CN116855113A - 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
- Publication number
- CN116855113A CN116855113A CN202310821423.9A CN202310821423A CN116855113A CN 116855113 A CN116855113 A CN 116855113A CN 202310821423 A CN202310821423 A CN 202310821423A CN 116855113 A CN116855113 A CN 116855113A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- resistant coating
- composite oxide
- ball milling
- entropy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 239000011248 coating agent Substances 0.000 title claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000003980 solgel method Methods 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 18
- 238000000713 high-energy ball milling Methods 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon 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
- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000009837 dry grinding Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol 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
- 239000008096 xylene Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006776 Si—Zn Inorganic materials 0.000 description 1
- 229910007541 Zn O Inorganic materials 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
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a high-entropy composite oxide hydrogen-resistant coating, which consists of oxygen elements and non-oxygen elements, wherein the mole ratio of Al in the non-oxygen elements is 50-70%, the balance is Cr, fe, ga, si, zn and Cr, fe, ga, si, zn, the mole ratio is equal, and the thickness of the hydrogen-resistant coating is 0.1-100 microns. According to the invention, the atomic level mixing of raw materials is realized by a sol-gel method, so that the energy barrier required for synthesizing the high-entropy material is reduced, and then the low-temperature synthesis of the high-entropy ceramic is realized by fully roasting at a relatively low temperature. The method has the advantages of mild reaction conditions, controllable product particle size, purer product and the like, and effectively improves the overall hydrogen resistance and stability of the coating.
Description
Technical Field
The invention belongs to the technical field of hydrogen-resistant coatings, and particularly relates to a high-entropy composite oxide coating and a preparation method thereof.
Background
With the great development of hydrogen energy, the storage, transportation and controllable use of the hydrogen energy become important links in the current hydrogen energy industrialization development. However, hydrogen and its isotopes are extremely easy to diffuse into the lattice structures of the inner walls of the pipelines and the peripheral structural components due to the too small radius, and are destroyedThe mechanical properties of the material bring about great potential safety hazards, which must be resolved especially in the case of nuclear reactions involving hydrogen and its isotopes. Therefore, constructing a hydrogen-resistant coating on the surfaces of the corresponding pipeline and the component becomes a necessary condition for safely using hydrogen energy. Existing coating materials mainly include metal oxides, metal nitrides or metal carbides, etc., wherein oxide-type materials exhibit extremely high hydrogen barrier advantages. Currently, high entropy oxide ceramics can exhibit preferential, slow kinetics, lattice distortion and a series of other properties of single-phase solid phases with simple crystal structures through a highly disordered multi-component system, and are expected to improve the problems of weak bonding force between the current single oxide coating and a substrate, and the like. Thus, at Al 2 O 3 The multi-component high-entropy oxide ceramic is designed on the basis of the base coating, and has important significance in realizing low-cost and simple preparation.
Disclosure of Invention
In order to solve the technical problems, the invention provides an Al-Cr-Fe-Ga-Si-Zn-O high-entropy composite oxide hydrogen-resistant coating and a preparation method thereof, so as to solve the problems of weak bonding force with a substrate and the like generated by a single oxide coating.
The high-entropy composite oxide hydrogen-resistant coating consists of oxygen elements and non-oxygen elements, wherein the mole ratio of Al in the non-oxygen elements is 50% -70%, the balance is Cr, fe, ga, si, zn and Cr, fe, ga, si, zn, the mole ratio of Al in the non-oxygen elements is equal, and the thickness of the hydrogen-resistant coating is 0.1-100 microns, preferably 10-100 microns. The composite oxide may be Al 2 O 3 -Cr 2 O 3 -Fe 2 O 3 -Ga 2 O 3 -SiO 2 -ZnO. In addition, the inventor researches and discovers that the composite material structure constructed by adopting the aluminum oxide has poor hydrogen resistance effect if the aluminum oxide is simple in composition and not strong in binding force with a matrix, and the specific composition of the invention is not adopted. The high entropy generally has complex composition and high ion arrangement confusion. Simple alumina generally does not lend itself to the concept of high entropy.
