for 15 hours, cooling to room temperature, and grinding to obtain pretreated cobalt; the homogenization treatment temperature is 700 ℃, the heat preservation time is 20 hours, and the temperature change rate is 15 ℃/min; mixing in a V-shaped mixer at the rotating speed of 50r/min for 30h;
(2) Mixing the pretreated cobalt, titanium powder and copper powder obtained in the step (1), vacuum smelting at 1300 ℃, then adding micro-carbon ferrochrome powder, molybdenum powder, tungsten powder and chromium powder, heating to 1800 ℃, smelting at the temperature, and casting ingots to obtain alloy ingots; before smelting, vacuumizing a furnace body, and filling inert gas into the furnace when the vacuum degree in the furnace is less than or equal to 0.65Pa and pressurizing to 0.05MPa; the inert gas is nitrogen; pretreating cobalt, titanium powder, copper powder, micro-carbon ferrochromium powder, molybdenum powder, tungsten powder and chromium powder in a mass ratio of 40:2:0.1:8:5:4:2; pretreating cobalt, titanium powder, copper powder, micro-carbon ferrochromium powder, molybdenum powder, tungsten powder and chromium powder, and dehydrating in vacuum before mixing; the molybdenum powder is modified molybdenum powder, and the preparation method of the modified molybdenum powder comprises the following steps: mixing alumina and sodium hydroxide solution according to a mass ratio of 1:8, magnetically stirring for 20min, filtering, and drying at 100 ℃ for 5h to obtain pretreated alumina I; wherein the mass concentration of the sodium hydroxide solution is 5mol/L; mixing the pretreated alumina I and dilute hydrochloric acid for 10min according to the mass ratio of 1:8, filtering, and drying at 100 ℃ for 5h to obtain pretreated alumina II; the mass concentration of the dilute hydrochloric acid is 1mol/L; mixing the pretreated aluminum oxide II and the stannic chloride solution according to the mass ratio of 1:5 for 20min, magnetically stirring, filtering, and drying at 100 ℃ for 5h to obtain pretreated aluminum oxide III; the mass concentration of the substances of the tin chloride solution is 1mol/L; mixing pretreated alumina III and palladium chloride solution for 20min according to the mass ratio of 1:5, magnetically stirring, filtering, and drying at 100 ℃ for 5h to obtain pretreated alumina IV; the mass concentration of the substance of the palladium chloride solution is 1mol/L; adjusting the pH of the plating solution to 11 by adopting a sodium hydroxide solution, placing pretreated aluminum oxide IV in the plating solution for plating, heating in a water bath at 70 ℃ for reaction for 50min, centrifuging, cleaning and drying to obtain the aluminum oxide, wherein the drying condition is 100 ℃ and drying for 5h; each liter of plating solution comprises the following raw materials by weight: 30g of molybdenum sulfate, 30g of hydrazine hydrate, 5g of ethylenediamine tetraacetic acid, 10g of tartaric acid and the balance of water; the mass ratio of the plating solution to the pretreated aluminum oxide is 10:1;
(3) Carrying out homogenization treatment on the alloy ingot obtained in the step (2) for 4 times to obtain a pretreated alloy ingot I; the temperature of each homogenization treatment is 1000 ℃ and the treatment time is 30 hours; the heating and cooling speeds are 200 ℃/h;
(4) Transferring the pretreated alloy ingot I obtained in the step (3) into a vacuum annealing furnace, sequentially treating for 1h at 1100 ℃, then treating for 2h at 700 ℃, and cooling to obtain a pretreated alloy ingot II; the cooling is liquid nitrogen cooling, and the cooling comprises the following stages: s1, cooling the temperature from 700 ℃ to 15 ℃ at a cooling rate of 10 ℃/S; s2, maintaining at 15 ℃ for 200S;
(5) And (3) carrying out heat treatment on the pretreated alloy ingot II obtained in the step (4), wherein the heat treatment comprises the following steps: step one, raising the temperature from room temperature to 500 ℃ at a heating rate of 14 ℃/h; step two, preserving heat for 10 hours at 500 ℃; and step three, cooling from 500 ℃ to room temperature, wherein the cooling rate is 14 ℃/h.
