CN114015959A - 一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法 - Google Patents
一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法 Download PDFInfo
- Publication number
- CN114015959A CN114015959A CN202111313422.0A CN202111313422A CN114015959A CN 114015959 A CN114015959 A CN 114015959A CN 202111313422 A CN202111313422 A CN 202111313422A CN 114015959 A CN114015959 A CN 114015959A
- Authority
- CN
- China
- Prior art keywords
- resistant
- layer
- wear
- zirconium alloy
- coating
- 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.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- 238000000576 coating method Methods 0.000 title claims abstract description 67
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 62
- 238000005253 cladding Methods 0.000 title claims abstract description 61
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 54
- 230000007797 corrosion Effects 0.000 claims abstract description 53
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 17
- 229910003470 tongbaite Inorganic materials 0.000 claims abstract description 16
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims description 152
- 239000000919 ceramic Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium dioxide Chemical compound O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000000231 atomic layer deposition Methods 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- 238000007733 ion plating Methods 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910021359 Chromium(II) silicide Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910010293 ceramic material Inorganic materials 0.000 claims description 6
- 238000010288 cold spraying Methods 0.000 claims description 6
- 239000007769 metal material Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000007751 thermal spraying Methods 0.000 claims description 6
- 229910021354 zirconium(IV) silicide Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910007873 ZrAl3 Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005488 sandblasting Methods 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 8
- 239000003758 nuclear fuel Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 40
