CN116516291A - Cr-Si coating on surface of zirconium alloy for nuclear and preparation method thereof - Google Patents
Cr-Si coating on surface of zirconium alloy for nuclear and preparation method thereof Download PDFInfo
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- CN116516291A CN116516291A CN202310520282.7A CN202310520282A CN116516291A CN 116516291 A CN116516291 A CN 116516291A CN 202310520282 A CN202310520282 A CN 202310520282A CN 116516291 A CN116516291 A CN 116516291A
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- 238000000576 coating method Methods 0.000 title claims abstract description 117
- 239000011248 coating agent Substances 0.000 title claims abstract description 109
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 44
- 229910019819 Cr—Si Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 238000004544 sputter deposition Methods 0.000 claims abstract description 19
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims description 41
- 238000000151 deposition Methods 0.000 claims description 37
- 230000008021 deposition Effects 0.000 claims description 37
- 229910045601 alloy Inorganic materials 0.000 claims description 35
- 239000000956 alloy Substances 0.000 claims description 35
- 244000137852 Petrea volubilis Species 0.000 claims description 28
- 238000005498 polishing Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 229910003460 diamond Inorganic materials 0.000 claims description 7
- 239000010432 diamond Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 230000002441 reversible effect Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 abstract description 28
- 238000007254 oxidation reaction Methods 0.000 abstract description 28
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 22
- 238000005253 cladding Methods 0.000 description 8
- 230000004584 weight gain Effects 0.000 description 6
- 235000019786 weight gain Nutrition 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 3
- 229910019974 CrSi Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000003758 nuclear fuel Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910007735 Zr—Si Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 description 2
- 229910019580 Cr Zr Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
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
- 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
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
-
- 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
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
A Cr-Si coating on the surface of a zirconium alloy for a core is prepared by magnetron sputtering a Cr target and a Si target, wherein the content of Si in the coating is controlled to be 7.5-22.0 at%, the power drives of the Cr target and the Si target are respectively a direct current power supply and a radio frequency power supply, the sputtering power of the Cr target is 300W, and the power of the Si target is 100-300W. The Cr-Si coating prepared on the surface of the zirconium alloy substrate has excellent high-temperature oxidation resistance, and Cr is formed at the interface of the substrate and the coating in the oxidation process 2 O 3 /SiO 2 Double oxide layers, effectively delay Cr 2 O 3 Is oxidized in the water vapor environment at 1200 ℃ to reduce the oxidation weight to 1.4mg/cm 2 Meanwhile, through doping of Si, the mechanical property of the coating is effectively improved, the hardness reaches 14.64GPa, and the wear resistance and antifriction performance of the coating are enhanced。
Description
Technical Field
The invention relates to the technical field of preparation of alloy protective coatings, in particular to a Cr-Si coating on the surface of a zirconium alloy for a core and a preparation method thereof.
Background
The nuclear fuel cladding is the first safety barrier of the nuclear power plant. Zirconium alloy is the preferred material for nuclear fuel cladding due to its extremely low thermal neutron absorption cross section, good mechanical properties and corrosion resistance. However, in the event of loss of coolant (LOCA), zirconium alloy reacts with high temperature steam violently with zirconium-water, resulting in core fusion, eventually causing hydrogen explosion and nuclear leakage, with a great potential safety hazard. Therefore, it is critical to improve the safety of nuclear reactors by developing accident fault tolerant fuels (ATFs) to slow down or prevent the zirconium-water reaction.
The surface modification of the zirconium alloy can not only effectively improve the high-temperature oxidation resistance of the nuclear fuel cladding, but also keep the existing nuclear system and cladding tube production process, and is a relatively economical and efficient solution at present. The specific implementation method is that a coating containing Si, cr and Al elements is prepared on the surface of the zirconium alloy, and the purpose of improving the oxidation resistance of the zirconium alloy cladding is achieved by generating corresponding oxides in a high-temperature vapor environment to prevent or slow down the diffusion of O to a matrix.