The high-temperature-resistant cobalt-chromium alloy of the embodiment is prepared by adopting the preparation method.
Example 2
The preparation method of the high temperature resistant cobalt-chromium alloy in the embodiment is different from that in the embodiment 1 in that the preparation method comprises the following steps:
(1) Mixing cobalt, iron, aluminum, zirconium carbide and boron according to a mass ratio of 30:10:3:3:2 to obtain a mixture, carrying out vacuum smelting on the mixture, casting an ingot at 1700 ℃, carrying out homogenization treatment to obtain a blank, heating the blank to 1120 ℃, preserving heat for 9 hours, cooling to 870 ℃ at 10 ℃/min, preserving heat for 16 hours, cooling to room temperature, and grinding to obtain pretreated cobalt; the homogenization treatment temperature is 800 ℃, the heat preservation time is 30 hours, and the temperature change rate is 20 ℃/min; mixing in a V-shaped mixer at the rotating speed of 60r/min for 40h;
(2) Mixing the pretreated cobalt, titanium powder and copper powder obtained in the step (1), vacuum smelting at 1500 ℃, then adding micro-carbon ferrochrome powder, molybdenum powder, tungsten powder and chromium powder, heating to 2000 ℃, smelting, and casting ingots to obtain alloy ingots; before smelting, vacuumizing a furnace body, and filling inert gas into the furnace when the vacuum degree in the furnace is less than or equal to 0.65Pa and pressurizing to 0.06MPa; the inert gas is argon; pretreating cobalt, titanium powder, copper powder, micro-carbon ferrochromium powder, molybdenum powder, tungsten powder and chromium powder in a mass ratio of 50:3:0.5:10:6:5:3; pretreating cobalt, titanium powder, copper powder, micro-carbon ferrochromium powder, molybdenum powder, tungsten powder and chromium powder, and dehydrating in vacuum before mixing; the molybdenum powder is modified molybdenum powder, and the preparation method of the modified molybdenum powder comprises the following steps: mixing alumina and sodium hydroxide solution according to a mass ratio of 1:8, magnetically stirring for 20min, filtering, and drying at 100 ℃ for 5h to obtain pretreated alumina I; wherein the mass concentration of the sodium hydroxide solution is 5mol/L; mixing the pretreated alumina I and dilute hydrochloric acid for 10min according to the mass ratio of 1:8, filtering, and drying at 100 ℃ for 5h to obtain pretreated alumina II; the mass concentration of the dilute hydrochloric acid is 1mol/L; mixing the pretreated aluminum oxide II and the stannic chloride solution according to the mass ratio of 1:5 for 20min, magnetically stirring, filtering, and drying at 100 ℃ for 5h to obtain pretreated aluminum oxide III; the mass concentration of the substances of the tin chloride solution is 1mol/L; mixing pretreated alumina III and palladium chloride solution for 20min according to the mass ratio of 1:5, magnetically stirring, filtering, and drying at 100 ℃ for 5h to obtain pretreated alumina IV; the mass concentration of the substance of the palladium chloride solution is 1mol/L; adjusting the pH of the plating solution to 11 by adopting a sodium hydroxide solution, placing pretreated aluminum oxide IV in the plating solution for plating, heating in a water bath at 70 ℃ for reaction for 50min, centrifuging, cleaning and drying to obtain the aluminum oxide, wherein the drying condition is 100 ℃ and drying for 5h; each liter of plating solution comprises the following raw materials by weight: 31g of molybdenum sulfate, 31g of hydrazine hydrate, 8g of ethylenediamine tetraacetic acid, 12g of tartaric acid and the balance of water; the mass ratio of the plating solution to the pretreated aluminum oxide is 10:1;
(3) Carrying out homogenization treatment on the alloy ingot obtained in the step (2) for 5 times to obtain a pretreated alloy ingot I; the temperature of each homogenization treatment is 1100 ℃, and the treatment time is 35 hours; the heating and cooling speeds are 200 ℃/h;
(4) Sequentially treating the pretreated alloy ingot I obtained in the step (3) at 1200 ℃ for 2 hours, then treating at 800 ℃ for 3 hours, and cooling to obtain a pretreated alloy ingot II; the cooling is liquid nitrogen cooling, and the cooling comprises the following stages: s1, cooling the temperature from 800 ℃ to 20 ℃ at a cooling rate of 12 ℃/S; s2, maintaining at 20 ℃ for 250S;
(5) And (3) carrying out heat treatment on the pretreated alloy ingot II obtained in the step (4), wherein the heat treatment comprises the following steps: step one, raising the temperature from room temperature to 500 ℃ at a heating rate of 14 ℃/h; step two, preserving heat for 10 hours at 500 ℃; and step three, cooling from 500 ℃ to room temperature, wherein the cooling rate is 14 ℃/h.
