CN113957438A - Preparation method of metal tungsten high-temperature oxidation-resistant gallium-based composite coating - Google Patents
Preparation method of metal tungsten high-temperature oxidation-resistant gallium-based composite coating Download PDFInfo
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- CN113957438A CN113957438A CN202111245035.8A CN202111245035A CN113957438A CN 113957438 A CN113957438 A CN 113957438A CN 202111245035 A CN202111245035 A CN 202111245035A CN 113957438 A CN113957438 A CN 113957438A
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 165
- 239000002184 metal Substances 0.000 title claims abstract description 117
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 114
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000010937 tungsten Substances 0.000 title claims abstract description 108
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 107
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 238000000576 coating method Methods 0.000 title claims abstract description 74
- 230000003647 oxidation Effects 0.000 title claims abstract description 62
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 76
- 239000011159 matrix material Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 14
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 14
- 238000003723 Smelting Methods 0.000 claims abstract description 12
- 238000005238 degreasing Methods 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 229910052738 indium Inorganic materials 0.000 claims abstract description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000001680 brushing effect Effects 0.000 claims abstract description 10
- 238000005498 polishing Methods 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- 239000011669 selenium Substances 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 239000002344 surface layer Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 3
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 230000003064 anti-oxidating effect Effects 0.000 claims 6
- 239000000463 material Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 244000137852 Petrea volubilis Species 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 229910021332 silicide Inorganic materials 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention relates to a preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating, belonging to the technical field of material preparation. The method comprises the steps of removing oxide skin on the surface of a metal tungsten matrix, and sequentially carrying out polishing, degreasing and acid activation treatment to obtain a pretreated metal tungsten matrix; smelting gallium and metal A to obtain gallium-based liquid metal, wherein the metal A is one or more of aluminum, zinc, selenium, indium, tin, lead and bismuth; pouring gallium-based liquid metal into a container, stirring and oxidizing to obtain gallium-based liquid metal with oxidized surface; brushing the gallium-based liquid metal after stirring and oxidation on a pretreated metal tungsten substrate to obtain the metal tungsten high-temperature oxidation-resistant gallium-based composite coating. The invention adopts gallium-based liquid metal after stirring and oxidation, the surface of the gallium-based liquid metal exists in the form of oxide, the interior of the gallium-based liquid metal exists in the form of metal and/or intermetallic compound, and the prepared high-temperature oxidation-resistant composite coating is compact and uniform, has low cost, simple operation, no need of sintering, is suitable for coating special-shaped parts, and can be applied to industrial production.
Description
Technical Field
The invention relates to a preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating, belonging to the technical field of material preparation.
Background
The refractory metal tungsten has excellent physical and chemical properties such as high melting point, good creep resistance, corrosion resistance, low expansion coefficient, low tritium retention rate and the like, and is widely applied to the fields of aerospace, nuclear reactors, electronic industry and the like. However, its main drawback is poor oxidation resistance, which occurs at 300-. In order to solve the problems of poor oxidation resistance of metal tungsten and prolonged service life in a high-temperature environment, the most effective and convenient method is to prepare a protective coating on the surface.
The embedding method can prepare a coating on the surface of a matrix, a high-temperature oxidation resistant layer on the surface of metal tungsten and the preparation method thereof, wherein the embedding method of molybdenum infiltration-nitridation-silicification is adopted on the surface of the metal tungsten to prepare a silicide coating, and the silicide coating is formed on the surface of the metal tungsten (W)xMo1-x)Si2A solid solution phase as a main component and a small amount of Si3N4The composite layer of the phase increases the bonding strength between the coating and the substrate. The introduction of Mo element reduces the diffusion rate of Si element in the matrix during the high-temperature oxidation process, slows down the 'degradation' of the silicide coating and effectively improves the oxidation resistance of the metal tungsten. Mohmander Zaffel Aramer and the like adopt an embedding method to prepare WSi on the surface of metal tungsten2And provides short-term cyclic oxidation protection for up to about 2 hours over a temperature range of 1100-1300 ℃. However, the embedding method is complex in process and high in production cost.