Currently, studies on fault tolerant coatings have been mainly conducted around ceramic coatings (MAX-phase ceramic coatings, nitride coatings, carbide coatings, etc.) and metal coatings (FeCrAl coatings, cr coatings, etc.). Wherein, the metallic Cr coating has higher heat conduction coefficient (94W/mK), excellent mechanical property and corrosion resistance, and good compatibility with the production process of the zirconium alloy cladding tube, and Cr can be generated in the use process 2 O 3 Oxide film, reducing the oxidation rate of zirconium alloy, is considered to be the best choice for improving the fault tolerance of zirconium alloy cladding in a short period of time. However, cr 2 O 3 The highest withstand temperature in the high temperature vapor environment is 1042 ℃, when the temperature is too high, cr 2 O 3 Can form volatile CrO 2 (OH) 2 Or Cr (OH) 3 And fails. In addition, the Zr matrix and the Cr coating mutually diffuse, so that eutectic reaction occurs at the coating interface in the environment above 1330 ℃, the membrane-based interface is unstable, and the protective performance of the Cr coating is reduced.
Disclosure of Invention
The invention aims to provide a Cr-Si coating on the surface of a zirconium alloy for nuclear use.
Another object of the present invention is to provide a method for preparing a Cr-Si-based coating on the surface of the zirconium alloy for nuclear use, wherein the prepared Cr-Si-based coating effectively retards Cr by doping Si atoms into the Cr coating 2 O 3 The failure of the oxide layer effectively prevents the interdiffusion of the interface Zr and Cr, and effectively improves the mechanical property, the wear resistance and the antifriction property of the coating.
The invention aims at realizing the following technical scheme:
the invention has the following technical effects:
a Cr-Si coating on the surface of a zirconium alloy for nuclear use, which is characterized in that: the Cr-Si coating is prepared by magnetron sputtering a Cr target and a Si target, wherein the content of Si in the coating is controlled to be 7.5-22.0 at%, the power supplies of the Cr target and the Si target are respectively a direct current power supply and a radio frequency power supply, the sputtering power of the Cr target is 300W, and the power of the Si target is 100-300W.
Further, in the magnetron sputtering process, the vacuum degree is 8×10 -4 Pa, the deposition temperature is 380-420 ℃, the substrate bias voltage is-40 to-60V, the deposition air pressure is 0.3-0.5 Pa, and the deposition time is 4-6 h.
The preparation reverse of the Cr-Si coating on the surface of the zirconium alloy for the nuclear is characterized in that: the Cr-Si coating with Si content of 7.5-22.0 at.% is formed on the surface of the zirconium alloy substrate by magnetron sputtering with a Cr target and a Si target.
Further, the power drives of the Cr target and the Si target are respectively a direct current power supply and a radio frequency power supply, wherein the sputtering power of the Cr target is 300W, and the power of the Si target is 100-300W.
Further, the vacuum degree of the magnetron sputtering is 8×10 -4 Pa, the deposition temperature is 380-420 ℃, the substrate bias voltage is-40 to-60V, the deposition air pressure is 0.3-0.5 Pa, and the deposition time is 4-6 h.
Preferably, the deposition temperature is 400 ℃, the substrate bias is-50V, the deposition air pressure is 0.4Pa, and the deposition time period is 5 hours.
The preparation method of the Cr-Si coating on the surface of the zirconium alloy for the core is characterized by comprising the following steps of:
(1) pretreatment of a zirconium alloy matrix: sequentially polishing the surface of a Zry-4 alloy matrix by using 100# SiC sand paper, 400# SiC sand paper, 1000# SiC sand paper and 2000# SiC sand paper, sequentially polishing the polished Zry-4 alloy matrix by using diamond polishing liquid with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the polished Zry-4 alloy matrix by using acetone and absolute ethyl alcohol for 10min, and drying the polished Zry-4 alloy matrix for later use;
(2) preparing Cr-Si series coating: preparing a coating by magnetron sputtering, driving a Cr target and a Si target by a Direct Current (DC) power supply and a Radio Frequency (RF) power supply respectively, and performing vacuum of 8 multiplied by 10 -4 Pa, the deposition temperature is 380-420 ℃, the substrate bias voltage is-40 to-60V, the deposition air pressure is 0.3-0.5 Pa, and the deposition time is 4-6 h; wherein the sputtering power of the Cr target is fixed to 300W, the sputtering power of the Si target is 100-300W, and the Si content of the coating is controlled between 7.5 and 22.0at percent.
The beneficial effects are that:
the Cr-Si coating prepared on the surface of the zirconium alloy substrate has excellent high-temperature oxidation resistance, and Cr is formed at the interface of the substrate and the coating in the higher-temperature steam oxidation process 2 O 3 /SiO 2 Double oxide layers, effectively delay Cr 2 O 3 Is oxidized in the water vapor environment at 1200 ℃ to reduce the oxidation weight to 1.4mg/cm 2 Meanwhile, through doping of Si, the mechanical property of the coating is effectively improved, the hardness reaches 14.64GPa, and the wear resistance and antifriction performance of the coating are enhanced.