- 239000000446 fuel Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010011906 Death Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- ORSHEMWJSSJJPJ-UHFFFAOYSA-N [O-2].[Zr+4].[U+6].[O-2].[O-2].[O-2].[O-2] Chemical compound [O-2].[Zr+4].[U+6].[O-2].[O-2].[O-2].[O-2] ORSHEMWJSSJJPJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21C—NUCLEAR REACTORS
- G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
- G21C3/02—Fuel elements
- G21C3/04—Constructional details
- G21C3/06—Casings; Jackets
- G21C3/07—Casings; Jackets characterised by their material, e.g. alloys
-
- 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
- Y02E30/30—Nuclear fission reactors
Abstract
本发明属于核燃料技术领域，具体公开了一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法，包括锆合金包壳管基体、粘结层、耐腐蚀层和耐磨层；本发明外部中的耐磨层可采用多层膜层，并且多层膜层可采用CrN、Cr3C2、ZrO2等材料实现表面硬度的提升，提高锆合金包壳管的耐磨性能，并采用金属Cr、Nb、Zr等缓冲热膨胀系数差异，减少应力集中，该材料在事故工况下和在高温水蒸气腐蚀环境中，可在最初防护阶段可形成Cr2O3致密氧化膜，减少高温蒸汽环境的影响，在内部粘结层可利用与锆合金匹配的热膨胀系数，避免在升降温过程中产生裂纹或涂层脱落，通过以上对涂层的结构与物相设计，使得涂层具有优异的耐磨损性能和优异的抗高温水蒸汽腐蚀性能。
Description
技术领域
本发明涉及核燃料技术领域，具体为一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法。
背景技术
轻水反应堆是核电站的主要堆型，采用棒状核燃料元件(以下简称“燃料棒”)。燃料棒由短圆柱状的UO2燃料芯块、锆合金包壳、端塞、贮气腔压紧弹簧等构成，燃料芯块与包壳之间留有一定的间隙，燃料元件充填了惰性气体，如图1所示，图1中：1、端塞，2、锆合金包壳，3、压紧弹簧，4、短圆柱状的UO2燃料芯块。
继2011年福岛核电站发生灾难之后，为了提高核电站的安全性以应对全厂断电事故，国际核燃料界提出了增强事故容耐受能力的抗事故燃料(Accident Tolerant Fuel)的概念。目前，在压水堆中使用锆-氧化铀系统作为核燃料，而在失水事故工况下，锆合金在1200℃下将与水蒸气发生如下反应：
Zr+2H2O＝ZrO2+2H2
该反应所产生的氢气不断积聚，将产生氢爆，威胁反应堆安全。在锆合金包壳管表面制备涂层以隔绝失水事故下的水蒸气与锆合金的直接接触，从而减缓事故的发生，增强压水反应堆的安全性。
对于燃料棒锆合金包壳管，除了抗高温水蒸气腐蚀性能亟需提升外，在寿期末状态下锆合金格架，格架弹簧与燃料棒包壳管间将出现间隙，在冷却剂的冲刷作用下将导致燃料棒振动，格架与燃料棒包壳管之间出现碰撞、摩擦，产生包壳管的微动磨损，严重者将导致包壳管破裂，甚至出现核泄漏。因此，需要提高包壳管的耐磨性能，减少摩擦对包壳管的影响。
研究表明，含有Cr、Al、Si等元素的材料，如：金属Cr、FeCrAl合金、SiC陶瓷等，在高温水蒸气环境中常可形成Cr2O3、Al2O3、SiO2等致密膜，该膜层可阻碍高温水蒸气向内侵蚀，从而使材料具有抗高温水蒸气腐蚀性能。因此可将该材料作为耐腐蚀涂层使用。
过渡族金属(Cr、Fe、Zr)的碳化物、氮化物、氧化物，具有优异的耐磨性能。简中华等人采用超音速喷涂制备NiCr-Cr3C2，涂层显微硬度达到950HV0.3，具有优良的抗磨损性能。【简中华，马壮，曹素红，等，超音速火焰喷涂WC-Co与NiCr-Cr2C3涂层磨损性能研究，材料工程，2007(7)：21-24】钟厉等人通过磁控溅射技术在钢具表面制备CrN涂层，结果表明膜层结合强度可达31.6N，在5N载荷下涂层具有优异的耐磨损性能。【钟厉，龙永杰，韩西，刀具表面磁控溅射CrN涂层及其耐磨性能研究，表面技术，2018(10)：151-156】林松盛等人在钛合金表面制备了Ti-TiN-Zr-ZrN多层膜，膜厚度约为5.8μm，显微硬度为28.1Gpa，膜基结合力为56N，具有优异的耐磨性能。【林松盛，周克崧，代明江等，钛合金表面Ti-TiN-Zr-ZrN多层膜制备及性能，材料工程，2017(6)：31-35】裴旭等人在45号钢表面表面制备了Ni-ZrO2纳米复合涂层，该涂层的显微硬度可达934.19HV0.1，并且具有优异的耐磨性能。【裴旭，易剑，Ni-ZrO2纳米复合涂层制备及其耐磨耐蚀性能研究，浙江理工大学学报，2015(5)：336-339】。
对于锆合金包壳管的抗高温水蒸气腐蚀性能与耐磨性能亟需提升的情况，虽然有研究人员改善其相关性能，但无法实现2项性能同时大幅提升。本发明将过渡族金属的碳化物、氮化物、氧化物(Cr3C2、CrN、ZrN、ZrO2等物质)制备为涂层外层，将增强锆合金包壳管的耐磨性能，并且可将外层制备为多层膜结构，如：制备陶瓷相与金属相交叠多层膜，该结构中金属相增加薄膜韧性，并缓冲热膨胀系数差异，减少应力集中，增强涂层的服役性能。膜层所选用的材料中含有Cr、Si、Al、Ti等易于分别形成Cr2O3、SiO2、Al2O3、TiO2等致密氧化膜的元素，使得膜层兼有抗高温水蒸气腐蚀性能。该发明可使得锆合金包壳管的抗高温水蒸气腐蚀性能与耐磨性能均有大幅提升。