Example 3
The preparation method of the high temperature resistant cobalt-chromium alloy of the present embodiment is different from embodiment 2 in that the heat treatment in step (5) includes the following stages: step one, raising the temperature from room temperature to 300 ℃ at a heating rate of 15 ℃/h; step two, preserving heat for 8 hours at 300 ℃; step three, heating from 300 ℃ to 400 ℃ at a heating rate of 15 ℃/h; step four, preserving heat for 15 hours at 400 ℃; step five, cooling from 400 ℃ to 300 ℃ at a cooling rate of 8 ℃/h; step six, preserving heat for 5 hours at 300 ℃; step seven, heating from 300 ℃ to 450 ℃ at a heating rate of 15 ℃/h; step eight, preserving heat for 8 hours at 450 ℃; step nine, cooling from 450 ℃ to 250 ℃ at a cooling rate of 8 ℃/h; and step ten, cooling from 250 ℃ to room temperature, wherein the cooling rate is 15 ℃/min.
Example 4
The preparation method of the high temperature resistant cobalt-chromium alloy of the present embodiment is different from embodiment 2 in that the heat treatment in step (5) includes the following stages: step one, raising the temperature from room temperature to 350 ℃ at a heating rate of 18 ℃/h; step two, preserving heat for 10 hours at 350 ℃; step three, heating from 350 ℃ to 500 ℃ at a heating rate of 18 ℃/h; step four, preserving heat for 20 hours at 500 ℃; step five, cooling from 500 ℃ to 350 ℃ at a cooling rate of 10 ℃/h; step six, preserving heat for 8 hours at 350 ℃; step seven, heating from 350 ℃ to 480 ℃ at a heating rate of 18 ℃/h; step eight, heat preservation is carried out for 12 hours at 480 ℃; step nine, cooling from 480 ℃ to 270 ℃ at a cooling rate of 10 ℃/h; and step ten, cooling from 270 ℃ to room temperature, wherein the cooling rate is 20 ℃/min.
