CN115110067A - Ternary composite novel hydrogen/deuterium/tritium permeation resistant coating and preparation method thereof - Google Patents
Ternary composite novel hydrogen/deuterium/tritium permeation resistant coating and preparation method thereof Download PDFInfo
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- CN115110067A CN115110067A CN202210648734.5A CN202210648734A CN115110067A CN 115110067 A CN115110067 A CN 115110067A CN 202210648734 A CN202210648734 A CN 202210648734A CN 115110067 A CN115110067 A CN 115110067A
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- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 229910052805 deuterium Inorganic materials 0.000 title claims abstract description 49
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 title claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 title claims abstract description 31
- 229910052722 tritium Inorganic materials 0.000 title claims abstract description 31
- 239000011206 ternary composite Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000011651 chromium Substances 0.000 claims abstract description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- -1 aluminum-chromium-zirconium salt Chemical compound 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 10
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 150000001844 chromium Chemical class 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000003754 zirconium Chemical class 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000423 chromium oxide Inorganic materials 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000003618 dip coating Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000005764 inhibitory process Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- 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
Abstract
The invention provides a ternary composite novel hydrogen/deuterium/tritium permeation resistant coating and a preparation method thereof 2 O 3 、Cr 2 O 3 And ZrO 2 Three phases are compounded. The composite coating integrates Al 2 O 3 And Cr 2 O 3 The excellent hydrogen/deuterium/tritium permeation resistance is characterized in that zirconia is used as a coating substrate, and chromium oxide and aluminum oxide are used as a second phase and are dispersedly distributed in or on the zirconia. Its deuterium permeation-inhibiting reduction factor (PRF) value ratio unit ZrO 2 The coating is improved by two orders of magnitude compared with the two-component ZrO 2 /Cr 2 O 3 The composite coating system is improved by one order of magnitude, and shows extremely excellent high-temperature deuterium resistance. The preparation process of combining sol-gel with dip-coating is simple and mature, has low cost, can meet the requirements of coating the surfaces of structural components with complex shapes and the inside of pipelines, and has higher practical value.
Description
Technical Field
The invention belongs to the field of coating materials, and particularly relates to a ternary composite novel hydrogen/deuterium/tritium permeation resistant coating and a preparation method thereof.
Background
The hydrogen isotopes tritium and deuterium are the main fuels of the controllable thermal nuclear reactor, and have important application in the field of fusion energy. However, the atomic radii of hydrogen, deuterium and tritium are very small, so that the hydrogen, deuterium and tritium are very easy to permeate into the metal structure material, the performance of the structure material is deteriorated, the service safety is damaged, and even the environmental radioactive pollution and other damages are caused. At present, one of the effective solutions is to prepare a hydrogen/deuterium/tritium permeation barrier ceramic coating on the surface of the structural material.
The single coating is limited by the hydrogen permeation characteristic and the high-temperature thermal mismatch characteristic with the base material, and the hydrogen permeation blocking capability of the structural material, the film-substrate combination, the thermal cycle stability and the like are required to be further improved. In recent years, the composite coating research shows better hydrogen permeation resistance and mechanical comprehensive performance, and CN104708863A adopts organic chemical vapor deposition or magnetron sputtering to prepare Al 2 O 3 /Cr 2 O 3 The composite coating combines the hydrogen permeation resistance of the chromium oxide and the aluminum oxide, but the hydrogen permeation resistance factor of the composite coating is only about 200 at 600 ℃, and the problems of complex preparation process and incapability of completely covering parts with complex shapes still exist.
In conclusion, the prior art also lacks a high-performance hydrogen/deuterium/tritium permeation resistant composite coating which is formed by compounding three components, has a simple preparation process and meets the covering requirements of complex parts.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel ternary composite hydrogen/deuterium/tritium permeation resistant coating and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a ternary composite hydrogen/deuterium/tritium permeation resistant coating is prepared from Al 2 O 3 、Cr 2 O 3 And ZrO 2 Three phases are compounded.
Further, the coating is formed by single-layer compounding or multi-layer compounding, and the thickness of the coating is 20nm-5 um.