The preparation method of the high-entropy composite oxide hydrogen-resistant coating comprises the following steps:
s1: preparing high-activity precursor powder of the composite oxide:
mixing the Al, cr, fe, ga, zn soluble salt with a silicon-based organic solvent to prepare xerogel by a sol-gel method, performing heat treatment in an oxygen-containing atmosphere, and sintering to obtain oxide mixed powder; then, performing high-energy ball milling, and further grinding and crushing to obtain high-activity precursor powder;
s2: preparing a coating by an immersion method:
mixing the precursor powder obtained in the step S1 with a solution, preparing slurry by ball milling, magnetic stirring or grinding to ensure that the solid content of the precursor is 20% -40%, repeatedly immersing the iron-based metal sample piece into the slurry for a period of time for one time or multiple times, taking out and drying;
s3: preparing a hydrogen-resistant coating by high-temperature heat treatment:
and (3) forming a high-entropy composite oxide hydrogen-resistant coating on the surface of the sample piece obtained through the treatment in the step (S2) through a high-temperature sintering and rapid cooling mode.
In the above preparation method, the soluble salt of Al, cr, fe, ga, zn in step S1 includes one or more of nitrate, acetate, ammonium salt, etc., and the silicon-based organic solvent includes silicone oil, methyl silicone oil, etc.;
in the preparation method, the sol-gel method in the step S1 comprises the steps of using one or more of citric acid, ethylenediamine tetraacetic acid and polyvinyl alcohol as an additive, and adjusting the pH to 6-7 with or without using one or more of nitric acid and ammonia water; the method also comprises heating and stirring the mixture at 70-90deg.C to obtain a viscous sol.
In the preparation method, the heat treatment process in the step S1 comprises sintering for 30-300 minutes at 200-600 ℃ in air or oxygen atmosphere; preferably at 500-600 deg.c for 2-3 hours.
In the preparation method, the high-energy ball milling mode in the step S1 comprises dry milling or using one of water, ethanol and acetone as a dispersing agent, wherein the ball milling rotating speed is 300-800rpm, and the ball milling time is 10-300 minutes. The particle size of the powder can be further reduced by adopting high-energy ball milling, and the reactivity of the powder can be improved; and the common ball milling mainly generates a mixing effect, and the influence on the particle size of the powder is far weaker than that of the high-energy ball milling. The rotating speed and the ball milling time of the high-energy ball milling have larger influence on the particle size of the powder, and the high-energy ball milling rotating speed is 400-600rpm and the ball milling time is 100-300 minutes in comprehensive consideration. The high-energy ball mill can be a common planetary ball mill.
In the above preparation method, the solution in the step S2 contains one or more of deionized water, ethanol, acetone, ethylene glycol, glycerol, polyethylene glycol, and xylene; the solution is preferably at least one of ethanol, acetone, glycol and glycerol; more preferably, any two of ethanol, acetone, ethylene glycol and glycerol are mixed according to a volume ratio of 1:1 combination. Wherein, any one or more of dibutyl phthalate, polyvinyl butyral, polyvinylidene fluoride, polytetrafluoroethylene and sodium carboxymethyl cellulose can be added into the solution for improving the viscosity of the mixed solution.
The drying mode comprises one of room temperature vacuum drying and low temperature drying at 50-120 ℃.
In the preparation method, the high-temperature heat treatment in the step S3 is carried out under the atmosphere of air or oxygen, sintering is carried out for 30-300 minutes at 600-900 ℃, and air cooling, water cooling or liquid nitrogen cooling is carried out, so that cooling along with furnace cooling is not needed, and the cooling is slow. Preferably at 800-900 c for 1-3 hours.