Disclosure of Invention
The invention provides a preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating, aiming at the problems of complex process, high cost and the like in an embedding method technology, namely, gallium-based liquid metal after stirring and oxidation is adopted, the surface of the gallium-based liquid metal exists in an oxide form, and the interior of the gallium-based liquid metal exists in a metal and/or intermetallic compound form.
A preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating comprises the following specific steps:
(1) removing oxide skin on the surface of the metal tungsten matrix, and then sequentially carrying out polishing, degreasing and acid activation treatment to obtain a pretreated metal tungsten matrix;
(2) smelting gallium and metal A to obtain gallium-based liquid metal, wherein the metal A is one or more of aluminum, zinc, selenium, indium, tin, lead and bismuth;
(3) pouring gallium-based liquid metal into a container, stirring and oxidizing to obtain gallium-based liquid metal with oxidized surface;
(4) brushing the gallium-based liquid metal after stirring and oxidation on a pretreated metal tungsten substrate to obtain a metal tungsten high-temperature oxidation-resistant gallium-based composite coating;
the solvent for degreasing in the step (1) is acetone, ethanol, toluene or tetrachloroethylene, the acid for acid activation treatment is hydrofluoric acid, the mass concentration of the hydrofluoric acid is 35-45%, the temperature for acid activation treatment is 25-35 ℃, and the time is 2-4 min;
the mass of the gallium-based liquid metal in the step (2) is 100%, the metal A accounts for 0-50%, and the balance is gallium;
the smelting temperature in the step (2) is 30-150 ℃;
the temperature of stirring and oxidizing in the step (3) is 30-150 ℃, the time is 5-24 h, and the rotating speed is 500-2000 r/min;
the surface layer of the gallium-based liquid metal oxidized on the surface layer in the step (3) is gallium-based metal oxide, and gallium and/or gallium-based intermetallic compounds are arranged inside the gallium-based liquid metal;
the thickness of the metal tungsten high-temperature oxidation resistant gallium-based composite coating in the step (4) is 5-100 mu m.
The invention has the beneficial effects that:
(1) according to the invention, the gallium-based liquid metal after stirring and oxidation exists on the surface in the form of oxide and exists inside in the form of metal and/or intermetallic compound, and the prepared high-temperature oxidation-resistant composite coating has the characteristics of compactness, uniformity, low cost, simplicity in operation and no need of sintering;
(2) the preparation process of the metal tungsten high-temperature oxidation-resistant gallium-based composite coating is simple, expensive equipment is not needed, the preparation process of the coating is simple, the cost is low, and the coating is suitable for various tungsten matrixes with complex shapes;
(3) the invention utilizes the oxide with compact surface and the gallium-based liquid metal to form the composite coating, so that the liquid metal in the composite coating has fluidity at room temperature, and the stress of the coating and the substrate can be reduced.
Drawings
FIG. 1 is an SEM image (magnification of 2000 times) of the high-temperature oxidation-resistant gallium-based composite coating of metal tungsten of example 2, which is insulated for 10 hours at the temperature of 800 ℃ in air;
FIG. 2 is a graph comparing the mass increase of the high-temperature oxidation-resistant gallium-based composite coating of metal tungsten and metal tungsten in example 2, which is kept at 800 ℃ for 9 hours in air.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating comprises the following specific steps:
(1) removing oxide skin on the surface of the metal tungsten matrix by using sand paper for grinding and polishing, then placing the metal tungsten matrix in acetone for degreasing, then placing the metal tungsten matrix in hydrofluoric acid with the mass concentration of 40%, and performing acid activation treatment for 4min at the temperature of 25 ℃ to obtain a pretreated metal tungsten matrix;
(2) smelting gallium at 30 ℃ to obtain gallium liquid metal;
(3) pouring the gallium liquid metal into a container at the temperature of 30 ℃, stirring and oxidizing for 10 hours at the rotating speed of 2000r/min to obtain gallium liquid metal with oxidized surface; the surface of the gallium liquid metal oxidized on the surface layer is gallium oxide, and the interior of the gallium liquid metal is gallium liquid metal;
(4) brushing the gallium liquid metal after stirring and oxidation on a pretreated metal tungsten substrate to obtain a metal tungsten high-temperature oxidation-resistant gallium-based composite coating; wherein the thickness of the metal tungsten high-temperature oxidation resistant gallium-based composite coating is 15 mu m;
the preparation method of the metal tungsten high-temperature oxidation-resistant gallium-based composite coating is simple in process, and the coating is compact and crack-free after high temperature.