发明内容
本发明的目的在于提供一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法，包括锆合金包壳管基体、粘结层、耐腐蚀层和耐磨层，所述锆合金包壳管基体表面涂覆有粘结层，所述粘结层表面涂覆有耐腐蚀层，所述耐腐蚀层表面涂覆有耐磨层。
优选的，所述粘结层包括金属材料和陶瓷材料，其中金属材料包括Zr、Cr、Nb和Ni，陶瓷材料包括ZrO2、ZrN、CrN和Cr3C2。
优选的，所述耐腐蚀层的成分包括Cr、FeCrAl、FeCrSi、ZrAlCrSi、ZrCr2、ZrAl3、ZrSi2、ZrO2、ZrN、ZrC、CrSi2、CrO2、CrN、Cr3C2，其中Cr、Al、Si、Ti为必须元素。
优选的，所述耐磨层为单一膜层，耐磨层的成分中需含有O、C、N其中的一种元素，并含有Cr、Al、Si、Ti、Zr一种或一种以上元素，包括但不限于以下物质：ZrSi2、ZrO2、ZrN、ZrC、CrSi2、CrO2、CrN、Cr3C2等。
优选的，所述耐磨层为多层膜层，包括陶瓷相层和金属相层，且陶瓷相层与金属相层交叠往复，其中陶瓷相的组成需含有O、C、N一种元素，并含有Cr、Al、Si、Ti、Zr一种和一种以上元素，金属相的组成由Cr、Fe、Al、Zr、Nb、Ni元素中的一种或多种组成；其中陶瓷相层和金属相层厚度为10-500nm。
优选的，所述粘结层厚度为0.1-10μm。
优选的，所述耐腐蚀层厚度为1-30μm。
优选的，所述耐磨层厚度为0.5-10μm。
本发明还提供一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层的制备方法，包括以下步骤：
S1.预处理：利用酒精、丙酮等清洗剂对锆合金包壳管进行清洗，去除表面污垢，进行喷沙处理，烘干后将包壳管无尘存放；
S2.涂覆粘结层：采用磁控溅射、多弧离子镀、热喷涂、冷喷涂、3D激光涂覆、原子层沉积技术在锆合金包壳管表面涂覆粘结层；
S3.涂覆耐腐蚀层：采用磁控溅射、多弧离子镀、热喷涂、冷喷涂、3D激光涂覆、原子层沉积技术在粘结层表面涂覆耐腐蚀层；
S4.涂覆耐磨层：采用磁控溅射、多弧离子镀、原子层沉积在耐腐蚀层表面涂覆耐磨层。
与现有技术相比，本发明的有益效果是：本发明外部中的耐磨层可采用多层膜层，多层膜层可采用CrN、Cr3C2、ZrO2等材料实现表面硬度的提升，从而提高锆合金包壳管的耐磨性能，并采用金属Cr、Nb、Zr等缓冲热膨胀系数差异，减少应力集中。该材料事故工况下，高温水蒸气腐蚀可在最初防护阶段可形成Cr2O3致密氧化膜，减少高温蒸汽环境的影响。如若高温蒸汽突破了最外防护层，到达耐腐蚀层后利用涂层优异的抗高温水蒸气腐蚀性能继续抵御蒸汽腐蚀，延长锆合金包壳管的服役时间。在内部粘结层可利用与锆合金匹配的热膨胀系数，减少热应力集中，避免在升降温过程中生成裂纹或涂层脱落，从而具有优异的耐磨损性能和优异的抗高温水蒸汽腐蚀性能。
附图说明
图1为现役核电站的棒状核燃料元件；
图2为本发明耐磨层为单一膜层时的横截面结构示意图；
图3为本发明耐磨层为多层膜层时的横截面结构示意图。
图中：1、锆合金包壳管基体；2、粘结层；3、耐腐蚀层；4、耐磨层；5、陶瓷相层；6、金属相层。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
如图2-3；本发明提供一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层，包括锆合金包壳管基体1、粘结层2、耐腐蚀层3和耐磨层4，锆合金包壳管基体1表面涂覆有粘结层2，粘结层2表面涂覆有耐腐蚀层3，耐腐蚀层3表面涂覆有耐磨层4；粘结层2包括金属材料和陶瓷材料，其中金属材料包括Zr、Cr、Nb和Ni，陶瓷材料包括ZrO2、ZrN、CrN和Cr3C2；
耐腐蚀层3的成分包括Cr、FeCrAl、FeCrSi、ZrAlCrSi、ZrCr2、ZrAl3、ZrSi2、ZrO2、ZrN、ZrC、CrSi2、CrO2、CrN、Cr3C2，其中Cr、Al、Si、Ti为必须元素，其在高温有氧环境初期可分别生成Cr2O3、Al2O3、SiO2、TiO2等致密氧化膜层，阻碍氧向基体扩散，实现腐蚀防护功能；
其中，耐磨层4可选为单一膜层或多层膜层，若为单一膜层，则为图2所示结构，此时耐磨层4的成分中需含有O、C、N其中的一种元素，并含有Cr、Al、Si、Ti、Zr一种或一种以上元素，包括但不限于以下物质：ZrSi2、ZrO2、ZrN、ZrC、CrSi2、CrO2、CrN、Cr3C2等；若为多层膜层，则为图3所示结构，此时耐磨层4包括陶瓷相层5和金属相层6，且陶瓷相层5与金属相层6交叠往复，其中陶瓷相的组成需含有O、C、N一种元素，并含有Cr、Al、Si、Ti、Zr一种和一种以上元素，金属相的组成由Cr、Fe、Al、Zr、Nb、Ni元素中的一种或多种组成；其中陶瓷相层5和金属相层6厚度为10-500nm；该结构可以利用陶瓷相的高硬度、耐磨损的特性提升锆合金包壳管耐磨性能，并利用金属相层6优异的延展性缓冲热膨胀系数的差异，并减少应力集中，降低薄膜开裂脱落的风险。
进一步的，所述粘结层2厚度为0.1-10μm。
进一步的，所述耐腐蚀层3厚度为1-30μm。
进一步的，所述耐磨层4厚度为0.5-10μm。