Comparative example
Comparative example 1
The preparation method of the high temperature resistant cobalt-chromium alloy of the comparative example is different from example 1 in that the preparation method comprises the following steps: (1) Mixing cobalt powder, titanium powder and copper powder, vacuum smelting at 1300 ℃, then adding micro-carbon chromium iron powder, molybdenum powder, tungsten powder and chromium powder, heating to 1800 ℃, smelting at the temperature of 1800 ℃, and casting ingots to obtain alloy ingots; before smelting, vacuumizing a furnace body, and filling inert gas into the furnace when the vacuum degree in the furnace is less than or equal to 0.65Pa and pressurizing to 0.05MPa; the inert gas is nitrogen; pretreating cobalt, titanium powder, copper powder, micro-carbon ferrochromium powder, molybdenum powder, tungsten powder and chromium powder in a mass ratio of 40:2:0.1:8:5:4:2;
(2) Carrying out homogenization treatment on the alloy ingot obtained in the step (1) for 4 times to obtain a pretreated alloy ingot I; the temperature of each homogenization treatment is 1000 ℃ and the treatment time is 30 hours; the heating and cooling speeds are 200 ℃/h;
(3) Sequentially treating the pretreated alloy ingot I obtained in the step (2) at 1100 ℃ for 1h, then treating at 700 ℃ for 2h, and cooling to obtain a pretreated alloy ingot II; the cooling is liquid nitrogen cooling, and the cooling comprises the following stages: s1, cooling the temperature from 700 ℃ to 15 ℃ at a cooling rate of 10 ℃/S; s2, maintaining at 15 ℃ for 200S;
(4) And (3) carrying out heat treatment on the pretreated alloy ingot II obtained in the step (3), wherein the heat treatment comprises the following steps: step one, raising the temperature from room temperature to 500 ℃ at a heating rate of 14 ℃/h; step two, preserving heat for 10 hours at 500 ℃; and step three, cooling from 500 ℃ to room temperature, wherein the cooling rate is 14 ℃/h.
Comparative example 2
The preparation method of the high temperature resistant cobalt-chromium alloy of the comparative example is different from example 1 in that the preparation method comprises the following steps: (1) Ball-milling and mixing cobalt, iron, aluminum, zirconium carbide and boron according to a mass ratio of 25:8:2:2:1 to obtain a mixture, vacuum smelting the mixture at a smelting temperature of 1700 ℃, casting an ingot, performing homogenization treatment to obtain a blank, heating the blank to 1100 ℃, preserving heat for 8 hours, cooling to 850 ℃ at a speed of 10 ℃/min, preserving heat for 15 hours, cooling to room temperature, and grinding to obtain pretreated cobalt; the homogenization treatment temperature is 700 ℃, the heat preservation time is 20 hours, and the temperature change rate is 15 ℃/min; mixing in a V-shaped mixer at the rotating speed of 50r/min for 30h;
(2) Mixing the pretreated cobalt, titanium powder and copper powder obtained in the step (1), vacuum smelting at 1300 ℃, then adding micro-carbon ferrochrome powder, molybdenum powder, tungsten powder and chromium powder, heating to 1800 ℃, smelting at the temperature, and casting ingots to obtain alloy ingots; before smelting, vacuumizing a furnace body, and filling inert gas into the furnace when the vacuum degree in the furnace is less than or equal to 0.65Pa and pressurizing to 0.05MPa; the inert gas is nitrogen; pretreating cobalt, titanium powder, copper powder, micro-carbon chromium iron powder, molybdenum powder the mass ratio of the tungsten powder to the chromium powder is 40:2:0.1:8:5:4:2.