Example 2: a preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating comprises the following specific steps:
(1) removing oxide skin on the surface of the metal tungsten matrix by using sand paper for grinding and polishing, then placing the metal tungsten matrix in ethanol for degreasing, then placing the metal tungsten matrix in 35% hydrofluoric acid by mass concentration, and performing acid activation treatment for 2.5min at the temperature of 28 ℃ to obtain a pretreated metal tungsten matrix;
(2) at the temperature of 80 ℃, smelting gallium and indium to obtain gallium-based liquid metal; wherein gallium accounts for 75.5 wt.% and indium accounts for 24.5 wt.% in the gallium-based liquid metal;
(3) pouring gallium-based liquid metal into a container at the temperature of 80 ℃, and stirring and oxidizing at the rotating speed of 1500r/min for 15 hours to obtain gallium-based liquid metal with oxidized surface; the surface of the gallium-based liquid metal oxidized on the surface layer is a gallium-based metal oxide, and the interior of the gallium-based liquid metal is a gallium-based intermetallic compound;
(4) brushing the gallium-based liquid metal with oxidized surface layer on the pretreated metal tungsten substrate to obtain a metal tungsten high-temperature oxidation-resistant gallium-based composite coating; wherein the thickness of the metal tungsten high-temperature oxidation resistant gallium-based composite coating is 20 mu m;
in the embodiment, an SEM picture (magnification factor of 2000 times) of the metal tungsten high-temperature oxidation-resistant gallium-based composite coating, which is kept at the temperature of 800 ℃ for 9 hours in the air, is shown in figure 1, and the coating is compact and has no cracks;
the oxidation weight gain graph of the metal tungsten coated with the gallium-based composite coating and the metal tungsten coated with the gallium-based composite coating is shown in figure 2, the oxidation weight gain of the metal tungsten coated with the gallium-based composite coating is obviously lower than that of the metal tungsten, and the metal tungsten coated with the gallium-based composite coating hardly increases within 9 hours at the temperature of 800 ℃, so that the gallium-based composite coating has good high-temperature oxidation resistance and can well protect the metal tungsten from oxidation within 9 hours at the temperature of 800 ℃.
Example 3: a preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating comprises the following specific steps:
(1) removing oxide skin on the surface of the metal tungsten matrix by using sand paper for grinding and polishing, then placing the metal tungsten matrix in methylbenzene for degreasing, then placing the metal tungsten matrix in hydrofluoric acid with the mass concentration of 38%, and performing acid activation treatment for 2min at the temperature of 32 ℃ to obtain a pretreated metal tungsten matrix;
(2) at the temperature of 60 ℃, smelting gallium and indium to obtain gallium-based liquid metal; wherein gallium accounts for 80 wt.% and indium accounts for 20 wt.% in the gallium-based liquid metal;
(3) pouring gallium-based liquid metal into a container at the temperature of 60 ℃, stirring and oxidizing for 12 hours at the rotating speed of 2000r/min to obtain gallium-based liquid metal with oxidized surface; the surface of the gallium-based liquid metal oxidized on the surface layer is a gallium-based metal oxide, and the interior of the gallium-based liquid metal is a gallium-based intermetallic compound;
(4) brushing the gallium-based liquid metal with oxidized surface layer on the pretreated metal tungsten substrate to obtain a metal tungsten high-temperature oxidation-resistant gallium-based composite coating; wherein the thickness of the metal tungsten high-temperature oxidation resistant gallium-based composite coating is 50 μm;
the preparation method of the metal tungsten high-temperature oxidation-resistant gallium-based composite coating is simple in process, and the coating is compact and crack-free after high temperature.