Drawings
Fig. 1: the surface topography of the as-deposited CrSi-100W coating prepared by the invention is analyzed for element content.
Fig. 2: the cross-sectional morphology diagram of the as-deposited CrSi-100W coating prepared by the invention.
Fig. 3: the surface topography of the as-deposited CrSi-200W coating prepared by the invention is analyzed for element content.
Fig. 4: the cross-sectional morphology diagram of the as-deposited CrSi-200W coating prepared by the invention.
Fig. 5: the surface topography and element content analysis of the as-deposited CrSi-300W coating prepared by the invention.
Fig. 6: the cross-sectional morphology diagram of the as-deposited CrSi-300W coating prepared by the invention.
Fig. 7: high temperature oxidation weight gain comparison graph for each coating.
Fig. 8: a double oxide layer structure formed after oxidation of the coating, wherein (a) is a cross-sectional view; (b) EDS face scanning; (c) a partial enlarged view; (d) a high resolution map and a SAED map of region (d); (e) high resolution map and SAED map of region (e).
Fig. 9: cross-sectional morphology and element distribution of CrSi-300W coating after oxidation in 1300 ℃/30min water vapor.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing disclosure.
Example 1
The preparation method of the Cr-Si coating on the surface of the zirconium alloy for the core comprises the following steps:
(1) pretreatment of a zirconium alloy matrix: sequentially polishing the surface of a Zry-4 alloy matrix by using 100# SiC sand paper, 400# SiC sand paper, 1000# SiC sand paper and 2000# SiC sand paper, sequentially polishing the polished Zry-4 alloy matrix by using diamond polishing liquid with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the polished Zry-4 alloy matrix by using acetone and absolute ethyl alcohol for 10min, and drying the polished Zry-4 alloy matrix for later use;
(2) preparing Cr-Si series coating: preparing a coating by magnetron sputtering, driving a Cr target and a Si target by a Direct Current (DC) power supply and a Radio Frequency (RF) power supply respectively, and performing vacuum of 8 multiplied by 10 -4 Pa, the deposition temperature is 400 ℃, the substrate bias voltage is-50V, the deposition air pressure is 0.4Pa, and the deposition time is 5h; wherein, the sputtering power of the Cr target is fixed to 300W, the sputtering power of the Si target is 100W, and the Si content of the coating is 7.8at percent, which is expressed as CrSi-100W.
Fig. 1 shows the surface morphology and element content of the as-deposited CrSi-100W coating, and it can be seen that the coating has a dense surface structure, no defects such as cracks and holes, and the Si content in the coating is 7.8 at%. FIG. 2 is a cross-sectional morphology of a CrSi-200W coating, which bonds well with a Zry-4 alloy substrate, and has a compact and uniform coating structure and a thickness of 11.4 μm.
Example 2
The preparation method of the Cr-Si coating on the surface of the zirconium alloy for the core comprises the following steps:
(1) pretreatment of a zirconium alloy matrix: sequentially polishing the surface of a Zry-4 alloy matrix by using 100# SiC sand paper, 400# SiC sand paper, 1000# SiC sand paper and 2000# SiC sand paper, sequentially polishing the polished Zry-4 alloy matrix by using diamond polishing liquid with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the polished Zry-4 alloy matrix by using acetone and absolute ethyl alcohol for 10min, and drying the polished Zry-4 alloy matrix for later use;
(2) preparing Cr-Si series coating: preparing a coating by magnetron sputtering, driving a Cr target and a Si target by a Direct Current (DC) power supply and a Radio Frequency (RF) power supply respectively, and performing vacuum of 8 multiplied by 10 -4 Pa, the deposition temperature is 400 ℃, the substrate bias voltage is-50V, the deposition air pressure is 0.4Pa, and the deposition time is 5h; wherein the sputtering power of the Cr target is fixed to 300W, the sputtering power of the Si target is 200W, and the Si content of the coating is controlled to 14.3 at%, which is denoted as CrSi-200W.
Fig. 3 shows the surface morphology and element content of the as-deposited CrSi-200W coating, and it can be seen that the coating has a dense surface structure, no defects such as cracks and holes, and the Si content in the coating is 14.3 at%. FIG. 4 is a cross-sectional morphology of a CrSi-200W coating, showing that the coating bonds well with a Zry-4 alloy substrate, the coating structure is compact and uniform, and the thickness is 10.7 μm.