The invention fully utilizes the prior Al 2 O 3 The excellent hydrogen resistance effect of the base coating is achieved by mixing elements such as Cr-Fe-Ga-Si-Zn, the activity of a precursor is improved by means of sol-gel and high-energy ball milling, and the precursor is fully baked at the relatively low temperature after sintering by rapid reduction of Wen Shi, so that the low-temperature synthesis of the high-entropy ceramic is achieved.
The invention utilizes the disorder of the high-entropy alloy to construct a compact high-entropy coating, and can improve the bonding strength of the coating, so that the coating is tightly bonded with a matrix, thereby improving the hydrogen resistance of the material. The invention adopts high-energy ball milling to improve the disorder degree and the reactivity of the raw materials. Meanwhile, the material is usually cooled along with the furnace, but not cooled rapidly after the high temperature is adopted, but the invention needs to be cooled rapidly after the high temperature, because the disorder state of the raw material of the invention at the high temperature can be reserved through rapid cooling, so that the coating still keeps the high temperature phase at normal temperature. If slow cooling is employed, the atoms of the starting material will spontaneously arrange, thereby losing the effect of high entropy (high disorder), i.e., if slow cooling is employed, the high temperature phase will gradually transition to an ordered low temperature phase.
The method comprises the steps of preparing high-activity precursor powder by combining a soluble salt of Al, cr, fe, ga, zn and a silicon-based organic solvent through a sol-gel method with low-temperature oxidation sintering and high-energy ball milling, preparing slurry, dipping and drying a target iron-based sample in the slurry for multiple times, and forming the high-entropy composite oxide hydrogen-resistant coating through heat treatment and rapid cooling. The method realizes the atomic level mixing of the raw materials by a sol-gel method, assists in high-energy ball milling so as to reduce the energy barrier required by synthesizing the high-entropy material, and then carries out full roasting at a relatively low temperature and rapid cooling to realize the low-temperature synthesis of the high-entropy composite oxide coating or ceramic. The method has the advantages of mild reaction conditions, controllable product particle size, purer product and the like, and effectively improves the overall hydrogen resistance and stability of the coating.
Drawings
FIG. 1 is an Al alloy prepared in example 1 of the present invention 60 Cr 8 Fe 8 Ga 8 Si 8 Zn 8 O x High entropy composite oxide hydrogen-resistant coating morphology; the coating is tightly combined with the matrix, no obvious pores exist, and the thickness of the coating is about 16 microns.
Detailed Description
The following examples are further illustrative of the technical content of the present invention, but the essential content of the present invention is not limited to the examples described below, and those skilled in the art can and should know that any simple changes or substitutions based on the essential spirit of the present invention should fall within the scope of the present invention as claimed.
Example 1
Al (aluminum) alloy 60 Cr 8 Fe 8 Ga 8 Si 8 Zn 8 O x High entropy compoundingThe oxide hydrogen barrier coating comprises the following steps:
step S1:
weighing Al (NO) according to mole ratio 3 ) 3 、Cr(NO 3 ) 3 、Fe(NO 3 ) 3 、Ga(NO 3 ) 3 Methyl silicone oil, zn (NO) 3 ) 2 And dissolved in deionized water according to a molar ratio of metal salt to citric acid of 1:1 adding citric acid. Heating and stirring the solution at 80 ℃ until the solution forms a viscous sol, drying to form xerogel, sintering the xerogel in a muffle furnace at 500 ℃ for 2 hours, performing high-energy ball milling on the obtained powder, grinding the powder with absolute ethyl alcohol serving as a dispersing agent for 120 minutes at a rotating speed of 500rpm, and taking out and drying the powder to obtain the precursor powder.
Step S2:
the volume ratio of ethanol to glycerol is 1:1, adding precursor powder into the mixed solution, fully stirring and mixing to form uniform slurry, adding sodium carboxymethylcellulose into the mixed solution to improve the viscosity of the mixed solution, wherein the solid content of the precursor powder is 20%, soaking an iron-based sample in the slurry for 10 minutes, taking out, placing in a vacuum drying oven for suspension, and continuously maintaining low pressure at room temperature until the mixture is dried.