Example 4: a preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating comprises the following specific steps:
(1) removing oxide skin on the surface of the metal tungsten matrix by using sand paper for grinding and polishing, then placing the metal tungsten matrix in tetrachloroethylene for degreasing, then placing the metal tungsten matrix in hydrofluoric acid with the concentration of 45%, and performing acid activation treatment for 2min at the temperature of 25 ℃ to obtain a pretreated metal tungsten matrix;
(2) smelting gallium and tin at 50 ℃ to obtain gallium-based liquid metal; wherein gallium accounts for 86.5 wt.% and tin accounts for 13.5 wt.% in the gallium-based liquid metal;
(3) pouring gallium-based liquid metal into a container at the temperature of 50 ℃, stirring and oxidizing for 24 hours at the rotating speed of 500r/min to obtain gallium-based liquid metal with oxidized surface; the surface of the gallium-based liquid metal oxidized on the surface layer is a gallium-based metal oxide, and the interior of the gallium-based liquid metal is a gallium-based intermetallic compound;
(4) brushing the gallium-based liquid metal with oxidized surface layer on the pretreated metal tungsten substrate to obtain a metal tungsten high-temperature oxidation-resistant gallium-based composite coating; wherein the thickness of the metal tungsten high-temperature oxidation resistant gallium-based composite coating is 5 mu m;
the preparation method of the metal tungsten high-temperature oxidation-resistant gallium-based composite coating is simple in process, and the coating is compact and crack-free after high temperature.
Example 5: a preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating comprises the following specific steps:
(1) removing oxide skin on the surface of the metal tungsten matrix by using sand paper for grinding and polishing, then placing the metal tungsten matrix in acetone for degreasing, then placing the metal tungsten matrix in 35% hydrofluoric acid by mass concentration, and performing acid activation treatment for 4min at the temperature of 35 ℃ to obtain a pretreated metal tungsten matrix;
(2) smelting gallium and aluminum at the temperature of 60 ℃ to obtain gallium-based liquid metal; wherein the gallium-based liquid metal comprises 98 wt.% of gallium and 2 wt.% of aluminum;
(3) pouring gallium-based liquid metal into a container at the temperature of 60 ℃, and stirring and oxidizing for 6 hours at the rotating speed of 1000r/min to obtain gallium-based liquid metal with oxidized surface; the surface of the gallium-based liquid metal oxidized on the surface layer is a gallium-based metal oxide, and the interior of the gallium-based liquid metal is a gallium-based intermetallic compound;
(4) brushing the gallium-based liquid metal with oxidized surface layer on the pretreated metal tungsten substrate to obtain a metal tungsten high-temperature oxidation-resistant gallium-based composite coating; wherein the thickness of the metal tungsten high-temperature oxidation resistant gallium-based composite coating is 80 μm;
the preparation method of the metal tungsten high-temperature oxidation-resistant gallium-based composite coating is simple in process, and the coating is compact and crack-free after high temperature.
Example 6: a preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating comprises the following specific steps:
(1) removing oxide skin on the surface of the metal tungsten matrix by using sand paper for grinding and polishing, then placing the metal tungsten matrix in acetone for degreasing, then placing the metal tungsten matrix in hydrofluoric acid with the mass concentration of 40%, and performing acid activation treatment for 3min at the temperature of 30 ℃ to obtain a pretreated metal tungsten matrix;
(2) smelting gallium, indium and tin at the temperature of 100 ℃ to obtain gallium-based liquid metal; wherein gallium accounts for 68.5 wt.%, indium accounts for 25.5 wt.%, and tin accounts for 10 wt.% in the gallium-based liquid metal;
(3) pouring gallium-based liquid metal into a container at the temperature of 100 ℃, and stirring and oxidizing for 5 hours at the rotating speed of 800r/min to obtain gallium-based liquid metal with oxidized surface; the surface of the gallium-based liquid metal oxidized on the surface layer is a gallium-based metal oxide, and the interior of the gallium-based liquid metal is a gallium-based intermetallic compound;
(4) brushing the gallium-based liquid metal with oxidized surface layer on the pretreated metal tungsten substrate to obtain a metal tungsten high-temperature oxidation-resistant gallium-based composite coating; wherein the thickness of the metal tungsten high-temperature oxidation resistant gallium-based composite coating is 100 mu m;
the preparation method of the metal tungsten high-temperature oxidation-resistant gallium-based composite coating is simple in process, and the coating is compact and crack-free after high temperature.
