CN115971011A - High-entropy composite oxide hydrogen-resistant coating and preparation method thereof - Google Patents
High-entropy composite oxide hydrogen-resistant coating and preparation method thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 239000011248 coating agent Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 238000005507 spraying Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
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- Other Surface Treatments For Metallic Materials (AREA)
- Chemically Coating (AREA)
Abstract
The invention discloses a preparation method of a high-entropy composite oxide hydrogen-resistant coating, which comprises the following steps: s1, preparing xerogel from metal salt by a sol-gel method; s2, pre-sintering the xerogel at the temperature of 200-600 ℃, and grinding to obtain precursor powder; s3, fully dissolving the precursor powder in a solvent, and spraying the precursor powder on the surface of a metal sample piece under high pressure; s4, sintering the sprayed metal sample piece at high temperature and rapidly cooling at 600-850 ℃ to obtain a hydrogen-resistant coating attached to the surface of the metal sample piece; the invention makes full use of the existing Al 2 O 3 Based on a coatingThe high-entropy ceramic is fully roasted at a relatively low temperature and rapidly cooled by means of a sol-gel method through mixing elements such as Y-Cr-Fe-Er-Zr-Ti, so that low-temperature synthesis of the high-entropy ceramic is realized, and the high-entropy ceramic has the characteristics of low cost, simplicity in operation, excellent hydrogen resistance effect and the like.
Description
Technical Field
The invention relates to the technical field of hydrogen resistant coatings, in particular to a high-entropy composite oxide hydrogen resistant coating and a preparation method thereof.
Background
In the process of nuclear reaction of a fusion reactor, in order to prevent hydrogen and isotopes thereof from diffusing outwards from a breeder and a pipeline and ensure the safe tritium level in a liquid cladding system and a coolant, a hydrogen-resistant coating needs to be constructed on the surfaces of the corresponding pipeline and parts. The existing coating materials mainly comprise metal oxides, metal nitrides or metal carbides and the like, but the problems of weak bonding force between a single oxide coating and a substrate, mismatch of thermal expansion coefficients and the like under the severe conditions of irradiation, high temperature and the like are solved. The high-entropy ceramic is synthesized at high temperature and is rapidly cooled to obtain a metastable state, has a slow diffusion effect, can be stably kept in a wide temperature range, and has low thermal conductivity and high strength. Therefore, various oxide materials with high-efficiency hydrogen resistance are mixed to prepare the high-entropy ceramic hydrogen-resistant coating, so that the hydrogen resistance of the sample under extreme conditions is effectively improved.
Disclosure of Invention
The invention aims to provide a high-entropy composite oxide hydrogen-resistant coating and a preparation method thereof, which take alumina with excellent hydrogen-resistant capability as a main body to ensure that the coating has high hydrogen-resistant capability, and simultaneously add various oxides of Y, er, zr and Ti which also have certain hydrogen-resistant capability, and add Fe and Cr to contribute to improving the bonding property of the coating and a FeCrAl steel matrix. Through a sol-gel method, a plurality of metal elements are uniformly mixed at an atomic level to obtain high-activity precursor powder, and the precursor powder is quickly cooled after size mixing, spraying and high-temperature sintering to realize the preparation of the high-entropy ceramic coating on the surface of the FeCrAl steel.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention discloses a preparation method of a high-entropy composite oxide hydrogen-resistant coating, which comprises the following steps:
s1, preparing xerogel from metal salt by a sol-gel method;
s2, pre-sintering the xerogel at the temperature of 200-600 ℃, and grinding to obtain precursor powder;
s3, fully dissolving the precursor powder in a solvent to obtain slurry with the solid content of 30-60%, and spraying the slurry on the surface of a metal sample piece under high pressure;
s4, sintering the sprayed metal sample piece at high temperature and rapidly cooling at 600-850 ℃ to obtain a hydrogen-resistant coating attached to the surface of the metal sample piece;
as the hydrogen resistance of the aluminum oxide is far higher than that of other metal oxides, the mole number of Al element in the metal salt accounts for 50-70% of the total mole number of the metal elements in the whole metal salt, for other metal oxides, the oxides of Y, er, zr and Ti also have the hydrogen resistance, and Fe and Cr contribute to improving the bonding property of the coating and the FeCrAl steel matrix.
The metal salt is at least one of hydrolysable salts of Al, Y, cr, fe, er, zr and Ti; wherein the mole number of the Al element accounts for 50-70% of the total mole number of the metal elements in all the metal salts.
The method of claim 1, wherein the hydrolysable salts of Al, Y, cr, fe, er, zr comprise at least one of nitrate, acetate, and ammonium salts.
As a further scheme of the invention: the hydrolysable salt of Ti is n-butyl titanate.