Step S3:
and (2) placing the sample obtained in the step (S2) in a muffle furnace, sintering for 1h at 900 ℃, and then water-cooling to form a hydrogen-resistant coating on the surface of the sample. The coating thickness was about 16 microns, was tightly bonded to the substrate, had no apparent interfacial porosity, and had a hydrogen permeation reduction factor of about 1800 when the coating was tested by a gas phase hydrogen permeation device.
Example 2
Al (aluminum) alloy 50 Cr 10 Fe 10 Ga 10 Si 10 Zn 10 O x The high-entropy composite oxide hydrogen-resistant coating comprises the following steps:
step S1:
weighing Al (OAc) according to mole proportion 3 、Cr 2 (OAc) 4 、Ga(NO 3 ) 3 、Fe(NO 3 ) 3 Methyl silicone oil, zn (NO) 3 ) 2 And is dissolved in deionized waterAccording to the molar ratio of the metal salt to the citric acid of 1:1.1 adding citric acid, adding ammonia water to regulate pH to 6, heating and stirring the solution at 80 ℃ until the solution forms a viscous sol, and drying to form xerogel. Sintering the mixture in a muffle furnace at 550 ℃ for 3 hours, performing high-energy ball milling, adopting acetone as a dispersing agent, grinding for 240 minutes at 400rpm, and taking out and drying to obtain precursor powder.
Step S2:
the volume ratio of the acetone to the glycol is 1:1, adding the precursor powder into the mixed solution, fully stirring and mixing, adding dibutyl phthalate into the mixed solution to improve the viscosity of the mixed solution, wherein the solid content of the precursor is 30%, completely immersing the iron-based sample in the slurry for 3min, taking out and placing in a vacuum drying oven for suspension, completely immersing again in the slurry when no liquid drops fall down, and taking out and placing in the vacuum drying oven for suspension. After 4 times of repeated dipping, hanging the sample piece in a vacuum drying oven at room temperature, and continuously maintaining low pressure until the sample piece is dried.
Step S3:
and (3) placing the sample obtained in the step (S2) in a muffle furnace, sintering at 800 ℃ for 1h, and then air-cooling to form a hydrogen-resistant coating on the surface of the sample. The coating thickness was about 100 microns, was relatively tightly bonded to the substrate, had no significant interfacial porosity, and had a hydrogen permeation reduction factor of about 2300 as measured by a gas phase hydrogen permeation device.
Example 3
Al (aluminum) alloy 70 Cr 6 Fe 6 Ga 6 Si 6 Zn 6 O x The high-entropy composite oxide hydrogen-resistant coating comprises the following steps:
step S1:
weighing Al (OAc) according to mole proportion 3 、Cr 2 (OAc) 4 、Ga(NO 3 ) 3 、Fe(NO 3 ) 3 Methyl silicone oil, zn (NO) 3 ) 2 And dissolved in deionized water according to the molar ratio of metal salt to citric acid of 1:1.1 adding citric acid, adding ammonia water to regulate pH to 6, heating and stirring the solution at 80 ℃ until the solution forms a viscous sol, and drying to form xerogel. Sintering at 500 ℃ in a muffle furnaceAnd (3) grinding for 200 minutes at 600rpm by using acetone as a dispersing agent through high-energy ball milling after 2 hours, and taking out and drying to obtain precursor powder.
Step S2:
the volume ratio of the acetone to the glycol is 1: and 1, adding the precursor powder into the mixed solution, fully stirring and mixing, wherein the solid content of the precursor is 40%, fully immersing the iron-based sample in the slurry for 3 minutes, taking out and placing in a vacuum drying oven for suspension, fully immersing in the slurry again when no liquid drops fall down, and taking out and placing in the vacuum drying oven for suspension. After repeated dipping for 2 times, the sample is hung in a vacuum drying oven at room temperature, and the pressure is kept low until the sample is dried.