Comparative example 3
The preparation method of the high temperature resistant cobalt-chromium alloy of the comparative example is different from example 1 in that the preparation method comprises the following steps: (1) Ball-milling and mixing cobalt, iron, aluminum, zirconium carbide and boron according to a mass ratio of 25:8:2:2:1 to obtain a mixture, vacuum smelting the mixture at a smelting temperature of 1700 ℃, casting an ingot, performing homogenization treatment to obtain a blank, heating the blank to 1100 ℃, preserving heat for 8 hours, cooling to 850 ℃ at a speed of 10 ℃/min, preserving heat for 15 hours, cooling to room temperature, and grinding to obtain pretreated cobalt; the homogenization treatment temperature is 700 ℃, the heat preservation time is 20 hours, and the temperature change rate is 15 ℃/min; mixing in a V-shaped mixer at the rotating speed of 50r/min for 30h;
(2) Mixing the pretreated cobalt, titanium powder and copper powder obtained in the step (1), vacuum smelting at 1300 ℃, then adding micro-carbon ferrochrome powder, molybdenum powder, tungsten powder and chromium powder, heating to 1800 ℃, smelting at the temperature, and casting ingots to obtain alloy ingots; before smelting, vacuumizing a furnace body, and filling inert gas into the furnace when the vacuum degree in the furnace is less than or equal to 0.65Pa and pressurizing to 0.05MPa; the inert gas is nitrogen; pretreating cobalt, titanium powder, copper powder, micro-carbon ferrochromium powder, molybdenum powder, tungsten powder and chromium powder in a mass ratio of 40:2:0.1:8:5:4:2;
(3) Carrying out homogenization treatment on the alloy ingot obtained in the step (2) for 4 times to obtain a pretreated alloy ingot; the temperature of each homogenization treatment is 1000 ℃ and the treatment time is 30 hours; the heating and cooling speeds are 200 ℃/h;
(4) And (3) performing heat treatment on the pretreated alloy ingot obtained in the step (3), wherein the heat treatment comprises the following steps: step one, raising the temperature from room temperature to 500 ℃ at a heating rate of 14 ℃/h; step two, preserving heat for 10 hours at 500 ℃; and step three, cooling from 500 ℃ to room temperature, wherein the cooling rate is 14 ℃/h.
Performance test
Tensile property test: the high temperature resistant cobalt-chromium alloys of examples 1 to 4 and comparative examples 1 to 3 were drawn at room temperature and 800℃according to the methods prescribed in GB/T228.1-2021, respectively, and the drawing results are shown in Table 1.
Hardness testing: the high temperature resistant cobalt chromium alloys of examples 1 to 4 and comparative examples 1 to 3 were measured for vickers hardness using a vickers hardness tester, and the test results are shown in table 1.
Abrasion performance test: the wear rates of the alloys at room temperature and 600℃were measured using a pin-disc type frictional wear tester using the high temperature resistant cobalt-chromium alloys of examples 1 to 4 and comparative examples 1 to 3, and the wear rate detection results are shown in Table 1.
TABLE 1 high temperature Co-Cr alloy Performance test Standard for examples 1-4 and comparative examples 1-3
As can be seen by combining the data in Table 1, the high Wen Guge alloy prepared in examples 1-4 has good tensile strength, high hardness, good wear resistance and good heat resistance.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and modifications thereof without creative contribution may be made by those skilled in the art after reading the present specification.
Claims (8)
1. The preparation method of the high Wen Guge-resistant alloy is characterized by comprising the following steps of:
(1) Mixing cobalt, iron, aluminum, zirconium carbide and boron, wherein the mass ratio of the cobalt to the iron to the aluminum to the zirconium carbide to the boron is (25-30), the mass ratio of the cobalt to the iron to the aluminum to the zirconium carbide to the boron is (8-10), the mass ratio of the cobalt to the iron to the aluminum to the boron to the mass ratio of the cobalt to the 3 to the 2 to the 3 to the 1 to the 2 to the mixture to obtain a mixture, carrying out vacuum smelting on the mixture, casting an ingot, carrying out homogenization treatment to obtain a blank, heating the blank to 1100-1120 ℃, preserving the heat for 8-9h, cooling to 850-870 ℃, preserving the heat for 15-16h, finally cooling to room temperature, and grinding to obtain pretreated cobalt;
