CN117721416A - Zirconium alloy surface composite coating for cores and preparation method thereof - Google Patents
Zirconium alloy surface composite coating for cores and preparation method thereof Download PDFInfo
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- CN117721416A CN117721416A CN202311741971.7A CN202311741971A CN117721416A CN 117721416 A CN117721416 A CN 117721416A CN 202311741971 A CN202311741971 A CN 202311741971A CN 117721416 A CN117721416 A CN 117721416A
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- 238000000576 coating method Methods 0.000 title claims abstract description 78
- 239000011248 coating agent Substances 0.000 title claims abstract description 75
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 12
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910001120 nichrome Inorganic materials 0.000 claims abstract description 54
- 238000005253 cladding Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000004544 sputter deposition Methods 0.000 claims description 65
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 54
- 238000000151 deposition Methods 0.000 claims description 30
- 229910052786 argon Inorganic materials 0.000 claims description 27
- 230000008021 deposition Effects 0.000 claims description 21
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 10
- 239000013077 target material Substances 0.000 claims description 10
- 238000007747 plating Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 12
- 239000003758 nuclear fuel Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 47
- 229910045601 alloy Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005498 polishing Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 229910019580 Cr Zr Inorganic materials 0.000 description 5
- 229910019817 Cr—Zr Inorganic materials 0.000 description 5
- 238000001020 plasma etching Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 230000005496 eutectics Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 244000137852 Petrea volubilis Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a zirconium alloy surface composite coating for a nuclear and a preparation method thereof, belonging to the technical field of nuclear fuel cladding surface coatings. The composite coating comprises a Mo layer, a Cr layer and a NiCr layer from inside to outside in sequence. The Mo layer is composed of Mo pure metal; the Cr layer is composed of Cr pure metal; the NiCr layer comprises the following components: 25-30wt% of Ni and 70-75wt% of Cr. By a means ofThe thickness of the Mo layer is 0.5-3 mu m, the thickness of the Cr layer is 12-18 mu m, and the thickness of the NiCr layer is 0.5-6 mu m. NiCr layers of the outermost layer of the composite coating on the surface of the zirconium alloy for the nuclear, designed by the invention, can generate NiO in a high-temperature steam environment, and relieve and even inhibit Cr 2 O 3 Thereby improving the overall high temperature oxidation resistance of the coating.
Description
Technical Field
The invention relates to the technical field of nuclear fuel cladding surface coatings, in particular to a zirconium alloy surface composite coating for a nuclear and a preparation method thereof.
Background
The zirconium alloy has the advantages of corrosion resistance, neutron irradiation resistance, good thermal conductivity, low thermal neutron absorption section, moderate mechanical property, good processability and the like, so that the zirconium alloy is widely applied to the field of water-cooled reactor nuclear fuel cladding materials. However, when the reactor is in an accident condition of loss of coolant, the zirconium alloy cladding will undergo a severe oxidation reaction with high temperature steam, releasing a large amount of heat and hydrogen gas, causing hydrogen explosion. Therefore, there is a need to design a solution for improving the oxidation resistance of the zirconium alloy cladding to high temperature steam.
The zirconium alloy surface modification has the advantages of short research and development period, low cost and the like, and is considered as one of effective means for improving the high-temperature steam oxidation resistance. Among these, cr metal is considered as one of the potential candidate materials for the surface coating of the fuel cladding of zirconium alloy because of its advantages of higher melting point, higher heat conductivity, strong high-temperature oxidation resistance, and similar thermal expansion coefficient to zirconium alloy. However, cr coating layer is formed under high temperature environment and has protective effect 2 O 3 The oxide film volatilizes, so that the protection function is reduced or even lost; secondly, the eutectic reaction temperature of Cr-Zr is relatively low (about 1332 ℃), and when the reactor is in the over-design reference accident condition and the reactor core temperature reaches or even exceeds the eutectic reaction temperature, the Cr coating can rapidly lose the protection performance and still needs to be further improved.