Example 3
The preparation method of the Cr-Si coating on the surface of the zirconium alloy for the core comprises the following steps:
(1) pretreatment of a zirconium alloy matrix: sequentially polishing the surface of a Zry-4 alloy matrix by using 100# SiC sand paper, 400# SiC sand paper, 1000# SiC sand paper and 2000# SiC sand paper, sequentially polishing the polished Zry-4 alloy matrix by using diamond polishing liquid with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the polished Zry-4 alloy matrix by using acetone and absolute ethyl alcohol for 10min, and drying the polished Zry-4 alloy matrix for later use;
(2) preparing Cr-Si series coating: preparing a coating by magnetron sputtering, driving a Cr target and a Si target by a Direct Current (DC) power supply and a Radio Frequency (RF) power supply respectively, and performing vacuum of 8 multiplied by 10 -4 Pa, the deposition temperature is 400 ℃, the substrate bias voltage is-50V, the deposition air pressure is 0.4Pa, and the deposition time is 5h; wherein the sputtering power of the Cr target is fixed to 300W, the sputtering power of the Si target is 300W, and the Si content of the coating is controlled to 21.7 at%, which is expressed as CrSi-300W.
Fig. 5 shows the surface morphology and element content of the as-deposited CrSi-300W coating, and it can be seen that the coating has a dense surface structure, no defects such as cracks and holes, and the Si content in the coating is 21.7 at%. FIG. 6 is a cross-sectional morphology of a CrSi-300W coating, showing that the coating bonds well with a Zry-4 alloy substrate, the coating structure is compact and uniform, and the thickness is 12.8 μm.
Performance test:
(1) Mechanical properties
Generally, the higher the hardness of the material, the better its antifriction and wear-resistant properties, which is beneficial for improving the tribological properties of the zirconium cladding in normal operating conditions. The hardness and elastic modulus of the coating were effectively improved by doping Si atoms in the Cr coating, and the results of the hardness test of the pure Cr coating on the surface of the zirconium alloy and the Cr-Si-based coatings prepared in examples 1 to 3 are shown in table 1.
Table 1: microhardness of as-deposited coating
| Coating layer | Cr | CrSi-100W | CrSi-200W | CrSi-300W |
| Si content (at.) | 0 | 7.8 | 14.3 | 21.7 |
| Hardness (GPa) | 3.11 | 5.73 | 8.62 | 14.64 |
As can be seen from Table 1, the Cr-Si based coating enhances the hardness of the pure Cr coating. Meanwhile, the hardness of the Cr-Si coating increases as the Si content increases.
(2) High temperature oxidation resistance
Through testing Zry-4 alloy matrix and magnetron sputtering deposition of Cr-Si series coatings with different Si doping amounts on the surface of Zry-4 alloy matrix, oxidation weight gain after treatment for 30min under the high-temperature steam environment of 1200 ℃ is 90% at 50 ℃, high-temperature oxidation resistance of each coating is detected, and the result is shown in figure 7, it can be seen that after steam oxidation for 30min at 1200 ℃ of zirconium alloy without any coating protection, the oxidation weight gain reaches 29.9mg/cm 2 The oxidation weight gain of the Cr-Si based coating (CrSi-100W) prepared in example 1 was as low as 1.4mg/cm 2 And with the increase of Si content, the oxidation weight gain is gradually increased, and the CrSi-200W and the CrSi-300W are respectively 2.2mg/cm 2 And 4.6mg/cm 2 The change in the oxidation weight gain of each coating is not obvious with the increase in the subsequent oxidation time.
After oxidation test, the surface of the CrSi-100W, crSi-200W and CrSi-300W coating forms oxide layers, in particular Cr 2 O 3 /SiO 2 Double oxide layer structure, cr 2 O 3 /SiO 2 Double oxide layer delayed Cr 2 O 3 As can be seen from the structural analysis of CrSi-200W after oxidation, as shown in FIG. 8, wherein (a) is a cross-sectional view of the interface, it is evident that Cr is formed during oxidation 2 O 3 At the same time, siO is also generated 2 Cr is formed 2 O 3 /SiO 2 Double oxide layer structure. (b) is a corresponding EDS face scan. (c) Is a partial enlarged view, and (d) is a region (d) (Cr 2 O 3 ) (e) is a region (e) (SiO) 2 ) Is a high resolution map of (1) and a SAED map. The elemental analysis corresponding to the region (d) and the region (e) is shown in table 2.