本发明还提供一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层的制备方法，包括以下步骤：
S1.预处理：利用酒精、丙酮等清洗剂对锆合金包壳管进行清洗，去除表面污垢，进行喷沙处理，烘干后将包壳管无尘存放；
S2.涂覆粘结层2：采用磁控溅射、多弧离子镀、热喷涂、冷喷涂、3D激光涂覆、原子层沉积技术在锆合金包壳管表面涂覆粘结层2；
S3.涂覆耐腐蚀层3：采用磁控溅射、多弧离子镀、热喷涂、冷喷涂、3D激光涂覆、原子层沉积技术在粘结层2表面涂覆耐腐蚀层3；
S4.涂覆耐磨层4：采用磁控溅射、多弧离子镀、原子层沉积在耐腐蚀层3表面涂覆耐磨层4。
实施例1：
在锆合金包壳管表面制备金属Nb为粘结层2，该层厚度为2μm；制备Cr为耐腐蚀层3，该层厚度12μm；制备Cr3C2为耐磨层4，该层厚度为3μm。
本发明实施例中的特点是：1、利用Nb、Zr、Cr三者较为接近的热膨胀系数，从而采用Nb为粘结层2，缓冲热膨胀系数的差异，减少涂层开裂与剥落的风险，增强锆合金基体与功能涂层间的结合性能；2、采用Cr为耐腐蚀层3，在表面可生成致密Cr2O3膜，减少高温水蒸气向内部渗透。3、采用Cr3C2为耐磨层4，利用Cr3C2优异的耐磨性能增强锆合金的功能，并可在事故工况初期形成致密Cr2O3膜，增强抗腐蚀性能。
因此，通过本发明的涂层可显著提高锆合金包壳管的耐磨性能和抗高温水蒸气腐蚀性能。
实施例2：
在锆合金包壳管表面制备金属Nb为粘结层2，该层厚度为1μm；制备Cr为耐腐蚀层3，该层厚度10μm；制备Cr3C2/Cr耐磨层4，该层厚度为2μm，其中Cr3C2相层每层50nm，Cr相层每层50nm。
本发明实施例中的特点是：1、利用Nb、Zr、Cr三者较为接近的热膨胀系数，从而采用Nb为粘结层2，缓冲热膨胀系数的差异，减少涂层开裂与剥落的风险，增强锆合金基体与功能涂层间的结合性能；2、采用Cr为耐腐蚀层3，在表面可生成致密Cr2O3膜，减少高温水蒸气向内部渗透。3、Cr3C2/Cr耐磨多层膜中Cr3C2相层与Cr相层每层均为50nm，该结构利用Cr3C2优异的耐磨性能增强锆合金的功能，并将Cr相层制备为致密等轴晶层，减少腐蚀过程中氧通道，增强抗事故能力。
因此，通过本发明的涂层可显著提高锆合金包壳管的耐磨性能和抗高温水蒸气腐蚀性能。
实施例3：
在锆合金包壳管表面制备ZrN为粘结层2，该层厚度为2μm；制备CrN为耐腐蚀层3，厚度为10μm；制备CrN/FeCrAl为耐磨层4，该层厚度为1μm，其中CrN相层每层40nm，FeCrAl相层每层60nm。
本发明实施例中的特点是：1、采用ZrN为粘结层2，该层与锆合金有较好的化学相容性，并可以减缓锆合金与CrN间的热膨胀系数差异，增强涂层结合性能，减少涂层开裂与剥落的风险；2、采用CrN为耐腐蚀层3，利用CrN在高温水蒸气腐蚀环境中生成的致密Cr2O3膜，减少高温水蒸气向内部渗透；3、采用CrN/FeCrAl多层膜为耐磨层4，其中CrN相每层40nm，FeCrAl相每层60nm，该结构可形成致密CrN/FeCrAl层达100层，使表面兼具耐磨与耐腐蚀性能。
因此，通过本发明的涂层可显著提高锆合金包壳管的耐磨性能和抗高温水蒸气腐蚀性能。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (9)
1.一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层，其特征在于：包括锆合金包壳管基体(1)、粘结层(2)、耐腐蚀层(3)和耐磨层(4)，所述锆合金包壳管基体(1)表面涂覆有粘结层(2)，所述粘结层(2)表面涂覆有耐腐蚀层(3)，所述耐腐蚀层(3)表面涂覆有耐磨层(4)。
2.根据权利要求1所述的一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层，其特征在于：所述粘结层(2)包括金属材料和陶瓷材料，其中金属材料包括Zr、Cr、Nb和Ni，陶瓷材料包括ZrO2、ZrN、CrN和Cr3C2。
3.根据权利要求1所述的一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层，其特征在于：所述耐腐蚀层(3)的成分包括Cr、FeCrAl、FeCrSi、ZrAlCrSi、ZrCr2、ZrAl3、ZrSi2、ZrO2、ZrN、ZrC、CrSi2、CrO2、CrN、Cr3C2，其中Cr、Al、Si、Ti为必须元素。
4.根据权利要求1所述的一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层，其特征在于：所述耐磨层(4)为单一膜层，耐磨层(4)的成分中需含有O、C、N其中的一种元素，并含有Cr、Al、Si、Ti、Zr一种或一种以上元素，包括但不限于以下物质：ZrSi2、ZrO2、ZrN、ZrC、CrSi2、CrO2、CrN、Cr3C2等。
5.根据权利要求1所述的一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层，其特征在于：所述耐磨层(4)为多层膜层，包括陶瓷相层(5)和金属相层(6)，且陶瓷相层(5)与金属相层(6)交叠往复，其中陶瓷相的组成需含有O、C、N一种元素，并含有Cr、Al、Si、Ti、Zr一种和一种以上元素，金属相的组成由Cr、Fe、Al、Zr、Nb、Ni元素中的一种或多种组成；其中陶瓷相层(5)和金属相层(6)厚度为10-500nm。