The preparation method of the ternary composite novel hydrogen/deuterium/tritium permeation resistant coating comprises the following steps:
(1) preparing aluminum-chromium-zirconium salt mixed sol, namely taking aluminum salt, zirconium salt, chromium salt, absolute ethyl alcohol, acetone and glacial acetic acid as raw materials, fully stirring and dissolving to form clear and transparent mixed sol, wherein the molar ratio of the three metal salts can be randomly regulated and controlled, and the absolute ethyl alcohol is 10-150 ml, the acetone is 0.5-20 ml and the glacial acetic acid is 10-180 ul;
(2) uniformly coating the aluminum-chromium-zirconium salt mixed sol obtained in the step (1) on a stainless steel substrate by adopting a dipping and pulling method to obtain a precursor coating, namely, immersing a stainless steel substrate into the mixed sol, controlling the substrate lifting speed to be 50-500 um/s, putting the substrate into an oven for drying and shaping after the substrate completely emerges from the liquid level, wherein the drying temperature is 40-90 ℃, and the drying time is 0.5-3 h;
(3) placing the precursor coating obtained in the step (2) in a muffle furnace at 200-500 ℃ for heat preservation for 20-60 min to remove organic matters in the coating, and quickly taking out and cooling to room temperature;
(4) repeating the steps (1) - (3) for 1-20 times, and finally performing heat treatment for 0.5-5 h in a muffle furnace at 500-800 ℃ under the atmosphere, wherein the heating rate is 2-5 ℃/min, so as to form the coating.
Further, the aluminum salt comprises one of aluminum acetate, aluminum nitrate, aluminum isopropoxide or a mixture thereof.
Further, the chromium salt comprises one or a mixture of chromium acetate, chromium nitrate and chromium chloride.
Further, the zirconium salt comprises one or a mixture of zirconium acetate, zirconium nitrate and zirconium oxychloride.
The invention has the following beneficial effects:
1. the invention utilizes the excellent hydrogen permeation resistance of aluminum oxide, and the prepared ternary composite novel hydrogen/deuterium/tritium permeation resistance coating has excellent hydrogen/deuterium/tritium permeation resistance, and the permeation reduction factor of the coating to 321 stainless steel substrate can reach 3 orders of magnitude at most;
2. the invention combines the thermal expansion coefficient of the chromium oxide close to the base material and the good toughness of the zirconium oxide coating, and can adjust the composition proportion of the aluminum oxide, the chromium oxide and the zirconium oxide in the composite coating, thereby improving the thermal compatibility of the coating and the base body and enhancing the long-term reliability of the coating while enhancing the hydrogen/deuterium/tritium permeation resistance of the coating;
3. the preparation method is simple, the coating prepared by the dip-coating method has the unique characteristic of covering the surfaces of structural parts with complex shapes and the inner surface of a pipeline, has strong repeatability, and is suitable for large-scale production.
Drawings
FIG. 1 is an XRD pattern formed upon calcination at 700 ℃ of the ternary composite novel hydrogen/deuterium/tritium permeation resistant coating in accordance with example 2 of the present invention;
FIG. 2 is a steady-state current diagram of deuterium ion permeation in a high-temperature gas phase deuterium inhibition experiment at a calcination temperature of 650 ℃ in example 1 of the present invention;
FIG. 3 is a steady state current diagram of deuterium ion permeation in deuterium inhibition experiment at high temperature of 700 ℃ for calcination temperature in example 2 of the present invention;
FIG. 4 is a steady-state current diagram of deuterium ion permeation in high-temperature gas phase deuterium inhibition experiment at a calcination temperature of 750 ℃ in example 3 of the present invention;
FIG. 5 is a surface SEM image of a ternary composite novel hydrogen/deuterium/tritium permeation barrier coating of example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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 some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A ternary composite novel hydrogen/deuterium/tritium permeation resistant coating is prepared by the following method:
1. polishing 321 stainless steel to mirror surface, ultrasonically treating with ethanol for 15min, removing ions, and cleaning with acetone.
2. Weighing 1g of zirconium acetate, adding 18ml of absolute ethyl alcohol, 0.8ml of acetone and 16 mu L of glacial acetic acid, placing the mixture in a magnetic stirrer, stirring for about 10 hours until the mixture is fully dissolved to be in a clear transparent state, standing for 24 hours to obtain zirconium sol, weighing 0.95g of aluminum nitrate and 0.82g of chromium acetate, dissolving the aluminum nitrate and the chromium acetate in the zirconium sol, and stirring to obtain clear green mixed sol.
3. The dipping and pulling process is completed by a pulling machine, the pulling speed is uniform in the whole process, the pulling speed is set to be 300 mu m/s, the wet sol and the base material after pulling are placed at 80 ℃ for drying for 1h, the temperature is kept at 400 ℃ for 30min, the second layer is pulled after the wet sol and the base material are cooled, the previous operation is repeated, pulling is carried out for three times, finally, heat treatment is carried out, the temperature is carried out at 650 ℃ for 1h, and the temperature rising rate is 5 ℃/min.