Step S3:
and (3) placing the sample obtained in the step (S2) in a muffle furnace, sintering for 1h at 800 ℃ and then air-cooling to form a hydrogen-resistant coating on the surface of the sample. The coating thickness was about 80 microns, the bonding to the substrate was relatively tight, no apparent interfacial porosity, and the hydrogen permeation reduction factor of the coating was about 2000 as measured by a gas phase hydrogen permeation device.
Comparative example 1
Al (aluminum) alloy 60 Cr 8 Fe 8 Ga 8 Si 8 Zn 8 O x The composite oxide hydrogen-resistant coating comprises the following steps:
step S1:
weighing Al (NO) according to mole ratio 3 ) 3 、Cr(NO 3 ) 3 、Fe(NO 3 ) 3 、Ga(NO 3 ) 3 Methyl silicone oil, zn (NO) 3 ) 2 And dissolved in deionized water according to a molar ratio of metal salt to citric acid of 1:1 adding citric acid. The solution was heated to 80 ℃ and stirred until the solution formed a viscous sol and dried to form a xerogel. And grinding and crushing the xerogel by using a mortar, and sintering in a muffle furnace at 500 ℃ for 2 hours to obtain precursor powder.
Step S2:
the volume ratio of ethanol to glycerol is 1:1, adding precursor powder into the mixed solution, fully stirring and mixing to form uniform slurry, wherein the solid content of the precursor powder is 20%, soaking an iron-based sample in the slurry for 10 minutes, taking out and placing in a vacuum drying oven for suspension, and continuously maintaining low pressure at room temperature until the precursor powder is dried.
Step S3:
and (3) placing the sample obtained in the step (S2) in a muffle furnace, sintering at 900 ℃ for 1h, cooling along with the furnace, and forming a hydrogen-resistant coating on the surface of the sample. The thickness of the coating is about 14 microns, the precursor activity is weaker because the coating is not subjected to high-energy ball milling treatment, and meanwhile, the precursor is not rapidly cooled after heat treatment but is cooled along with a conventional slow furnace, so that partial coating has component segregation, cracking and stripping phenomena occur, and the hydrogen blocking function cannot be realized.
Comparative example 2
Step S1 replaces high-energy ball milling with ordinary ball milling, acetone is still used as a dispersing agent, and xerogel is ground at a rotating speed of 100 rpm. Other processes were the same as in example 2. The thickness of the finally obtained coating is about 300 microns, the bonding with the matrix is not tight enough, and the coating has obvious interface pores and cannot realize the hydrogen blocking function.
Comparative example 3
In step S3, air cooling is replaced by furnace cooling. Other processes were the same as in example 2. The thickness of the finally obtained coating is about 200 micrometers, the coating is not tightly combined with a matrix, and has obvious interface pores, so that the hydrogen blocking function cannot be realized.
It should be noted that the foregoing technical disclosure is only for explanation and illustration to enable one skilled in the art to know the technical spirit of the present invention, and the technical disclosure is not intended to limit the scope of the present invention. The essential scope of the invention is as defined in the appended claims. Those skilled in the art should understand that any modification, equivalent substitution, improvement, etc. made based on the spirit of the present invention should fall within the spirit and scope of the present invention.
Claims (8)
1. The high-entropy composite oxide hydrogen-resistant coating consists of oxygen elements and non-oxygen elements, wherein the molar ratio of Al in the non-oxygen elements is 50% -70%, the balance is Cr, fe, ga, si, zn and Cr, fe, ga, si, zn, the molar ratio is equal, and the thickness of the hydrogen-resistant coating is 0.1-100 microns.