Disclosure of Invention
The invention aims to provide a zirconium alloy surface composite coating for a core and a preparation method thereof. NiCr layers of the outermost layer of the composite coating on the surface of the zirconium alloy for the nuclear, designed by the invention, can generate NiO in a high-temperature steam environment, and relieve and even inhibit Cr 2 O 3 Thereby improving the overall high temperature oxidation resistance of the coating.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows: a composite coating is provided, which comprises a Mo layer, a Cr layer and a NiCr layer from inside to outside.
Preferably, the Mo layer has a composition of Mo pure metal; the Cr layer is composed of Cr pure metal; the NiCr layer comprises the following components: 25-30wt% of Ni and 70-75wt% of Cr.
Preferably, the thickness of the Mo layer is 0.5-3 μm, the thickness of the Cr layer is 12-18 μm, and the thickness of the NiCr layer is 0.5-6 μm.
The second technical scheme of the invention is as follows: the preparation method of the composite coating comprises the following steps:
and plating a Mo layer, a Cr layer and a NiCr layer on the substrate material in sequence through a high-power pulse magnetron sputtering process.
Preferably, in the Mo layer plating process, the parameters of the high-power pulse magnetron sputtering include: the target material is Mo, the sputtering gas is argon, the pulse frequency is 200-500 Hz, the pulse width is 50-150 mu s, the duty ratio is 1-4%, the sputtering power is 1000-4000W, the sputtering air pressure is 0.2-1.5 Pa, the bias voltage is-60 to-200V, the deposition temperature is 100-300 ℃, and the deposition time is 1-6 h.
Preferably, when plating the Cr layer, the parameters of the high-power pulse magnetron sputtering include: the target material is Cr, the sputtering gas is argon, the pulse frequency is 200-500 Hz, the pulse width is 50-150 mu s, the duty ratio is 1-4%, the sputtering power is 1000-4000W, the sputtering air pressure is 0.2-1.5 Pa, the bias voltage is-60 to-200V, the deposition temperature is 100-300 ℃, and the deposition time is 2-24 h.
Preferably, when plating the NiCr layer, the parameters of the high power pulse magnetron sputtering include: the target material is NiCr, the sputtering gas is argon, the pulse frequency is 200-500 Hz, the pulse width is 50-150 mu s, the duty ratio is 1-4%, the sputtering power is 1000-4000W, the sputtering air pressure is 0.2-1.5 Pa, the bias voltage is-60 to-200V, the deposition temperature is 100-300 ℃, and the deposition time is 1-6 h.
More preferably, the zirconium alloy substrate further comprises a zirconium alloy substrate pretreatment step prior to plating the Mo layer, the pretreatment step comprising grinding, polishing, ultrasonic cleaning and drying to remove impurities on the surface of the zirconium alloy substrate.
More preferably, after the zirconium alloy substrate is pretreated, the method further comprises a target pre-sputtering step, wherein the conditions of the target pre-sputtering step comprise: the power is 100-500W, the vacuum of the cavity is 1-3Pa, and the pre-sputtering time is 5-30min, so that the oxide and impurities on the surfaces of the Mo target, the Cr target and the NiCr target are removed.
More preferably, after the target material is pre-sputtered, an argon plasma etching step is further included, and the conditions of the argon plasma etching step include: the temperature is 150-350 ℃, the argon flow is 30-50 sccm, the ion source current is 0.2-2A, the bias voltage is-50 to-200V, and the etching time is 15-30 min, so that impurities on the surface of the substrate are further removed.
The third technical scheme of the invention: the application of the composite coating in improving the high-temperature service performance of the zirconium alloy cladding is provided.