Table 2: elemental analysis for region (d) and region (e)
| at.％ | O | Si | Cr | Zr |
| Zone (d) | 70.3 | 0.2 | 29.2 | 0.3 |
| Area (e) | 69.4 | 30.0 | 0.4 | 0.2 |
As can be seen from the above table, the elements in the region (d) are mainly composed of O and Cr, and the elements in the region (e) are mainly composed of O and Si, and the accuracy of the specific gravity of the elemental analysis is limited due to the test accuracy, but the overall analysis in conjunction with FIG. 8 shows that the main components of the regions (d) and (d) are Cr 2 O 3 And SiO 2 While trace Zr content proves that slight diffusion exists, which is favorable for improving the bonding force between the coating and the matrix. Whereas SiO of amorphous structure 2 Is reduced in CrSi residual layer and Cr 2 O 3 The difference in thermal expansion coefficient between the oxide layers reduces the generation of internal stress, resulting in enhanced coating stability.
(3) Interdiffusion Property of zirconium alloy and Cr-Si based coating
After the CrSi-300W coating prepared in example 3 was subjected to oxidation treatment in 1300 ℃/30min steam (humidity at 50 ℃) and then the cross-sectional morphology and element distribution were examined, as shown in fig. 5, a continuous Zr-Si interdiffusion layer (Diffusion layer) was formed in situ between the Cr-Si coating after oxidation treatment and the zirconium alloy interface, the surface was a CrSi Residual layer (Residual layer), the outermost surface was an Oxide layer, and the thickness of each layer was as shown in table 3.
Table 3:1300 ℃/30min thickness (μm) of each layer after oxidation
| CrSi-100W | CrSi-200W | CrSi-300W | |
| Oxidelayer | 1.45 | 3.13 | 3.7 |
| Residuallayer | 6.9 | 5.51 | 5.84 |
| Cr-Si | 5.6 | 5.8 | 8.3 |
Meanwhile, the Cr-Si coating has no Zr, and the zirconium alloy matrix has no Cr. This demonstrates that the continuous zr—si layer has a significant effect on hindering Zr and Cr interdiffusion.
In conclusion, the Cr-Si coating prepared on the surface of the Zry-4 alloy substrate by the method forms four layers of structures in the oxidation process, and Cr is sequentially arranged from outside to inside 2 O 3 Oxide layer, siO 2 An oxide layer CrSi residual layer and a Zr-Si inter-diffusion layer.
Example 4
The preparation method of the Cr-Si coating on the surface of the zirconium alloy for the core comprises the following steps:
(1) pretreatment of a zirconium alloy matrix: sequentially polishing the surface of a Zry-4 alloy matrix by using 100# SiC sand paper, 400# SiC sand paper, 1000# SiC sand paper and 2000# SiC sand paper, sequentially polishing the polished Zry-4 alloy matrix by using diamond polishing liquid with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the polished Zry-4 alloy matrix by using acetone and absolute ethyl alcohol for 10min, and drying the polished Zry-4 alloy matrix for later use;
(2) preparing Cr-Si series coating: preparing a coating by magnetron sputtering, driving a Cr target and a Si target by a Direct Current (DC) power supply and a Radio Frequency (RF) power supply respectively, and performing vacuum of 8 multiplied by 10 -4 Pa, deposition temperature 380 ℃, substrate bias of-60V, the deposition air pressure is 0.5Pa, and the deposition time is 4 hours; wherein, the sputtering power of the Cr target is fixed to 300W, the sputtering power of the Si target is 200W, and the Si content of the coating is 16at percent.
Example 5
The preparation method of the Cr-Si coating on the surface of the zirconium alloy for the core comprises the following steps:
(1) pretreatment of a zirconium alloy matrix: sequentially polishing the surface of a Zry-4 alloy matrix by using 100# SiC sand paper, 400# SiC sand paper, 1000# SiC sand paper and 2000# SiC sand paper, sequentially polishing the polished Zry-4 alloy matrix by using diamond polishing liquid with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the polished Zry-4 alloy matrix by using acetone and absolute ethyl alcohol for 10min, and drying the polished Zry-4 alloy matrix for later use;
(2) preparing Cr-Si series coating: preparing a coating by magnetron sputtering, driving a Cr target and a Si target by a Direct Current (DC) power supply and a Radio Frequency (RF) power supply respectively, and performing vacuum of 8 multiplied by 10 -4 Pa, the deposition temperature is 420 ℃, the substrate bias voltage is-40V, the deposition air pressure is 0.3Pa, and the deposition time is 6h; wherein, the sputtering power of the Cr target is fixed to 300W, the sputtering power of the Si target is 300W, and the Si content of the coating is 21.9at.%.