Example 7: a preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating comprises the following specific steps:
(1) removing oxide skin on the surface of the metal tungsten matrix by using sand paper for grinding and polishing, then placing the metal tungsten matrix in acetone for degreasing, then placing the metal tungsten matrix in hydrofluoric acid with the mass concentration of 40%, and performing acid activation treatment for 3min at the temperature of 25 ℃ to obtain a pretreated metal tungsten matrix;
(2) smelting gallium, indium, tin and zinc at 120 ℃ to obtain gallium-based liquid metal; wherein gallium accounts for 70 wt.%, indium accounts for 10 wt.%, tin accounts for 10 wt.%, and zinc accounts for 10 wt.% in the gallium-based liquid metal;
(3) pouring gallium-based liquid metal into a container at the temperature of 120 ℃, stirring and oxidizing for 10 hours at the rotating speed of 600r/min to obtain gallium-based liquid metal with oxidized surface; the surface of the gallium-based liquid metal oxidized on the surface layer is a gallium-based metal oxide, and the interior of the gallium-based liquid metal is a gallium-based intermetallic compound;
(4) brushing the gallium-based liquid metal with oxidized surface layer on the pretreated metal tungsten substrate to obtain a metal tungsten high-temperature oxidation-resistant gallium-based composite coating; wherein the thickness of the metal tungsten high-temperature oxidation resistant gallium-based composite coating is 25 μm;
the preparation method of the metal tungsten high-temperature oxidation-resistant gallium-based composite coating is simple in process, and the coating is compact and crack-free after high temperature.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (7)
1. A preparation method of a metal tungsten high-temperature oxidation-resistant gallium-based composite coating is characterized by comprising the following specific steps:
(1) removing oxide skin on the surface of the metal tungsten matrix, and then sequentially carrying out polishing, degreasing and acid activation treatment to obtain a pretreated metal tungsten matrix;
(2) smelting gallium and metal A to obtain gallium-based liquid metal, wherein the metal A is one or more of aluminum, zinc, selenium, indium, tin, lead and bismuth;
(3) pouring gallium-based liquid metal into a container, stirring and oxidizing to obtain gallium-based liquid metal with oxidized surface;
(4) brushing the gallium-based liquid metal after stirring and oxidation on a pretreated metal tungsten substrate to obtain the metal tungsten high-temperature oxidation-resistant gallium-based composite coating.
2. The method for preparing the metal tungsten high-temperature anti-oxidation gallium-based composite coating according to claim 1, characterized in that: the solvent for degreasing in the step (1) is acetone, ethanol, toluene or tetrachloroethylene, the acid for acid activation treatment is hydrofluoric acid, the mass concentration of the hydrofluoric acid is 35-45%, the temperature for acid activation treatment is 25-35 ℃, and the time is 2-4 min.
3. The method for preparing the metal tungsten high-temperature anti-oxidation gallium-based composite coating according to claim 1, characterized in that: and (3) the mass of the gallium-based liquid metal in the step (2) is 100%, the metal A accounts for 0-50%, and the balance is gallium.
4. The method for preparing the metal tungsten high-temperature anti-oxidation gallium-based composite coating according to claim 1, characterized in that: the smelting temperature in the step (2) is 30-150 ℃.
5. The method for preparing the metal tungsten high-temperature anti-oxidation gallium-based composite coating according to claim 1, characterized in that: the temperature of stirring and oxidizing in the step (3) is 30-150 ℃, the time is 5-24 h, and the rotating speed is 500-2000 r/min.
6. The method for preparing the metal tungsten high-temperature anti-oxidation gallium-based composite coating according to claim 1, characterized in that: the surface layer of the gallium-based liquid metal oxidized on the surface layer in the step (3) is gallium-based metal oxide, and the interior of the gallium-based liquid metal is gallium and/or gallium-based intermetallic compound.
7. The method for preparing the metal tungsten high-temperature anti-oxidation gallium-based composite coating according to claim 1, characterized in that: and (4) the thickness of the metal tungsten high-temperature oxidation-resistant gallium-based composite coating in the step (4) is 5-100 mu m.
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