The beneficial technical effects of the invention are as follows:
the zirconium alloy surface composite coating for the nuclear, which is designed by the invention, sequentially comprises a Mo layer, a Cr layer and a NiCr layer from inside to outside, and has better combination property with a zirconium alloy matrix, compact structure and better surface quality. The Mo layer is positioned between the zirconium alloy matrix and the Cr layer, so that mutual diffusion between the Cr layer and the zirconium alloy matrix can be effectively inhibited, and the formation of a Cr-Zr intermediate layer is avoided. Part of Mo diffuses into the zirconium alloy matrix to form a Mo-Zr layer, the minimum eutectic temperature of the Mo-Zr system is about 1500 ℃, and compared with the eutectic temperature of about 1332 ℃ between Cr and Zr, the capability of the fuel cladding for resisting serious accidents of a reactor can be obviously improved. Zr will preferentially form ZrO with no protective effect after entering Cr 2 Cr cannot be formed efficiently 2 O 3 The diffusion rate of Zr in Mo is about 6-7 orders of magnitude lower than that of Zr in Cr, so that the preparation of the Mo layer between Cr and zirconium alloy can improve the interface stability between the coating and the matrix in a high-temperature steam environment under accident working conditions and improve the service reliability of the coating.
In addition, niCr layers of the outermost layer of the composite coating on the surface of the zirconium alloy for the nuclear, designed by the invention, can generate NiO in a high-temperature steam environment, and relieve and even inhibit Cr 2 O 3 Thereby improving the overall high temperature oxidation resistance of the coating.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic illustration of the NiCr/Cr/Mo composite coatings prepared in examples 1-3.
FIG. 2 is a cross-sectional morphology of the NiCr/Cr/Mo composite coating prepared in example 1.
FIG. 3 is a cross-sectional morphology diagram and an element distribution diagram of the NiCr/Cr/Mo composite coating prepared in example 2.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
The terms "comprising," "including," "having," "containing," and the like as used herein are open-ended terms, meaning including, but not limited to.
The composition of the NiCr layer used in the following examples and comparative examples of the present invention was: 30wt% of Ni and 70wt% of Cr.
The raw materials used in the following examples and comparative examples of the present invention are all commercially available products.
Example 1
Preparation of zirconium alloy deposited with NiCr/Cr/Mo coating:
(1) Pretreatment of a matrix: preparing Zr-4 alloy with the size of 15mm multiplied by 12mm multiplied by 2mm, polishing the surface of the alloy by using 400# to 5000# sand paper, polishing, ultrasonically cleaning the alloy for 10min by using acetone, taking out and drying the alloy, fixing the alloy on a sample table of a magnetron sputtering instrument cavity, heating the magnetron sputtering instrument cavity to 280 ℃, and vacuumizing the cavity to 5 multiplied by 10 -4 Pa；
(2) Target material pre-sputtering treatment: argon is introduced into a cavity of a magnetron sputtering instrument until the vacuum of the cavity is 1.2Pa, and the Mo target, the Cr target and the NiCr target are subjected to pre-sputtering for 15min under the power of 300W;
(3) Argon plasma etching: etching for 15min under the conditions of 300 ℃ and argon flow of 30sccm, ion source current of 1A and bias voltage of-100V;
(4) Sputtering a Mo coating: adjusting the distance between a sample table and a Mo target to be 10cm, introducing argon, starting a high-power pulse sputtering power supply, controlling the sputtering air pressure to be 0.5Pa, the bias voltage to be 100V, the pulse frequency to be 400Hz, the pulse width to be 50 mu s, the duty ratio to be 2%, the sputtering power to be 2800W, the deposition temperature to be 280 ℃, and depositing for 2 hours to obtain a zirconium alloy sample deposited with a Mo coating;
(5) Sputtering Cr coating: adjusting the distance between a sample table and a Cr target to be 10cm, introducing argon, starting a high-power pulse sputtering power supply, controlling the sputtering air pressure to be 0.5Pa, the bias voltage to be 100V, the pulse frequency to be 400Hz, the pulse width to be 50 mu s, the duty ratio to be 2%, the sputtering power to be 2800W, the deposition temperature to be 280 ℃, and depositing for 20 hours to obtain a zirconium alloy sample deposited with a Cr/Mo coating;
(5) Sputtering a NiCr coating: adjusting the distance between the sample stage and the NiCr target to be 12cm, introducing argon, starting a high-power pulse sputtering power supply, controlling the sputtering air pressure to be 0.5Pa, the bias voltage to be 100V, the pulse frequency to be 400Hz, the pulse width to be 60 mu s, the duty ratio to be 2%, the sputtering power to be 2800W, the deposition temperature to be 280 ℃, depositing for 2 hours, and taking out the sample after the isothermal temperature is reduced to room temperature to obtain the zirconium alloy deposited with the NiCr/Cr/Mo coating.