As a further scheme of the invention: the solvent is at least one of deionized water, ethanol, acetone, isopropanol, propanol, ethylene glycol, butanol, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, polyvinyl butyral, polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose and styrene butadiene rubber.
As a further scheme of the invention: the thickness of the hydrogen-resistant coating is 0.1-100 μm.
As a further scheme of the invention: the xerogel is prepared by the following specific method:
dissolving metal salt in deionized water, adding a complexing agent according to the mole number of 0.8-1.5 times of the metal salt, adjusting the pH value to 5.5-6.5, stirring at 50-90 ℃ until the metal salt is viscous and sol-like, and drying in an oven to obtain the xerogel.
As a further scheme of the invention: the complexing agent is at least one of citric acid, ethylene diamine tetraacetic acid and polyvinyl alcohol.
As a further scheme of the invention: the metal sample piece is made of FeCrAl steel.
On the other hand, the invention discloses the high-entropy composite oxide hydrogen-resistant coating prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares a high-entropy composite oxide ceramic hydrogen-resistant coating, shows the preference, slow dynamics, lattice distortion and a series of other performances of a single-phase solid phase with a simple crystal structure through a highly disordered multi-component system, and can solve a series of problems of weak bonding force between the current single oxide coating and a substrate, mismatched thermal expansion coefficients and the like. Thus, in Al 2 O 3 The multi-component high-entropy oxide ceramic is designed on the basis of the base coating, and the realization of low cost and simple preparation of the multi-component high-entropy oxide ceramic is of great significance.
The invention makes full use of the existing Al 2 O 3 The base coating has excellent hydrogen resistance effect, and the elements such as Y-Cr-Fe-Er-Zr-Ti are mixed, and the full roasting and the rapid cooling are realized at relatively low temperature by means of a sol-gel method, so that the low-temperature synthesis of the high-entropy ceramic is realized, and the base coating has the characteristics of low cost, simple operation, excellent hydrogen resistance effect and the like.
Drawings
FIG. 1 shows Al prepared in example 1 of the present invention 70 (YCrFeErZrTi) 30 O x The appearance of the hydrogen-resistant coating of the high-entropy composite oxide.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
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 invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
All materials are conventional and commonly used products in the market.
It is understood that the above raw material reagents are only examples of some specific embodiments of the present invention, so as to make the technical scheme of the present invention more clear, and do not represent that the present invention can only adopt the above reagents, specifically, the scope in the claims is subject to. In addition, "parts" described in examples and comparative examples mean molar parts unless otherwise specified.
Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
Example 1
Weighing 7 parts of Al (NO) 3 ) 3 0.5 part of Cr (NO) 3 ) 3 0.5 part of Y (NO) 3 ) 3 0.5 part of Fe (NO) 3 ) 3 0.5 part of Er (NO) 3 ) 3 0.5 part of Zr (NO) 3 ) 4 0.5 part of tetrabutyl titanate, dissolving in deionized water, adding 10 parts of citric acid, adding ammonia water to adjust the pH value to 5.5, stirring at 80 ℃ until the mixture is viscous and sol-like, and drying in an oven at 120 ℃ to obtain xerogel. And grinding and crushing the xerogel, putting the ground xerogel into a muffle furnace, and sintering for 2h at 500 ℃ in the air atmosphere to obtain precursor powder.
Adding precursor powder into a mixed solvent of sodium carboxymethylcellulose aqueous solution and acetone, fully stirring and mixing, and uniformly spraying the precursor powder on the surface of a FeCrAl steel sample by using a high-pressure spray gun.
And (3) placing the sprayed iron-based sample piece in a muffle furnace, sintering for 1h at 850 ℃ in air atmosphere, taking out and quenching with water to obtain a hydrogen-resistant coating attached to the surface of the FeCrAl steel sample piece, wherein the thickness of the hydrogen-resistant coating is 40 mu m, the coating is tightly combined with a matrix, no obvious pore exists in an interface, and the result of testing the hydrogen permeation reduction factor of the coating by a gas-phase hydrogen permeation device is 2300.
Example 2
Weighing 5.2 parts of Al (OAc) 3 0.8 parts of Cr (OAc) 3 0.8 part of Y (OAc) 3 0.8 part of ammonium ferric citrate and 0.8 part of Er (NO) 3 ) 3 0.8 part of Zr (NO) 3 ) 4 And 0.8 part of n-butyl titanate. And dissolved in deionized water and acetone in a volume ratio of 2:1, adding 15 parts of citric acid, adding ammonia water to adjust the pH value to 6, stirring at 80 ℃ until the solution is viscous and sol-like, and drying in a 120 ℃ oven to obtain xerogel. And grinding and crushing the xerogel, putting the ground xerogel into a tube furnace, and sintering for 4 hours at 500 ℃ under the oxygen condition to obtain precursor powder.