2. The method for preparing the high-entropy composite oxide hydrogen-resistant coating as claimed in claim 1, comprising the steps of:
s1: preparing high-activity precursor powder of the composite oxide:
mixing the Al, cr, fe, ga, zn soluble salt with a silicon-based organic solvent to prepare xerogel by a sol-gel method, performing heat treatment in an oxygen-containing atmosphere, and sintering to obtain oxide mixed powder; then, performing high-energy ball milling, and further grinding and crushing to obtain high-activity precursor powder;
s2: preparing a coating by an immersion method:
mixing the precursor powder obtained in the step S1 with a solution, preparing slurry by ball milling, magnetic stirring or grinding to ensure that the solid content of the precursor is 20% -40%, repeatedly immersing the iron-based metal sample piece into the slurry for a period of time for one time or multiple times, taking out and drying;
s3: preparing a hydrogen-resistant coating by high-temperature heat treatment:
and (3) forming a high-entropy composite oxide hydrogen-resistant coating on the surface of the sample piece obtained through the treatment in the step (S2) through a high-temperature sintering and rapid cooling mode.
3. The method of claim 2, wherein the soluble salt of Al, cr, fe, ga, zn in step S1 comprises one or more of nitrate, acetate, and ammonium salts, and the silicone-based organic solvent comprises methyl silicone oil.
4. The method of claim 2, wherein the sol-gel process of step S1 comprises adjusting pH6-7 with or without one or more of nitric acid, ammonia, using one or more of citric acid, ethylenediamine tetraacetic acid, polyvinyl alcohol as an additive; the method also comprises heating and stirring the mixture at 70-90deg.C to obtain a viscous sol.
5. The method of claim 2, wherein the heat treatment process of step S1 comprises sintering at 200-600 ℃ for 30-300 minutes in an air or oxygen atmosphere.
6. The method according to claim 2, wherein the high-energy ball milling method in the step S1 comprises dry milling or using any one or more of water, ethanol and acetone as a dispersing agent, wherein the ball milling speed is 300-800rpm, and the ball milling time is 10-300 minutes.
7. The method according to claim 2, wherein the solution in step S2 comprises one or more of deionized water, ethanol, acetone, ethylene glycol, glycerol, polyethylene glycol, xylene, dibutyl phthalate, polyvinyl butyral, polyvinylidene fluoride, polytetrafluoroethylene, and sodium carboxymethyl cellulose.
8. The preparation method according to claim 2, wherein the high-temperature heat treatment in the step S3 is sintering at 600-900 ℃ for 30-300 minutes in an air or oxygen atmosphere, and air cooling, water cooling or liquid nitrogen cooling is performed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310821423.9A CN116855113B (en) | 2023-07-06 | High-entropy composite oxide hydrogen-resistant coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310821423.9A CN116855113B (en) | 2023-07-06 | High-entropy composite oxide hydrogen-resistant coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116855113A true CN116855113A (en) | 2023-10-10 |
| CN116855113B CN116855113B (en) | 2024-05-31 |
Family
ID=
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108315686A (en) * | 2017-12-08 | 2018-07-24 | 水利部杭州机械设计研究所 | A kind of puppet high-entropy alloy coating formula and its coating production |
| CN115837275A (en) * | 2022-11-04 | 2023-03-24 | 天津大学 | Perovskite type high-entropy oxide and preparation method and application thereof |
| CN115872725A (en) * | 2022-12-08 | 2023-03-31 | 中国科学院合肥物质科学研究院 | Al-Y-Cr-Fe-Zr-Nb-Ti-Ta-O high-entropy composite oxide hydrogen-resistant coating |
| WO2023091595A1 (en) * | 2021-11-18 | 2023-05-25 | Lehigh University | Medium to high entropy alloys and methods of making the same |