FIG. 1 is a schematic view of a NiCr/Cr/Mo composite coating prepared in example 1. FIG. 2 is a cross-sectional morphology of the NiCr/Cr/Mo composite coating prepared in example 1.
The thicknesses of the Mo coating, the Cr coating and the NiCr coating in the zirconium alloy deposited with the NiCr/Cr/Mo coating were 2.59 μm, 16.37 μm and 2.23 μm, respectively, as measured by a scanning electron microscope.
Example 2
Preparation of zirconium alloy deposited with NiCr/Cr/Mo coating:
(1) Pretreatment of a matrix: preparing Zr-4 alloy with the size of 15mm multiplied by 12mm multiplied by 2mm, polishing the surface of the alloy by using 400# to 5000# sand paper, polishing, ultrasonically cleaning the alloy for 10min by using acetone, taking out and drying the alloy, fixing the alloy on a sample table of a magnetron sputtering instrument cavity, heating the magnetron sputtering instrument cavity to 280 ℃, and vacuumizing the cavity to 5 multiplied by 10 -4 Pa；
(2) Target material pre-sputtering treatment: argon is introduced into a cavity of a magnetron sputtering instrument until the vacuum of the cavity is 1.2Pa, and the Mo target, the Cr target and the NiCr target are subjected to pre-sputtering for 15min under the power of 300W;
(3) Argon plasma etching: etching for 15min under the conditions of 300 ℃ and argon flow of 30sccm, ion source current of 1A and bias voltage of-100V;
(4) Sputtering a Mo coating: adjusting the distance between a sample table and a Mo target to be 10cm, introducing argon, starting a high-power pulse sputtering power supply, controlling the sputtering air pressure to be 0.5Pa, the bias voltage to be 100V, the pulse frequency to be 360Hz, the pulse width to be 55 mu s, the duty ratio to be 2%, the sputtering power to be 3000W, the deposition temperature to be 260 ℃, and depositing for 2.5 hours to obtain a zirconium alloy sample deposited with a Mo coating;
(5) Sputtering Cr coating: adjusting the distance between a sample table and a Cr target to be 10cm, introducing argon, starting a high-power pulse sputtering power supply, controlling the sputtering air pressure to be 0.5Pa, the bias voltage to be 100V, the pulse frequency to be 360Hz, the pulse width to be 55 mu s, the duty ratio to be 2%, the sputtering power to be 3000W, the deposition temperature to be 260 ℃, and depositing for 16 hours to obtain a zirconium alloy sample deposited with a Cr/Mo coating;
(5) Sputtering a NiCr coating: adjusting the distance between the sample stage and the NiCr target to be 12cm, introducing argon, starting a high-power pulse sputtering power supply, controlling the sputtering air pressure to be 0.5Pa, the bias voltage to be 100V, the pulse frequency to be 360Hz, the pulse width to be 65 mu s, the duty ratio to be 2%, the sputtering power to be 3000W, the deposition temperature to be 260 ℃, depositing for 3 hours, and taking out the sample after the isothermal temperature is reduced to room temperature to obtain the zirconium alloy deposited with the NiCr/Cr/Mo coating.
The thicknesses of the Mo coating, the Cr coating and the NiCr coating in the zirconium alloy deposited with the NiCr/Cr/Mo coating were 2.48 μm, 16.52 μm and 2.35 μm respectively, as measured by a scanning electron microscope.
FIG. 3 is a cross-sectional morphology diagram and an element distribution diagram of the NiCr/Cr/Mo composite coating prepared in example 2.