The deuterium ion permeation steady-state current in the high temperature gas phase deuterium inhibition experiment of the present example is shown in fig. 2.
Example 2
A ternary composite novel hydrogen/deuterium/tritium permeation resistant coating is prepared by the following method:
1. polishing 321 stainless steel to mirror surface, ultrasonically treating with ethanol for 15min, removing ions, and cleaning with acetone.
2. Weighing 1g of zirconium acetate, adding 18ml of absolute ethyl alcohol, 0.8ml of acetone and 16 mu L of glacial acetic acid, placing the mixture in a magnetic stirrer, stirring for about 10 hours until the mixture is fully dissolved to be in a clear transparent state, standing for 24 hours to obtain zirconium sol, weighing 0.95g of aluminum nitrate and 0.82g of chromium acetate, dissolving the aluminum nitrate and the chromium acetate in the zirconium sol, and stirring to obtain clear green mixed sol.
3. The dipping and pulling process is completed by a pulling machine, the pulling speed is uniform in the whole process, the pulling speed is set to be 300 mu m/s, the wet sol and the base material after pulling are placed at 80 ℃ for drying for 1h, the temperature is kept at 400 ℃ for 30min, the second layer is pulled after the wet sol and the base material are cooled, the previous operation is repeated, pulling is carried out for three times, finally, heat treatment is carried out, the temperature is carried out at 700 ℃ for 1h, and the temperature rising rate is 5 ℃/min.
The deuterium ion permeation steady-state current in the high temperature gas phase deuterium inhibition experiment of the present example is shown in fig. 3.
Example 3
A ternary composite novel hydrogen/deuterium/tritium permeation resistant coating is prepared by the following method:
1. polishing 321 stainless steel to mirror surface, ultrasonically treating with ethanol for 15min, removing ions, and cleaning with acetone.
2. Weighing 1g of zirconium acetate, adding 18ml of absolute ethyl alcohol, 0.8ml of acetone and 16 mu L of glacial acetic acid, placing the mixture in a magnetic stirrer, stirring for about 10 hours until the mixture is fully dissolved to be in a clear transparent state, standing for 24 hours to obtain zirconium sol, weighing 0.95g of aluminum nitrate and 0.82g of chromium acetate, dissolving the aluminum nitrate and the chromium acetate in the zirconium sol, and stirring to obtain clear green mixed sol.
3. The dipping and pulling process is completed by a pulling machine, the pulling speed is uniform in the whole process, the pulling speed is set to be 300 mu m/s, the wet sol and the base material after pulling are placed at 80 ℃ for drying for 1h, the temperature is kept at 400 ℃ for 30min, the second layer is pulled after the wet sol and the base material are cooled, the previous operation is repeated, pulling is carried out for three times, finally, heat treatment is carried out, the heat treatment is carried out at 750 ℃ for 1h, and the temperature rising rate is 5 ℃/min.
The deuterium ion permeation steady-state current in the high temperature gas phase deuterium inhibition experiment of the present example is shown in fig. 4.
Example 4
A ternary composite novel hydrogen/deuterium/tritium permeation resistant coating is prepared by the following method:
1. polishing 321 stainless steel to mirror surface, ultrasonically treating with ethanol for 15min, removing ions, and cleaning with acetone.
2. Weighing 1g of zirconium acetate, adding 18ml of absolute ethyl alcohol, 0.8ml of acetone and 16 mu L of glacial acetic acid, placing the mixture in a magnetic stirrer, stirring for about 10 hours until the mixture is fully dissolved to be in a clear transparent state, standing for 24 hours to obtain zirconium sol, weighing 1.9g of aluminum nitrate and 0.82g of chromium acetate, dissolving the aluminum nitrate and the chromium acetate in the zirconium sol, and stirring to obtain clear green mixed sol.
3. The dipping and pulling process is completed by a pulling machine, the pulling speed is uniform in the whole process, the pulling speed is set to be 300 mu m/s, the wet sol and the base material after pulling are placed at 80 ℃ for drying for 1h, the temperature is kept at 400 ℃ for 30min, the second layer is pulled after the wet sol and the base material are cooled, the previous operation is repeated, pulling is carried out for three times, finally, heat treatment is carried out, the temperature is carried out at 700 ℃ for 1h, and the temperature rising rate is 5 ℃/min.
Referring to fig. 1, it can be seen that the XRD pattern of the composite coating prepared by heat treatment in air at 700 c shows that the coating is confirmed to be composed of three components of alumina, chromia and zirconia.