Claims (6)
1. A Cr-Si coating on the surface of a zirconium alloy for nuclear use, which is characterized in that: the Cr-Si coating is prepared by magnetron sputtering a Cr target and a Si target, wherein the content of Si in the coating is controlled to be 7.5-22.0 at%, the power supplies of the Cr target and the Si target are respectively a direct current power supply and a radio frequency power supply, the sputtering power of the Cr target is 300W, and the power of the Si target is 100-300W.
2. A Cr-Si based coating for a zirconium alloy surface for a core as claimed in claim 1, wherein: in the magnetron sputtering process, the vacuum degree is 8 multiplied by 10 -4 Pa, the deposition temperature is 380-420 ℃, the substrate bias voltage is-40 to-60V, the deposition air pressure is 0.3-0.5 Pa, and the deposition time is 4-6 h.
3. The preparation reverse of the Cr-Si coating on the surface of the zirconium alloy for the nuclear is characterized in that: the Cr-Si coating with Si content of 7.5-22.0 at.% is formed on the surface of the zirconium alloy substrate by magnetron sputtering with a Cr target and a Si target.
4. A reverse preparation of Cr-Si based coating on the surface of zirconium alloy for nuclear use as claimed in claim 3, wherein: the power drives of the Cr target and the Si target are respectively a direct current power supply and a radio frequency power supply, wherein the sputtering power of the Cr target is 300W, and the power of the Si target is 100-300W.
5. The reverse of the preparation of a cr—si based coating on a zirconium alloy surface for a core as claimed in claim 3 or 4, wherein: the vacuum degree of the magnetron sputtering is 8 multiplied by 10 -4 Pa, the deposition temperature is 380-420 ℃, the substrate bias voltage is-40 to-60V, the deposition air pressure is 0.3-0.5 Pa, and the deposition time is 4-6 h.
6. The preparation method of the Cr-Si coating on the surface of the zirconium alloy for the core is characterized by comprising the following steps:
(1) pretreatment of a zirconium alloy matrix: sequentially polishing the surface of a Zry-4 alloy matrix by using 100# SiC sand paper, 400# SiC sand paper, 1000# SiC sand paper and 2000# SiC sand paper, sequentially polishing the polished Zry-4 alloy matrix by using diamond polishing liquid with the granularity of 1.5 mu m and silica suspension with the granularity of 0.06 mu m, sequentially ultrasonically cleaning the polished Zry-4 alloy matrix by using acetone and absolute ethyl alcohol for 10min, and drying the polished Zry-4 alloy matrix for later use;
(2) preparing Cr-Si series coating: preparing a coating by magnetron sputtering, driving a Cr target and a Si target by a Direct Current (DC) power supply and a Radio Frequency (RF) power supply respectively, and performing vacuum of 8 multiplied by 10 -4 Pa, the deposition temperature is 380-420 ℃, the substrate bias voltage is-40 to-60V, the deposition air pressure is 0.3-0.5 Pa, and the deposition time is 4-6 h; wherein the sputtering power of the Cr target is fixed to 300W, the sputtering power of the Si target is 100-300W, and the Si content of the coating is 7.5-22.0 at%.
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| KR20130125985A (en) * | 2012-05-10 | 2013-11-20 | 한국원자력연구원 | Plasma spray surface coating on zirconium alloy for increasing the corrosion resistance at very high temperature |
| CN112853287A (en) * | 2020-12-31 | 2021-05-28 | 中国科学院宁波材料技术与工程研究所 | Protective coating with long-time high-temperature-resistant steam oxidation and preparation method thereof |
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| KR20130125985A (en) * | 2012-05-10 | 2013-11-20 | 한국원자력연구원 | Plasma spray surface coating on zirconium alloy for increasing the corrosion resistance at very high temperature |
| CN112853287A (en) * | 2020-12-31 | 2021-05-28 | 中国科学院宁波材料技术与工程研究所 | Protective coating with long-time high-temperature-resistant steam oxidation and preparation method thereof |
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| 张世宏等: "气相沉积技术原理及应用", 31 December 2020, 冶金工业出版社, pages: 57 * |
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