Example 3
Preparation of zirconium alloy deposited with NiCr/Cr/Mo coating:
(1) Pretreatment of a matrix: preparing Zr-4 alloy with the size of 15mm multiplied by 12mm multiplied by 2mm, polishing the surface of the alloy by using 400# to 5000# sand paper, polishing, ultrasonically cleaning the alloy for 10min by using acetone, taking out and drying the alloy, fixing the alloy on a sample table of a magnetron sputtering instrument cavity, heating the magnetron sputtering instrument cavity to 280 ℃, and vacuumizing the cavity to 5 multiplied by 10 -4 Pa；
(2) Target material pre-sputtering treatment: argon is introduced into a cavity of a magnetron sputtering instrument until the vacuum of the cavity is 1.2Pa, and the Mo target, the Cr target and the NiCr target are subjected to pre-sputtering for 15min under the power of 300W;
(3) Argon plasma etching: etching for 15min under the conditions of 300 ℃ and argon flow of 30sccm, ion source current of 1A and bias voltage of-100V;
(4) Sputtering a Mo coating: adjusting the distance between a sample table and a Mo target to be 10cm, introducing argon, starting a high-power pulse sputtering power supply, controlling the sputtering air pressure to be 0.5Pa, the bias voltage to be-150V, the pulse frequency to be 350Hz, the duty ratio to be 2%, the pulse width to be 80 mu s, the sputtering power to be 2500W, the deposition temperature to be 250 ℃, and depositing for 3.5 hours to obtain a zirconium alloy sample deposited with a Mo coating;
(5) Sputtering Cr coating: adjusting the distance between a sample table and a Cr target to be 10cm, introducing argon, starting a high-power pulse sputtering power supply, controlling the sputtering air pressure to be 0.5Pa, the bias voltage to be-150V, the pulse frequency to be 350Hz, the pulse width to be 80 mu s, the duty ratio to be 2%, the sputtering power to be 2500W, the deposition temperature to be 250 ℃, and depositing for 18 hours to obtain a zirconium alloy sample deposited with a Cr/Mo coating;
(5) Sputtering a NiCr coating: adjusting the distance between the sample stage and the NiCr target to be 12cm, introducing argon, starting a high-power pulse sputtering power supply, controlling the sputtering air pressure to be 0.5Pa, the bias voltage to be 150V, the pulse frequency to be 350Hz, the pulse width to be 90 mu s, the duty ratio to be 2%, the sputtering power to be 2500W, the deposition temperature to be 250 ℃, depositing for 5 hours, and taking out the sample after the isothermal temperature is reduced to room temperature to obtain the zirconium alloy deposited with the NiCr/Cr/Mo coating.
In the zirconium alloy deposited with the NiCr/Cr/Mo coating, the thicknesses of the Mo coating, the Cr coating and the NiCr coating were 2.85 μm, 15.24 μm and 4.23 μm, respectively, as measured by a scanning electron microscope.
Comparative example 1
The only difference from example 1 is that the step of sputtering Mo coating was omitted, only Cr coating and NiCr coating were sputtered, and other preparation processes were identical to example 1, finally obtaining a zirconium alloy sample with a NiCr/Cr composite coating covered on the surface.
Comparative example 2
The only difference from example 1 is that the step of sputtering the NiCr coating was omitted, only the Mo coating and the Cr coating were sputtered, and the other preparation processes were identical to example 1, finally obtaining a zirconium alloy sample with a Cr/Mo composite coating covered on the surface.
Effect verification
High temperature oxidation resistance test:
the products of examples 1-3 and comparative examples 1-2 were oxidized at 8000S in a 1200℃steam environment with a steam flow of 50g/min. The oxidized sample was examined by scanning electron microscopy.
The test results show that the surface oxide film of the products of examples 1-3 is divided into two layers and the outermost layer after oxidation testThe oxide film is a compact NiO layer, and the inner oxide film is compact Cr 2 O 3 The layer, zirconium alloy matrix was not oxidized, and no Cr element was detected in the mo—zr layer. This demonstrates that the NiCr/Cr/Mo coating deposited zirconium alloys prepared in examples 1-3 have good resistance to high temperature oxidation and that the NiO layer formed on the surface helps to reduce Cr 2 O 3 The Mo layer can effectively inhibit mutual diffusion between the Cr layer and the zirconium alloy matrix, and the formation of a Cr-Zr intermediate layer is avoided, so that the high-temperature service performance of the coating is improved.