6.根据权利要求1所述的一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层，其特征在于：所述粘结层(2)厚度为0.1-10μm。
7.根据权利要求1所述的一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层，其特征在于：所述耐腐蚀层(3)厚度为1-30μm。
8.根据权利要求1所述的一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层，其特征在于：所述耐磨层(4)厚度为0.5-10μm。
9.根据权利要求1-8任一所述的一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层的制备方法，其特征在于，包括以下步骤：
S1.预处理：利用酒精、丙酮等清洗剂对锆合金包壳管进行清洗，去除表面污垢，进行喷沙处理，烘干后将包壳管无尘存放；
S2.涂覆粘结层(2)：采用磁控溅射、多弧离子镀、热喷涂、冷喷涂、3D激光涂覆、原子层沉积技术在锆合金包壳管表面涂覆粘结层(2)；
S3.涂覆耐腐蚀层(3)：采用磁控溅射、多弧离子镀、热喷涂、冷喷涂、3D激光涂覆、原子层沉积技术在粘结层(2)表面涂覆耐腐蚀层(3)；
S4.涂覆耐磨层(4)：采用磁控溅射、多弧离子镀、原子层沉积在耐腐蚀层(3)表面涂覆耐磨层(4)。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111313422.0A CN114015959A (zh) | 2021-11-08 | 2021-11-08 | 一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111313422.0A CN114015959A (zh) | 2021-11-08 | 2021-11-08 | 一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114015959A true CN114015959A (zh) | 2022-02-08 |
Family
ID=80062018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111313422.0A Pending CN114015959A (zh) | 2021-11-08 | 2021-11-08 | 一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114015959A (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114951691A (zh) * | 2022-03-28 | 2022-08-30 | 上海大学 | 一种核燃料包壳用ZrC颗粒增强FeCrAl金属基复合材料的激光增材制造方法 |
| CN117174354A (zh) * | 2023-11-02 | 2023-12-05 | 上海核工程研究设计院股份有限公司 | 核反应堆燃料元件用复合包壳管材及其制备方法、燃料棒 |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130344348A1 (en) * | 2012-06-25 | 2013-12-26 | Korea Hydro And Nuclear Power Co., Ltd. | Zirconium alloy with coating layer containing mixed layer formed on surface, and preparation method thereof |
| CN106128532A (zh) * | 2016-06-12 | 2016-11-16 | 上海核工程研究设计院 | 一种核燃料元件包壳锆合金钛合金复合管及其制备方法 |
| US20180025794A1 (en) * | 2016-07-22 | 2018-01-25 | Westinghouse Electric Company Llc | Spray methods for coating nuclear fuel rods to add corrosion resistant barrier |
| CN108624882A (zh) * | 2018-05-18 | 2018-10-09 | 天津师范大学 | 锆合金表面氧化锆/氮化铬复合膜及其制备方法与应用 |
| US20180294062A1 (en) * | 2015-10-06 | 2018-10-11 | The Penn State Research Foundation | Ceramic coating for corrosion resistance of nuclear fuel cladding |
| CN110791730A (zh) * | 2019-12-07 | 2020-02-14 | 西北有色金属研究院 | 一种核燃料用锆合金包壳表面复合涂层的制备方法 |
| CN111139434A (zh) * | 2020-01-08 | 2020-05-12 | 西安交通大学 | 一种锆合金表面用事故容错核燃料包壳涂层 |
| CN111172503A (zh) * | 2019-12-26 | 2020-05-19 | 西安交通大学 | 一种锆合金包壳表面多层复合涂层及其制备方法 |