Adding the precursor powder into a mixed solvent of ethanol and ethyl acetate, fully stirring and mixing, and uniformly spraying the precursor powder on the surface of a FeCrAl steel sample by using a high-pressure spray gun.
And placing the sprayed iron-based sample piece in a muffle furnace, sintering for 5h at 750 ℃, taking out, air-cooling, and obtaining a hydrogen-resistant coating attached to the surface of the FeCrAl steel sample piece, wherein the interface is tightly combined, the thickness of the hydrogen-resistant coating is 60 mu m, and the hydrogen permeation reduction factor result of the coating is 1700 by testing through a gas-phase hydrogen permeation device.
Example 3
6.4 parts of Al (NO) are weighed out 3 ) 3 0.6 parts of Cr 2 (OAc) 4 0.6 part of Y (NO) 3 ) 3 0.6 part of Fe (NO) 3 ) 3 0.6 part Er (OAc) 3 0.6 part of ammonium zirconium carbonate and 0.6 part of n-butyl titanate. And dissolving the mixture in deionized water and ethanol in a volume ratio of 1:1, adding 8 parts of citric acid, adding ammonia water to adjust the pH value to 6.5, stirring at 90 ℃ until the mixture is viscous and sol-like, and drying in a drying oven at 140 ℃ to obtain the productA xerogel. And grinding and crushing the xerogel, putting the ground xerogel into a muffle furnace, and sintering for 2h at 600 ℃ under the air condition to obtain precursor powder.
Adding precursor powder into a solvent of ethanol and glycol, fully stirring and mixing, and uniformly spraying the precursor powder on the surface of a FeCrAl steel sample by using a high-pressure spray gun.
And placing the sprayed iron-based sample piece in a muffle furnace, sintering for 1h at 800 ℃, taking out and quenching with water to obtain a hydrogen-resistant coating attached to the surface of the iron-based sample piece, wherein the interface is tightly bonded, the thickness of the hydrogen-resistant coating is 70 mu m, and the hydrogen permeation reduction factor result of the coating is 2200 by testing through a gas-phase hydrogen permeation device.
Although the present description is described in terms of embodiments, not every embodiment includes only a single embodiment, and such description is for clarity only, and those skilled in the art should be able to integrate the description as a whole, and the embodiments can be appropriately combined to form other embodiments as will be understood by those skilled in the art.
Therefore, the above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application; all the equivalent changes made within the scope of the claims of the present application are the protection scope of the claims of the present application.
Claims (9)
1. A preparation method of a high-entropy composite oxide hydrogen-resistant coating is characterized by comprising the following steps:
s1, preparing xerogel from metal salt by a sol-gel method;
s2, pre-sintering the xerogel at the temperature of 200-600 ℃, and grinding to obtain precursor powder;
s3, fully dissolving the precursor powder in a solvent to obtain slurry with the solid content of 30-60%, and spraying the slurry on the surface of a metal sample piece under high pressure;
s4, sintering the sprayed metal sample piece at high temperature and rapidly cooling at 600-850 ℃ to obtain a hydrogen-resistant coating attached to the surface of the metal sample piece;
the metal salt is at least one of hydrolysable salts of Al, Y, cr, fe, er, zr and Ti; wherein the mole number of the Al element accounts for 50-70% of the total mole number of the metal elements in all the metal salts.
2. The method of claim 1, wherein the hydrolysable salts of Al, Y, cr, fe, er, zr comprise at least one of nitrate, acetate, and ammonium salts.
3. The method according to claim 1, wherein the hydrolyzable salt of Ti is n-butyl titanate.
4. The method according to claim 1, wherein the solvent is at least one selected from deionized water, ethanol, acetone, isopropanol, propanol, ethylene glycol, butanol, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, polyvinyl butyral, polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, and styrene butadiene rubber.
5. The method of claim 1, wherein the hydrogen barrier coating has a thickness of 0.1 to 100 μm.
6. The method of claim 1, wherein the xerogel is prepared by the following steps:
dissolving metal salt in deionized water, adding a complexing agent according to the mole number of 0.8-1.5 times of the metal salt, adjusting the pH value to 5.5-6.5, stirring at 50-90 ℃ until the metal salt is viscous and sol-like, and drying in an oven to obtain the xerogel.
7. The method according to claim 6, wherein the complexing agent is at least one of citric acid, ethylenediamine tetraacetic acid and polyvinyl alcohol.
8. The method according to claim 1, wherein the metal sample is made of FeCrAl steel.
9. A high-entropy composite oxide hydrogen-barrier coating, which is prepared by the preparation method according to any one of claims 1 to 8.
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Citations (7)
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