On the surface of the product of comparative example 1, the outermost layer was a NiO layer, and interdiffusion phenomenon was present between Cr-Zr, and the thickness of the interdiffusion layer was 2.36. Mu.m.
After oxidation test, the product of comparative example 2 formed loose and porous Cr on the surface 2 O 3 Layer, i.e. part of Cr 2 O 3 The volatilization occurs, the thickness of the oxide film is reduced, the density is reduced, the protection performance is declined, and the diffusion of the oxidation medium to the zirconium alloy matrix can not be effectively blocked, so that the zirconium alloy matrix is oxidized; no Cr element was detected in the mo—zr layer.
As can be seen from the phenomena and data in examples 1-3 and comparative examples 1-2, the present invention prepares a NiCr/Cr/Mo composite coating on the surface of zirconium alloy, and the NiCr layer oxidation product film has the function of inhibiting Cr 2 O 3 Volatilizing; the Mo layer has the function of preventing interdiffusion between Cr and Zr and inhibiting formation of Cr-Zr intermediate layer. This shows that the NiCr/Cr/Mo composite coating designed and prepared by the invention effectively enhances the accident resistance of the zirconium alloy cladding.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (8)
1. The composite coating is characterized by sequentially comprising a Mo layer, a Cr layer and a NiCr layer from inside to outside.
2. The composite coating of claim 1, wherein the Mo layer is composed of Mo pure metal; the Cr layer is composed of Cr pure metal; the NiCr layer comprises the following components: 25-30wt% of Ni and 70-75wt% of Cr.
3. The composite coating according to claim 1, wherein the Mo layer has a thickness of 0.5 to 3 μm, the Cr layer has a thickness of 12 to 18 μm, and the NiCr layer has a thickness of 0.5 to 6 μm.
4. A method of producing a composite coating according to any one of claims 1 to 3, comprising the steps of:
and plating a Mo layer, a Cr layer and a NiCr layer on the substrate material in sequence through a high-power pulse magnetron sputtering process.
5. The method according to claim 4, wherein the parameters of the high power pulse magnetron sputtering when plating the Mo layer include: the target material is Mo, the sputtering gas is argon, the pulse frequency is 200-500 Hz, the pulse width is 50-150 mu s, the duty ratio is 1-4%, the sputtering power is 1000-4000W, the sputtering air pressure is 0.2-1.5 Pa, the bias voltage is-60 to-200V, the deposition temperature is 100-300 ℃, and the deposition time is 1-6 h.
6. The method according to claim 4, wherein the parameters of the high power pulse magnetron sputtering when plating the Cr layer include: the target material is Cr, the sputtering gas is argon, the pulse frequency is 200-500 Hz, the pulse width is 50-150 mu s, the duty ratio is 1-4%, the sputtering power is 1000-4000W, the sputtering air pressure is 0.2-1.5 Pa, the bias voltage is-60 to-200V, the deposition temperature is 100-300 ℃, and the deposition time is 2-24 h.
7. The method according to claim 4, wherein the parameters of the high power pulse magnetron sputtering when plating the NiCr layer include: the target material is NiCr, the sputtering gas is argon, the pulse frequency is 200-500 Hz, the pulse width is 50-150 mu s, the duty ratio is 1-4%, the sputtering power is 1000-4000W, the sputtering air pressure is 0.2-1.5 Pa, the bias voltage is-60 to-200V, the deposition temperature is 100-300 ℃, and the deposition time is 1-6 h.
8. Use of a composite coating according to any one of claims 1 to 3 for improving the high temperature service performance of a zirconium alloy cladding.
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| CN202311741971.7A CN117721416A (en) | 2023-12-18 | 2023-12-18 | Zirconium alloy surface composite coating for cores and preparation method thereof |
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| CN (1) | CN117721416A (en) |
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2023
- 2023-12-18 CN CN202311741971.7A patent/CN117721416A/en active Pending
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