| CN112795875A (zh) * | 2020-12-15 | 2021-05-14 | 西安稀有金属材料研究院有限公司 | 核燃料锆合金包壳元件 |
| CN113293374A (zh) * | 2021-05-07 | 2021-08-24 | 上海核工程研究设计院有限公司 | 一种用于锆合金包壳管外表面的涂层及制作方法 |
| CN114438493A (zh) * | 2021-11-08 | 2022-05-06 | 上海核工程研究设计院有限公司 | 一种核电厂锆合金包壳管表面用抗高温水蒸气腐蚀涂层及其制备方法 |
| CN217556266U (zh) * | 2021-11-08 | 2022-10-11 | 上海核工程研究设计院有限公司 | 一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层 |
-
2021
- 2021-11-08 CN CN202111313422.0A patent/CN114015959A/zh active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130344348A1 (en) * | 2012-06-25 | 2013-12-26 | Korea Hydro And Nuclear Power Co., Ltd. | Zirconium alloy with coating layer containing mixed layer formed on surface, and preparation method thereof |
| US20180294062A1 (en) * | 2015-10-06 | 2018-10-11 | The Penn State Research Foundation | Ceramic coating for corrosion resistance of nuclear fuel cladding |
| CN106128532A (zh) * | 2016-06-12 | 2016-11-16 | 上海核工程研究设计院 | 一种核燃料元件包壳锆合金钛合金复合管及其制备方法 |
| US20180025794A1 (en) * | 2016-07-22 | 2018-01-25 | Westinghouse Electric Company Llc | Spray methods for coating nuclear fuel rods to add corrosion resistant barrier |
| CN108624882A (zh) * | 2018-05-18 | 2018-10-09 | 天津师范大学 | 锆合金表面氧化锆/氮化铬复合膜及其制备方法与应用 |
| CN110791730A (zh) * | 2019-12-07 | 2020-02-14 | 西北有色金属研究院 | 一种核燃料用锆合金包壳表面复合涂层的制备方法 |
| CN111172503A (zh) * | 2019-12-26 | 2020-05-19 | 西安交通大学 | 一种锆合金包壳表面多层复合涂层及其制备方法 |
| CN111139434A (zh) * | 2020-01-08 | 2020-05-12 | 西安交通大学 | 一种锆合金表面用事故容错核燃料包壳涂层 |
| CN112795875A (zh) * | 2020-12-15 | 2021-05-14 | 西安稀有金属材料研究院有限公司 | 核燃料锆合金包壳元件 |
| CN113293374A (zh) * | 2021-05-07 | 2021-08-24 | 上海核工程研究设计院有限公司 | 一种用于锆合金包壳管外表面的涂层及制作方法 |
| CN114438493A (zh) * | 2021-11-08 | 2022-05-06 | 上海核工程研究设计院有限公司 | 一种核电厂锆合金包壳管表面用抗高温水蒸气腐蚀涂层及其制备方法 |
| CN217556266U (zh) * | 2021-11-08 | 2022-10-11 | 上海核工程研究设计院有限公司 | 一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114951691A (zh) * | 2022-03-28 | 2022-08-30 | 上海大学 | 一种核燃料包壳用ZrC颗粒增强FeCrAl金属基复合材料的激光增材制造方法 |
| CN117174354A (zh) * | 2023-11-02 | 2023-12-05 | 上海核工程研究设计院股份有限公司 | 核反应堆燃料元件用复合包壳管材及其制备方法、燃料棒 |
| CN117174354B (zh) * | 2023-11-02 | 2024-02-02 | 上海核工程研究设计院股份有限公司 | 核反应堆燃料元件用复合包壳管材及其制备方法、燃料棒 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Protective coatings on zirconium-based alloys as accident-tolerant fuel (ATF) claddings | |