(2) Mixing the pretreated cobalt, titanium powder and copper powder obtained in the step (1), wherein the mass ratio of the pretreated cobalt, titanium powder, copper powder, micro-carbon ferrochrome powder, molybdenum powder, tungsten powder and chromium powder is (40-50): (2-3) (0.1-0.5) (8-10) (5-6) (4-5) (2-3), vacuum smelting at 1300-1500 ℃, then adding micro-carbon chromium iron powder, molybdenum powder, tungsten powder and chromium powder, heating to 1800-2000 ℃, smelting, casting ingot, and obtaining alloy ingot; the molybdenum powder is modified molybdenum powder, and the preparation method of the modified molybdenum powder comprises the following steps: mixing alumina with sodium hydroxide solution, magnetically stirring, filtering and drying to obtain pretreated alumina I; mixing the pretreated alumina I with dilute hydrochloric acid, filtering and drying to obtain pretreated alumina II; mixing the pretreated aluminum oxide II and the tin chloride solution, magnetically stirring, filtering and drying to obtain pretreated aluminum oxide III; mixing the pretreated alumina III and the palladium chloride solution, magnetically stirring, filtering and drying to obtain pretreated alumina IV; adjusting the pH value of the plating solution to be alkaline by adopting a sodium hydroxide solution, placing pretreated aluminum oxide four into the plating solution for plating, heating in a water bath, centrifuging, cleaning and drying to obtain the plating solution, wherein each liter of the plating solution is mainly prepared from the following raw materials in parts by weight: 30-31 parts of molybdenum sulfate, 30-31 parts of hydrazine hydrate, 5-8 parts of ethylenediamine tetraacetic acid, 10-12 parts of tartaric acid and the balance of water;
(3) Homogenizing the alloy ingot obtained in the step (2) for 4-5 times to obtain a pretreated alloy ingot I; the temperature of each homogenization treatment is 1000-1100 ℃, and the treatment time is 30-35h;
(4) Sequentially treating the pretreated alloy ingot I obtained in the step (3) at 1100-1200 ℃ for 1-2h, then treating at 700-800 ℃ for 2-3h, and cooling to obtain a pretreated alloy ingot II;
(5) And (3) carrying out heat treatment on the pretreated alloy ingot II obtained in the step (4) to obtain the alloy.
2. The method of claim 1, wherein the cooling in step (4) is liquid nitrogen cooling, and the cooling comprises the following steps: s1, cooling from 700-800 ℃ to 15-20 ℃ at a cooling rate of 10-12 ℃/S; s2, maintaining the temperature at 15-20 ℃ for 200-250S.
3. The method for producing a refractory Wen Guge alloy according to claim 2, wherein the heat treatment in step (5) includes the steps of: step one, raising the temperature from room temperature to 300-350 ℃ at a heating rate of 15-18 ℃/h; step two, preserving heat for 8 to 10 hours at the temperature of 300 to 350 ℃; step three, heating from 300-350 ℃ to 400-500 ℃ at a heating rate of 15-18 ℃/h; step four, preserving heat for 15-20h at 400-500 ℃; step five, cooling from 400-500 ℃ to 300-350 ℃ at a cooling rate of 8-10 ℃/h; step six, preserving heat for 5 to 8 hours at the temperature of 300 to 350 ℃; step seven, heating from 300-350 ℃ to 450-480 ℃ at a heating rate of 15-18 ℃/h; step eight, preserving heat for 8-12h at 450-480 ℃; step nine, cooling from 450-480 ℃ to 250-270 ℃ at a cooling rate of 8-10 ℃/h; and step ten, cooling from 250-270 ℃ to room temperature, wherein the cooling rate is 15-20 ℃/min.
4. The method for preparing a refractory Wen Guge alloy according to claim 1, wherein the homogenization treatment in step (1) is carried out at a temperature of 700-800 ℃, a holding time of 20-30h, and a temperature change rate of 15-20 ℃/min.
5. The method for producing a refractory Wen Guge alloy according to claim 1, wherein before the melting in the step (2), the furnace body is evacuated, and when the vacuum degree in the furnace is less than or equal to 0.65Pa, inert gas is filled into the furnace to a pressure of 0.05-0.06MPa.
6. The method of claim 5, wherein the inert gas in step (2) is any one of nitrogen and argon.
7. The method for preparing the high-strength Wen Guge alloy according to claim 1, wherein the mixing in the step (1) is performed in a V-type mixer at a rotation speed of 50-60r/min for 30-40h.
8. A high temperature resistant Wen Guge alloy produced by the method of producing a high temperature resistant cobalt chromium alloy as claimed in any one of claims 1 to 7.
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