Ternary complex new hydrogen/deuterium/tritium permeation barriers prepared by comparative examples 1, 2 and 3Deuterium ion permeation current chart of high-temperature gas phase deuterium inhibition experiment of the coating can be seen, the high-temperature gas phase deuterium ion permeation current of the composite coating is in a lower level at the steady state under different temperatures, wherein the steady state current value of the coating prepared by heat treatment at 700 ℃ is the lowest and is about 1/2333 of a base material without the coating, and through calculation, deuterium Permeation Reduction Factors (PRF) of the coating prepared by heat treatment at 650 ℃, 700 ℃ and 750 ℃ of the composite coating are respectively 280, 2333 and 1610; thus, the PRF values of the coatings prepared in example 2 were up to three orders of magnitude, due to the pure ZrO 2 PRF value of coating is about 50, Cr 2 O 3 /ZrO 2 The PRF value of the composite coating is about 256 optimally, Al 2 O 3 /Cr 2 O 3 /ZrO 2 The PRF value of the composite coating is 2333, so that the addition of the aluminum oxide has a remarkable improvement on the deuterium permeation resistance of the coating.
FIG. 5 is an SEM image of the surface of the ternary complex novel hydrogen/deuterium/tritium permeation resistant coating of example 2, showing that the coating is entirely dense and free of defects, and the matrix phase of the coating is very fine ZrO 2 Crystal grains and larger Al precipitated on the surface 2 O 3 /Cr 2 O 3 Second phase grains, and bi-component Cr 2 O 3 /ZrO 2 Compared with the prior art, the composite coating has more excellent hydrogen/deuterium/tritium permeation resistance, so that the permeation retarding effect of the composite coating on hydrogen and isotopes can be further improved.
Example 4 the molar ratio of the three metal salts of the aluminum chromium zirconium sol, Al, was adjusted: cr: zr is 2:1:1, clear green sol can still be formed, and the surface of the formed ternary composite coating is still flat, compact and crack-free, which indicates that the preparation of the novel ternary composite coating is not influenced by changing the molar ratio of any metal salt.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A ternary composite novel hydrogen/deuterium/tritium permeation resistant coating is characterized in that: the coating is made of Al 2 O 3 、Cr 2 O 3 And ZrO 2 Three phases are compounded.
2. The ternary composite new hydrogen/deuterium/tritium permeation barrier coating of claim 1, wherein: the coating is formed by single-layer compounding or multi-layer compounding, and the thickness of the coating is 20nm-5 um.
3. A method for preparing the ternary complex novel hydrogen/deuterium/tritium permeation resistant coating according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) preparing aluminum-chromium-zirconium salt mixed sol, namely taking aluminum salt, zirconium salt, chromium salt, absolute ethyl alcohol, acetone and glacial acetic acid as raw materials, fully stirring and dissolving to form clear and transparent mixed sol, wherein the molar ratio of the three metal salts can be randomly regulated and controlled, and the absolute ethyl alcohol is 10-150 ml, the acetone is 0.5-20 ml and the glacial acetic acid is 10-180 ul;
(2) uniformly coating the aluminum-chromium-zirconium salt mixed sol obtained in the step (1) on a stainless steel substrate by adopting a dipping and pulling method to obtain a precursor coating, namely, immersing a stainless steel substrate into the mixed sol, controlling the substrate lifting speed to be 50-500 um/s, putting the substrate into an oven for drying and shaping after the substrate completely emerges from the liquid level, wherein the drying temperature is 40-90 ℃, and the drying time is 0.5-3 h;
(3) placing the precursor coating obtained in the step (2) in a muffle furnace at 200-500 ℃ for heat preservation for 20-60 min to remove organic matters in the coating, and quickly taking out and cooling to room temperature;
(4) repeating the steps (1) - (3) for 1-20 times, and finally performing heat treatment for 0.5-5 h in a muffle furnace at 500-800 ℃ under the atmosphere, wherein the heating rate is 2-5 ℃/min, so as to form the coating.
4. The method for preparing the ternary complex novel hydrogen/deuterium/tritium permeation resistant coating as claimed in claim 3, characterized in that: the aluminum salt comprises one or a mixture of aluminum acetate, aluminum nitrate and aluminum isopropoxide.
5. The method for preparing the ternary complex novel hydrogen/deuterium/tritium permeation resistant coating as claimed in claim 3, characterized in that: the chromium salt comprises one or a mixture of chromium acetate, chromium nitrate and chromium chloride.
6. The method for preparing the ternary complex novel hydrogen/deuterium/tritium permeation resistant coating as claimed in claim 3, characterized in that: the zirconium salt comprises one or a mixture of zirconium acetate, zirconium nitrate and zirconium oxychloride.
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