| CN114015959A (zh) | 一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层及其制备方法 | |
| CN111172503B (zh) | 一种锆合金包壳表面多层复合涂层及其制备方法 | |
| EP3004420B1 (en) | A KINETICALLY APPLIED GRADATED Zr-Al-C CERAMIC OR Ti-Al-C CERAMIC OR AMORPHOUS OR SEMI-AMORPHOUS STAINLESS STEEL WITH NUCLEAR GRADE ZIRCONIUM ALLOY METAL STRUCTURE | |
| WO2019052315A1 (zh) | 燃料包壳及燃料组件 | |
| EP3884503B1 (en) | Coatings and surface modifications to mitigate sic cladding during operation in light water reactors | |
| CN111139434A (zh) | 一种锆合金表面用事故容错核燃料包壳涂层 | |
| CN113388811B (zh) | 一种事故容错燃料包壳用双层Cr/Cr2AlC涂层及其制备方法 | |
| CN217556266U (zh) | 一种核电厂锆合金包壳管用耐磨损抗氧化复合涂层 | |
| CN109355611A (zh) | 一种用于锆合金包壳的复合陶瓷涂层制备方法 | |
| KR20130125985A (ko) | 초고온 내산화성 증진을 위한 지르코늄 합금 및 이의 제조방법 | |
| JP2022519444A (ja) | 超合金及びその製造方法 | |
| CN217948265U (zh) | 一种核电厂锆合金包壳管表面用抗高温水蒸气腐蚀涂层 | |
| CN109811322B (zh) | 一种具有空间环境适应性的超润滑固体薄膜 | |
| CN114438493A (zh) | 一种核电厂锆合金包壳管表面用抗高温水蒸气腐蚀涂层及其制备方法 | |
| FR2946663A1 (fr) | Revetement thermique, piece thermomecanique comportant un tel revetement thermique, turbomachine, moteur d'aeronef, d'astronef ou de fusee comportant une telle piece thermomecanique | |
| CN108588532B (zh) | 多元合金涂层、锆合金包壳及燃料组件 | |
| Tang et al. | Metallic and ceramic coatings for enhanced accident tolerant fuel cladding | |
| FR2974581A1 (fr) | Piece comportant un revetement sur un substrat metallique en superalliage, le revetement comprenant une sous-couche metallique | |
| WO2020093246A1 (zh) | 核燃料组件的管材及燃料包壳 | |
| Sagiroun et al. | Zirconium-based cladding coating technique for oxidation, corrosion and embrittlement reduction at high-temperature: an overview | |
| Guan et al. | Effects of the different interlayer deposition processes on the microstructure of Cr/TiN coating | |
| JP2001295075A (ja) | 金属基材への耐食セラミックコ−ティング部材、その製造方法、およびその部材から構成される部品 | |
| US20220384062A1 (en) | Cathodic arc applied randomized grain structured coatings on zirconium alloy nuclear fuel cladding | |
| CN115341176B (zh) | 应用于热障涂层的多层粘结层材料及其制备方法 |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: No. 29 Hong Cao Road, Xuhui District, Shanghai Applicant after: Shanghai Nuclear Engineering Research and Design Institute Co.,Ltd. Address before: No. 29 Hong Cao Road, Xuhui District, Shanghai Applicant before: SHANGHAI NUCLEAR ENGINEERING RESEARCH & DESIGN INSTITUTE Co.,Ltd. |
|
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220208 |