| CN116237214A (en) * | 2022-12-13 | 2023-06-09 | 中国科学院合肥物质科学研究院 | Al-Y-Cr-Fe-Er-O high-entropy composite oxide hydrogen-resistant coating and preparation method thereof |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108315686A (en) * | 2017-12-08 | 2018-07-24 | 水利部杭州机械设计研究所 | A kind of puppet high-entropy alloy coating formula and its coating production |
| WO2023091595A1 (en) * | 2021-11-18 | 2023-05-25 | Lehigh University | Medium to high entropy alloys and methods of making the same |
| CN115837275A (en) * | 2022-11-04 | 2023-03-24 | 天津大学 | Perovskite type high-entropy oxide and preparation method and application thereof |
| CN115872725A (en) * | 2022-12-08 | 2023-03-31 | 中国科学院合肥物质科学研究院 | Al-Y-Cr-Fe-Zr-Nb-Ti-Ta-O high-entropy composite oxide hydrogen-resistant coating |
| CN116237214A (en) * | 2022-12-13 | 2023-06-09 | 中国科学院合肥物质科学研究院 | Al-Y-Cr-Fe-Er-O high-entropy composite oxide hydrogen-resistant coating and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| M. S. ARZHAKOV等: "Universal temperature dependence of the vapor pressure of chemical elements", DOKLADY PHYSICAL CHEMISTRY, vol. 418, 5 February 2011 (2011-02-05) * |
| 李工等: "高熵合金研究现状", 燕山大学学报, vol. 42, no. 02, pages 101 - 4 * |
| 项厚政;权峰;李文超;刘晓磊;冒爱琴;俞海云;: "高熵氧化物的制备及应用研究进展", 过程工程学报, no. 03, 31 March 2020 (2020-03-31) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2662488C1 (en) | Method of manufacture of ceramic material of high density with use of hexagonal boron nitride | |
| CN108751969B (en) | High-temperature-resistant, heat-insulating and wave-transmitting ceramic matrix composite and preparation method thereof | |
| CN103274696B (en) | Heat wave-transmission porous ceramic material and preparation method thereof | |
| CN108840683B (en) | Process for preparing zirconium nitride ceramic microspheres and zirconium nitride ceramic microspheres | |
| CN101898906B (en) | Preparation method of SiO2-mullite-Al2O3 gradient outer coating for carbon/carbon composite material | |
| CN113501543B (en) | High-entropy rare earth zirconate nano aerogel and preparation method and application thereof | |
| CN102730690A (en) | Al4SiC4 material synthetic method | |
| CN108383530B (en) | ZrB2Preparation process of-SiC ceramic composite powder by precursor conversion method | |
| CN104649709A (en) | Method for manufacturing porous silicon carbide ceramic | |
| CN116855113B (en) | High-entropy composite oxide hydrogen-resistant coating and preparation method thereof | |
| CN116855113A (en) | High-entropy composite oxide hydrogen-resistant coating and preparation method thereof | |
| CN112341207A (en) | Silicon nitride-silicon oxynitride column-hole composite ceramic material and preparation method thereof | |
| CN101700980A (en) | Method for preparing nano-mullite powder by sol-gel-hydrothermal method | |
| CN115872725B (en) | High-entropy composite oxide hydrogen-resistant coating of Al-Y-Cr-Fe-Zr-Nb-Ti-Ta-O | |
| CN115259901A (en) | Preparation method of TaC protective coating material on carbon material surface | |
| CN108358641B (en) | Al (aluminum)4SiC4Method for preparing ceramic material | |
| CN111099908B (en) | High-performance ceramic of carbon fiber composite rare earth lanthanum zirconate with surface coated with silicon oxide and preparation method thereof | |
| CN116237214B (en) | Al-Y-Cr-Fe-Er-O high-entropy composite oxide hydrogen-resistant coating and preparation method thereof | |
| CN115971011B (en) | High-entropy composite oxide hydrogen-resistant coating and preparation method thereof | |
| CN109650933B (en) | Porous Co3O4/Al2SiO5Low-density wave-absorbing type complex phase ceramic and preparation method thereof | |
| CN101700887B (en) | Method for preparing nano-mullite powder by sol-gel-microwave hydrothermal method | |
| CN110699566A (en) | CaMn7O12Reinforced low-expansion high-thermal-conductivity copper-based composite material and preparation method thereof | |
| CN117024129B (en) | Preparation method of chromium-doped lanthanum disilicate ceramic | |
| CN116003141B (en) | High-temperature-resistant multi-shell TAC-based absorbent and preparation method thereof | |
| CN116145127A (en) | Composite oxide hydrogen-resistant coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |