CN112813399A - High-entropy metal glass protective coating and preparation method thereof - Google Patents
High-entropy metal glass protective coating and preparation method thereof Download PDFInfo
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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
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- 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
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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
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- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
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Abstract
The invention provides a high-entropy metal glass protective coating and a preparation method thereof. The coating prepared by the technology is uniform in components, compact in structure and good in film-substrate binding force. In addition, the Zr-Fe-Nb-Cr-Al-Si-Mo-Ti-Ta (five or six mixed components) high-entropy metal glass protective coating prepared by the invention has excellent oxidation resistance and good corrosion resistance, can be applied to cladding materials of reactor elements and other fuel assembly structural components, and prolongs the service life.
Description
Technical Field
The invention relates to the field of protective coatings, in particular to a high-entropy metal glass protective coating and a preparation method thereof.
Background
The working conditions of the cladding materials used by the existing nuclear reactor are extremely harsh: the inner part is affected by fission products, the outer part is affected by corrosion of a coolant, temperature and pressure, and is affected by strong neutron radiation, scouring and vibration of the coolant, internal stress, thermal cycle (during startup and shutdown), stress, fuel swelling and the like, so the nuclear power generating device needs to be replaced every 12 months and belongs to a high-consumption product. The current commercial zirconium alloy cladding material has no protection in the conventional service. It is critical for the cladding material to moderate the oxidation kinetics of the cladding, thereby reducing heat generation and hydrogen evolution. In 2011, since the Japanese Fudao has a loss of coolant accident, Zr and high-temperature water vapor react violently in a high-temperature environment to release a large amount of heat and explosive gas H2Resulting in the occurrence of a reactor accident. The zirconium alloy with oxygen or hydrogen dissolved therein has weakened mechanical properties and is liable to cause corrosion and induced cracking. Researches prove that the Zr alloy cladding material has the defects of exposure of oxidation resistance, mechanical property and the like under the high-temperature environment of more than 800 ℃, so that the accident-resistant cladding material needs to be developed. The safety device can provide a larger safety margin as far as possible under the accident condition, and the problem of severe melting of the reactor core is avoided. Based on the above, the Chinese atomic energy research institute specially designs a set of reactor cladding material high-temperature steam oxidation quenching test device to simulate the loss of coolant accident.
Research and development of novel nuclear fuel cladding materials are underway, and SiC/SiCf composite materials, FeCrAl alloys, Ti-Al alloys, Mo materials and the like are developed as candidate materials. New material systems inevitably present new problems, such as the problem of SiC being soluble in water under normal working conditions and the difficulty of shaping. The development of new fuel clad requires longer cycle time and higher cost. The development of coating technology is the most effective way in the short term, and the introduction of micron-scale coatings does not change the basic properties of the whole structural material, but can significantly improve the corrosion resistance and reduce the amount of hydrogen absorption during operation. Coating technology plays an important role in the field of the color industry. Conventional deposition (or coating) techniques include chemical vapor deposition, low temperature spray coating, physical vapor deposition, and the like. In the case of the chemical vapor deposition method, a coating film having a uniform thickness is easily formed, but since the deposition temperature is very high, phase transition or deformation of the zirconium substrate is easily caused. In the case of low-temperature spraying, the deposition rate is high, but the compactness of the coating film is low, and thus it is difficult to apply as a nuclear fuel cladding coating technique. In the case of physical deposition methods, deposition at low temperatures is possible and coating densities close to the theoretical density can be achieved. Polycrystalline or amorphous may be formed depending on deposition conditions; the high-temperature oxidation resistance can be improved by optimizing the deposition conditions; therefore, the application is wide. The ideal coating not only satisfies the high-temperature oxidation resistance, but also considers the neutron economy, stability, compactness, irradiation resistance and the like. Matching of physicochemical properties between the coating and the substrate is also critical.
At present, nuclear energy in the world utilizes a protective material system with autonomous characteristics developed by the great nation. A large number of experimental researches show that the Cr, Fe-Cr-Al, MAX phase, SiC coating and the like have problems to a certain extent, such as instability of an oxidation film at high temperature, formation of a brittle phase induced by diffusion of a coating substrate interface, occurrence of holes caused by endless diffusion in the oxidation process of the coating, reduction of a protection effect and the like. In addition, the reactive dissolution of alumina-and silica-based coatings in high temperature, high pressure water is also a problem.
It has been found that by blending different components the properties of the material can be improved and the blended product can average the properties of the various components but enhanced or entirely new properties sometimes occur. In highly disordered multicomponent systems, high entropy yields very good performance. High entropy materials remain stable under extreme temperature, pressure and chemical environments. Disorder and microstructure engineering have been used to optimize the strength-ductility ratio of metal alloys; it is envisioned that similar methods will be applied to high entropy metallic glasses. The high mixing entropy enhances the intersolubility of elements, inhibits the formation of compounds and can play a role in stabilizing an amorphous system. Meanwhile, the amorphous phase exists stably due to high interfacial energy and kinetic barrier of atomic diffusion during crystallization (slow kinetics). Due to the high entropy effect, the alloy shows excellent properties such as high strength, high hardness, wear resistance and high temperature oxidation corrosion resistance. The method is characterized in that a multi-component amorphous coating is constructed on the basis of zirconium, and a coating material which accords with the intrinsic characteristics, interface compatibility and good oxygen blocking effect of zirconium alloy is obtained according to the regulation and control structure of components and bonding states and the structure-activity relationship between the protection effect and the protection effect. And the amorphous microstructure is combined with the radiation resistance and the corrosion resistance, so that the safety, the long service life and the sustainable development of the nuclear power material are facilitated.
Disclosure of Invention
The invention provides a high-entropy metal glass protective coating and a preparation method thereof. In addition, the Zr-Fe-Nb-Cr-Al-Si-Mo-Ti-Ta (five or six of the Zr-Fe-Nb-Cr-Al-Si-Mo-Ti-Ta) high-entropy metal glass protective coating prepared by the invention has excellent oxidation resistance and good corrosion resistance, forms a stable multilayer oxide film structure under a high-temperature oxidation condition, and shows an ultra-slow oxidation kinetics behavior. The composite material can be applied to cladding materials of reactor elements and other fuel assembly structural components, and the service life is prolonged.
The technical scheme for realizing the invention is as follows:
a preparation method of a high-entropy metal glass protective coating for a nuclear reactor comprises the following steps:
(1) cutting a zirconium-based multi-element target material to form a sputtering target material, independently using aluminum as a sputtering target material, respectively attaching monocrystalline silicon to the sputtering target material and the aluminum target material, and finely regulating and controlling the components of the high-entropy alloy coating by controlling the exposed areas of different target materials;
(2) connecting an aluminum target material attached with monocrystalline silicon to a target position connected with a direct-current power supply, connecting a sputtering target material attached with monocrystalline silicon to the target position connected with a radio-frequency power supply, confirming that the target material is insulated from an anode frame and a cavity, and placing a cleaned monocrystalline silicon piece or zirconium alloy into a magnetron sputtering vacuum bin and placing the monocrystalline silicon piece or the zirconium alloy on a rotary heating table; the vacuum chamber cover is closed, and the air pressure of the chamber is pumped to 5 x 10 by a mechanical pump and a molecular pump-4Pa or lessAnd after pre-sputtering, depositing the high-entropy metallic glass coating by adopting a co-sputtering method.
The zirconium-based multi-element target material in the step (1) comprises at least three of Fe, Nb, Cr, Mo, Ti or Ta besides Zr, the thickness of the sputtering target material and the aluminum target material is 3-10mm, the diameter of the sputtering target material is 3 inches, and the target material component is 99.999%.
And (2) taking the monocrystalline silicon wafer or the zirconium alloy as a coating substrate in the step (1).
The pre-sputtering step in the step (2) comprises the following steps: pumping the air pressure in the chamber to 5 × 10-4And introducing Ar gas below Pa, adjusting the working air pressure in the chamber to 3-5 Pa, starting a radio frequency power supply to preheat, after preheating is finished, opening a target head baffle plate of the sputtering target material, starting the radio frequency power supply, after the sputtering target material is started to glow, adjusting the air pressure in the chamber to 0.32-1.5 Pa, opening the target head baffle plate of the aluminum target material, starting a direct current power supply, and adjusting the voltage and the current of the direct current power supply.
And after the radio frequency power supply is turned on, the sputtering power of the radio frequency power supply is adjusted to 70-120W, after the direct current power supply is turned on, the voltage of the direct current power supply is adjusted to 50-80V, the current is adjusted to 0.06-0.1A, and the sputtering power of the direct current power supply is adjusted to 3-8W.
The co-sputtering condition in the step (2) is as follows: after the pre-sputtering, opening a substrate shielding plate, carrying out co-sputtering, setting the gas flow of Ar to be 20-30 sccm, adjusting the air pressure in the vacuum chamber to be 0.32-1.5 Pa, and adjusting the sputtering power of a direct-current power supply to be 3-8W and the sputtering power of a radio-frequency power supply to be 70-120W.
And after the co-sputtering is finished, closing the substrate baffle plate, the DC power supply, the RF power supply, the target head baffle plate, the process gas valve, the gas flowmeter, the molecular pump gate valve, the molecular pump and the mechanical pump in sequence, and finally breaking vacuum to take out the sample.
In the step (2), in the process of depositing the high-entropy metallic glass film, in order to improve the uniformity of the film layer, the substrate rotates at a certain speed.
In the step (2), high-energy plasma continuously bombards the surface of the target to generate high heat, circulating water is continuously introduced below the target to prevent the target from being melted, redundant heat is taken away, and meanwhile, the heat of the circulating water is taken away by an external water cooling machine, so that the temperature of the whole system is not too high.
The area of the monocrystalline silicon in the step (1) is 2-4cm2。
In the high-entropy metal glass protective coating, various elements are uniformly distributed, no crystalline phase appears, the coating structure is stable, and the thickness of the film is 1-3 um.
The high-entropy metal glass protective coating is applied to the oxidation resistance field.
The high-entropy metal glass protective coating is applied to surface protection of a nuclear fuel cladding.
The invention has the beneficial effects that: according to the invention, a multi-component high-entropy metal glass coating is prepared by using single-chamber three-target magnetron sputtering equipment through the design of a target material, and can be used for surface protection of a nuclear fuel cladding or other anti-oxidation fields. The coating can effectively improve the oxidation resistance and corrosion resistance of the cladding.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a TEM image of the air oxidation of a coating of the invention at 800 deg.C/20 hours.
FIG. 2 is a TEM image of the air oxidation of the coating at 1000 ℃ for 2 hours.
FIG. 3 is a TEM image of the high-entropy metallic glass coating after being oxidized at 800 ℃ for 0.5 hour, 4 hours, and 20 hours, respectively.
FIG. 4 is a graph showing the change of the thickness of an oxide film with the increase of the oxidation time after the high-entropy metallic glass film is oxidized at 800 deg.C, 900 deg.C and 1000 deg.C respectively for the same time.
FIG. 5 is a diagram of an optical mirror showing the difference between the thickness of an oxide film formed by steam oxidation at 1000 ℃ for 1 hour in a zirconium alloy position with or without a high-entropy metallic glass coating protection and a zirconium alloy position without a coating protection, and a plan view of the zirconium alloy position with or without a high-entropy coating protection.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The selected adhesive area is 2 cm2Al target material of monocrystalline silicon piece, and adhered area of 2 cm2Taking a Zr-Fe-Nb-Cr combined target of a monocrystalline silicon wafer as a sputtering target, taking the monocrystalline silicon wafer as a coating substrate, sequentially carrying out ultrasonic treatment on the monocrystalline silicon wafer for 20 minutes by using acetone, alcohol and deionized water, and then blowing the monocrystalline silicon wafer for later use by using a high-purity nitrogen air gun; when the vacuum degree of the chamber reaches 5 multiplied by 10-4 Deposition is started at mbar, and the area of the paste is 2 cm2The Al target material of the monocrystalline silicon piece is connected to a target position connected with a Direct Current (DC) power supply, and the area of the target position to be attached is 2 cm2The Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is connected to a target position connected with a Radio Frequency (RF) power supply.
When the air pressure of the chamber reaches 5 x 10-4When the pressure is lower than Pa, opening a process gas valve to introduce Ar, setting the gas flow of Ar to be 20sccm through a gas flowmeter, and adjusting the air pressure in the vacuum chamber to be 3 Pa (+ -0.01 Pa) through adjusting a gate valve of the molecular pump; starting a Radio Frequency (RF) power supply for preheating, after the Radio Frequency (RF) power supply is preheated, starting a target head baffle plate of the Zr-Fe-Nb-Cr combined target material, starting the Radio Frequency (RF) power supply, adjusting power, and adjusting molecules after the Zr-Fe-Nb-Cr combined target material is startedA pump gate valve for adjusting the air pressure in the vacuum chamber to 0.32 Pa; opening a target head baffle plate of the Al target material, opening a DC power supply, adjusting the voltage and the current of the DC power supply, adjusting the current to 0.06A, the voltage at the moment to 50V, and the power of the DC power supply to 3W; and opening the substrate shielding plate to carry out co-sputtering.
The control pasting area is 2 cm2The RF power of the Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is adjusted to 70W, and the attached area is 2 cm2The DC power supply power of the Al target of the monocrystalline silicon piece is 3W. Under the power of the power supply, the deposition thickness of the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass is about 1 um after the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass is co-sputtered for 4.5 hours.
Example 2
The selected adhesive area is 3 cm2Al target material of monocrystalline silicon piece, pasted area is 3 cm2Taking a Zr-Ta-Nb-Cr combined target of a monocrystalline silicon wafer as a sputtering target, taking the monocrystalline silicon wafer as a coating substrate, sequentially carrying out ultrasonic treatment on the monocrystalline silicon wafer for 20 minutes by using acetone, alcohol and deionized water, and then blowing the monocrystalline silicon wafer for later use by using a high-purity nitrogen air gun; when the vacuum degree of the chamber reaches 5 multiplied by 10-4 Deposition starts around mbar. The area of the paste is 3 cm2The Al target of the monocrystalline silicon piece is connected to a target position connected with a Direct Current (DC) power supply. The area of the paste is 3 cm2The Zr-Ta-Nb-Cr combined target material of the monocrystalline silicon piece is connected to a target position connected with a Radio Frequency (RF) power supply.
The air pressure of the chamber reaches 5 x 10-4When the pressure is lower than Pa, opening a process gas valve to introduce Ar, setting the gas flow of Ar to be 20sccm through a gas flowmeter, and adjusting the air pressure in the vacuum chamber to be 3 Pa (+ -0.01 Pa) through adjusting a gate valve of the molecular pump; starting a Radio Frequency (RF) power supply for preheating, after the Radio Frequency (RF) power supply is preheated, starting a target head baffle plate of the Zr-Ta-Nb-Cr combined target, starting the Radio Frequency (RF) power supply, adjusting power, and after the Zr-Ta-Nb-Cr combined target is started, adjusting a molecular pump gate valve to adjust the air pressure in the vacuum chamber to 0.32 Pa; opening a target head baffle plate of the Al target material, opening the target head baffle plate of the Al target material, opening a DC power supply, adjusting the voltage and the current of the DC power supply, adjusting the current to 0.08A, the voltage at the moment to 62.5V, and the power of the DC power supply to 5W; opening linerAnd a bottom shielding plate for co-sputtering.
The control pasting area is 3 cm2The RF power supply power of the Zr-Ta-Nb-Cr combined target material of the monocrystalline silicon piece is adjusted to be 100W, and the attaching area is 3 cm2The DC power supply power of the Al target of the monocrystalline silicon piece is 5W. Under the power of the power supply, the deposition thickness of the Zr-Ta-Nb-Cr-Al-Si high-entropy metallic glass is about 2um after the Zr-Ta-Nb-Cr-Al-Si high-entropy metallic glass is co-sputtered for 4.5 hours.
Example 3
The selected adhesive area is 4cm2Al target material of monocrystalline silicon piece, pasting area is 4cm2Taking a Zr-Fe-Nb-Cr combined target of a monocrystalline silicon wafer as a sputtering target, taking the monocrystalline silicon wafer as a coating substrate, sequentially carrying out ultrasonic treatment on the monocrystalline silicon wafer for 20 minutes by using acetone, alcohol and deionized water, and then blowing the monocrystalline silicon wafer for later use by using a high-purity nitrogen air gun; when the vacuum degree of the chamber reaches 5 multiplied by 10-4 Deposition starts around mbar. The area of the paste is 4cm2The Al target of the monocrystalline silicon piece is connected to a target position connected with a Direct Current (DC) power supply. The area of the paste is 4cm2The Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is connected to a target position connected with a Radio Frequency (RF) power supply.
The air pressure of the chamber reaches 5 x 10-4When the pressure is lower than Pa, opening a process gas valve to introduce Ar, setting the gas flow of Ar to be 20sccm through a gas flowmeter, and adjusting the air pressure in the vacuum chamber to be 3 Pa (+ -0.01 Pa) through adjusting a gate valve of the molecular pump; starting a Radio Frequency (RF) power supply for preheating, after the Radio Frequency (RF) power supply is preheated, starting a target head baffle plate of the Zr-Fe-Nb-Cr combined target, starting the Radio Frequency (RF) power supply, adjusting power, and after the Zr-Fe-Nb-Cr combined target is ignited, adjusting a molecular pump gate valve to adjust the air pressure in the vacuum chamber to 0.32 Pa; opening a target head baffle plate of the Al target material, opening the target head baffle plate of the Al target material, opening a DC power supply, adjusting the voltage and the current of the DC power supply, adjusting the current to 0.09A, the voltage at the moment to 66.7V, and the power of the DC power supply to 6W; and opening the substrate shielding plate to carry out co-sputtering.
The control pasting area is 4cm2The RF power of the Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is 100W, and the pasting area is 4cm2Al target material of monocrystalline silicon pieceThe DC power supply of (1) is 4W. Under the power of the power supply, the deposition thickness of the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass is about 2um after the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass is co-sputtered for 4.5 hours.
Example 4
The selected adhesive area is 2 cm2Al target material of monocrystalline silicon piece, and adhered area of 2 cm2Taking a Zr-Fe-Nb-Cr combined target material of a monocrystalline silicon wafer as a sputtering target material, taking a zirconium alloy as a coating substrate, firstly grinding and polishing the surface of the zirconium alloy by using silicon carbide abrasive paper with the granularity of 600, then sequentially carrying out ultrasonic treatment on the zirconium alloy by using acetone, alcohol and deionized water for 20 minutes, and finally blowing the zirconium alloy for later use by using a high-purity nitrogen gun. When the vacuum degree of the chamber reaches 5 multiplied by 10-4 Deposition starts around mbar. The area to be adhered is 2 cm2The Al target of the monocrystalline silicon piece is connected to a target position connected with a Direct Current (DC) power supply. The area to be adhered is 2 cm2The Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is connected to a target position connected with a Radio Frequency (RF) power supply.
The air pressure of the chamber reaches 5 x 10-4When the pressure is lower than Pa, opening a process gas valve to introduce Ar, setting the gas flow of Ar to be 20sccm through a gas flowmeter, and adjusting the air pressure in the vacuum chamber to be 3 Pa (+ -0.01 Pa) through adjusting a gate valve of the molecular pump; starting a Radio Frequency (RF) power supply for preheating, after the Radio Frequency (RF) power supply is preheated, starting a target head baffle plate of the Zr-Fe-Nb-Cr combined target, starting the Radio Frequency (RF) power supply, adjusting power, and after the Zr-Fe-Nb-Cr combined target is ignited, adjusting a molecular pump gate valve to adjust the air pressure in the vacuum chamber to 0.32 Pa; opening a target head baffle plate of the Al target material, opening a DC power supply, adjusting the voltage and the current of the DC power supply, adjusting the current to 0.06A, the voltage at the moment to 50V, and the power of the DC power supply to 3W; and opening the substrate shielding plate to carry out co-sputtering.
The control pasting area is 2 cm2The RF power supply power of the Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is adjusted to 90W, and the adhering area is 2 cm2The DC power supply power of the Al target of the monocrystalline silicon piece is 3W. Under the power of the power supply, the deposition thickness of the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass is about 1 um after the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass is co-sputtered for 4.5 hours.
Example 5
The selected adhesive area is 3 cm2Al target material of monocrystalline silicon piece, pasted area is 3 cm2Taking a Zr-Ta-Nb-Cr combined target material of a monocrystalline silicon wafer as a sputtering target material, taking a zirconium alloy as a coating substrate, firstly grinding and polishing the surface of the zirconium alloy by using silicon carbide abrasive paper with the granularity of 600, then sequentially carrying out ultrasonic treatment on the zirconium alloy surface by using acetone, alcohol and deionized water for 20 minutes, and finally blowing the zirconium alloy surface for later use by using a high-purity nitrogen gun; when the vacuum degree of the chamber reaches 5 multiplied by 10-4 Deposition starts around mbar. The area of the paste is 3 cm2The Al target of the monocrystalline silicon piece is connected to a target position connected with a Direct Current (DC) power supply. The area of the paste is 3 cm2The Zr-Ta-Nb-Cr combined target material of the monocrystalline silicon piece is connected to a target position connected with a Radio Frequency (RF) power supply.
The air pressure of the chamber reaches 5 x 10-4When the pressure is lower than Pa, opening a process gas valve to introduce Ar, setting the gas flow of Ar to be 20sccm through a gas flow meter, and adjusting the air pressure in the vacuum chamber to be 4 Pa (+ -0.01 Pa) through adjusting a gate valve of the molecular pump; starting a Radio Frequency (RF) power supply for preheating, after the Radio Frequency (RF) power supply is preheated, starting a target head baffle plate of the Zr-Ta-Nb-Cr combined target, starting the Radio Frequency (RF) power supply, adjusting power, after the Zr-Ta-Nb-Cr combined target is started, adjusting a molecular pump gate valve, and adjusting the air pressure in the vacuum chamber to 0.5 Pa; opening a target head baffle plate of the Al target material, opening the target head baffle plate of the Al target material, opening a DC power supply, adjusting the voltage and the current of the DC power supply, adjusting the current to 0.08A, the voltage at the moment to 62.5V, and the power of the DC power supply to 3W; and opening the substrate shielding plate to carry out co-sputtering.
The control pasting area is 3 cm2The RF power supply power of the Zr-Ta-Nb-Cr combined target material of the monocrystalline silicon piece is adjusted to be 100W, and the attaching area is 3 cm2The DC power supply power of the Al target of the monocrystalline silicon piece is 5W. Under the power of the power supply, the deposition thickness of the Zr-Ta-Nb-Cr-Al-Si high-entropy metallic glass is about 2um after the Zr-Ta-Nb-Cr-Al-Si high-entropy metallic glass is co-sputtered for 4.5 hours.
Example 6
The selected adhesive area is 4cm2Al target material of monocrystalline silicon piece, pasting area is 4cm2Zr-Fe-Nb-C of monocrystalline silicon waferr, taking the combined target material as a sputtering target material, taking the zirconium alloy as a coating substrate, firstly, grinding and polishing the surface of the zirconium alloy by using silicon carbide abrasive paper with the granularity of 600, then, sequentially carrying out ultrasonic treatment on the zirconium alloy by using acetone, alcohol and deionized water for 20 minutes, and finally, blowing the zirconium alloy for later use by using a high-purity nitrogen air gun; when the vacuum degree of the chamber reaches 5 multiplied by 10-4 Deposition starts around mbar. The area of the paste is 4cm2The Al target of the monocrystalline silicon piece is connected to a target position connected with a Direct Current (DC) power supply. The area of the paste is 4cm2The Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is connected to a target position connected with a Radio Frequency (RF) power supply.
The air pressure of the chamber reaches 5 x 10-4When the pressure is lower than Pa, opening a process gas valve to introduce Ar, setting the gas flow of Ar to be 20sccm through a gas flowmeter, and adjusting the air pressure in the vacuum chamber to be 5 Pa (+ -0.01 Pa) through adjusting a gate valve of the molecular pump; starting a Radio Frequency (RF) power supply for preheating, after the Radio Frequency (RF) power supply is preheated, starting a target head baffle plate of the Zr-Fe-Nb-Cr combined target, starting the Radio Frequency (RF) power supply, adjusting power, and after the Zr-Fe-Nb-Cr combined target is ignited, adjusting a molecular pump gate valve to adjust the air pressure in the vacuum chamber to 0.32 Pa; opening a target head baffle plate of the Al target material, opening the target head baffle plate of the Al target material, opening a DC power supply, adjusting the voltage and the current of the DC power supply, adjusting the current to 0.09A, the voltage at the moment to 66.7V, and the power of the DC power supply to 6W; and opening the substrate shielding plate to carry out co-sputtering.
The control pasting area is 4cm2The RF power of the Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is 100W, and the pasting area is 4cm2The DC power supply power of the Al target of the monocrystalline silicon piece is 6W. Under the power of the power supply, the deposition thickness of the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass is about 2um after the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass is co-sputtered for 4.5 hours.
Example 7
The selected adhesive area is 3 cm2Al target material of monocrystalline silicon piece, pasted area is 3 cm2Taking Zr-Ta-Nb-Cr combined target of a monocrystalline silicon wafer as a sputtering target, taking zirconium alloy as a coating substrate, firstly grinding and polishing the surface of the zirconium alloy by using silicon carbide abrasive paper with the granularity of 600, and then polishingPerforming ultrasonic treatment for 20 minutes by using acetone, alcohol and deionized water, and finally blowing the mixture for later use by using a high-purity nitrogen air gun; when the vacuum degree of the chamber reaches 5 multiplied by 10-4 Deposition starts around mbar. The area of the paste is 3 cm2The Al target of the monocrystalline silicon piece is connected to a target position connected with a Direct Current (DC) power supply. The area of the paste is 3 cm2The Zr-Ta-Nb-Cr combined target material of the monocrystalline silicon piece is connected to a target position connected with a Radio Frequency (RF) power supply.
The air pressure of the chamber reaches 5 x 10-4When the pressure is lower than Pa, opening a process gas valve to introduce Ar, setting the gas flow of Ar to be 20sccm through a gas flowmeter, and adjusting the air pressure in the vacuum chamber to be 5 Pa (+ -0.01 Pa) through adjusting a gate valve of the molecular pump; starting a Radio Frequency (RF) power supply for preheating, after the Radio Frequency (RF) power supply is preheated, starting a target head baffle plate of the Zr-Ta-Nb-Cr combined target, starting the Radio Frequency (RF) power supply, adjusting power, after the Zr-Ta-Nb-Cr combined target is started, adjusting a molecular pump gate valve, and adjusting the air pressure in the vacuum chamber to 1.5 Pa; opening a target head baffle plate of the Al target material, opening the target head baffle plate of the Al target material, opening a DC power supply, adjusting the voltage and the current of the DC power supply, adjusting the current to 0.1A, the voltage at the moment to 80V, and the power of the DC power supply to 8W; and opening the substrate shielding plate to carry out co-sputtering.
The control pasting area is 3 cm2The RF power supply power of the Zr-Ta-Nb-Cr combined target material of the monocrystalline silicon piece is adjusted to be 120W, and the attaching area is 3 cm2The DC power supply power of the Al target of the monocrystalline silicon piece is 8W. Under the power of the power supply, the deposition thickness of the Zr-Ta-Nb-Cr-Al-Si high-entropy metallic glass is about 3um after the Zr-Ta-Nb-Cr-Al-Si high-entropy metallic glass is co-sputtered for 4.5 hours.
The coating prepared in example 3 was examined and the results are as follows;
first, coating quality characterization
Using a transmission electron microscope (TEM, FEI TecnaiG)2F20) And analyzing the component distribution and the crystal structure of the coating section sample, and characterizing the surface morphology and the section morphology of the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass film by a JEOL field emission scanning electron microscope (FE-SEM).
Second, the oxidation resistance test of the coating
The oxidation resistance test of the coating is carried out in a muffle furnace, the temperature is set to be 800 ℃, 900 ℃ and 1000 ℃, and the time range is 2-20 hours. And preparing a TEM section sample from the oxidized sample by using an ion thinning instrument, and observing and analyzing the section appearance and components.
Using transmission electron microscopy (TEM, FEITecnaiG)2F20) And comparing the component change before and after oxidation, EDX line scanning and surface scanning analysis, judging the oxidation resistance and corrosion resistance of the coating according to the characteristic change of the section morphology of the sample, and judging the oxidized product by combining the component analysis. And (4) characterizing the surface topography change of the coating before and after oxidation by using a scanning electron microscope (FE-SEM).
A TEM image of the coating after air oxidation at 800 ℃/20 hours is shown in figure 1, a large amount of element diffusion phenomena occur inside the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass film, the element diffusion gradually tends to be stable, and the high-entropy coating generates crystallization phenomena. EDS (electric discharge machining) surface scanning and component analysis of a section oxidized at 800 ℃ for 20 hours show that a layering phenomenon appears in the Zr-Fe-Nb-Cr-Al-Si high-entropy coating, Al elements are gathered and oxidized at high temperature to form an inner alumina layer, and the formed alumina layer plays a good role in shielding and can prevent oxygen from continuously permeating into the coating.
A TEM image of the coating after being oxidized in air at 1000 ℃ for 2 hours is shown in FIG. 2, a large amount of element diffusion phenomenon appears in the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass film, the element diffusion is in the initial diffusion stage, the element diffusion tendency is consistent with that of the high-entropy coating when being oxidized at 800 ℃, and the high-entropy coating has crystallization phenomenon. EDS (electric discharge machining) surface scanning and component analysis of a cross section oxidized for 2 hours at 1000 ℃ show that a layering trend appears in the Zr-Fe-Nb-Cr-Al-Si high-entropy coating, Al elements are gradually gathered and oxidized at high temperature to form an inner alumina layer, and the formed alumina layer plays a good role in shielding and can prevent oxygen from continuously permeating into the coating.
And (3) characterizing the changes of the surface appearance of the coating before and after high-temperature oxidation, the thickness difference of the oxide films of the zirconium alloy position protected by the high-entropy metal glass coating and the zirconium alloy position without the coating protection, and the changes of the thickness of the oxide film with the extension of oxidation time of the high-entropy coating position and the coating protection position by using a scanning electron microscope (FE-SEM).
The scanning plane shape shows that the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass coating has complete surface shape and no crack. The combination of the high-entropy coating and the substrate zirconium alloy is good in the cross-sectional morphology, and compared with the thickness of the oxide film of the zirconium alloy at the high-entropy coating position of Zr-Fe-Nb-Cr-Al-Si, the thickness of the oxide film of the zirconium alloy at the high-entropy coating position of Zr-Fe-Nb-Cr-Al-Si can not be seen obviously, and the thickness of the oxide film at the coating position can not reach 20 mu m. Therefore, the Zr-Fe-Nb-Cr-Al-Si high-entropy metallic glass coating plays a good role in protecting the zirconium alloy.
FIG. 1 shows that a large amount of element diffusion phenomena occur in the high-entropy metallic glass coating after air oxidation at 800 ℃ for 20 hours, the element diffusion gradually tends to be stable, and the coating is layered and forms an alumina layer to play a good barrier role, so that oxygen can be prevented from continuously permeating into the coating.
FIG. 2 shows that after the high-entropy metallic glass coating is subjected to air oxidation at 1000 ℃ for 2 hours, the coating initially shows a layering trend, and an aluminum oxide layer is gradually formed through element diffusion, and the aluminum oxide layer can prevent oxygen from continuously permeating into the coating.
FIG. 3 shows TEM images of the high-entropy metallic glass coating after being oxidized at 800 ℃ for 0.5 hour, 4 hours and 20 hours respectively, and the images dynamically show the formation and evolution processes of the alumina oxygen barrier layer. During the oxidation process, a large amount of elements are diffused to gradually form an alumina oxygen barrier layer and tend to be stable.
FIG. 4 is a graph showing the change of the thickness of an oxide film with the increase of the oxidation time after the high-entropy metallic glass thin film is oxidized at the same time of 800 deg.C, 900 deg.C, 1000 deg.C, respectively. This graph shows that the oxide film thickness gradually increases slowly with the increase in oxidation time and finally approaches a stable value when oxidized at the same temperature. After the oxidation for the same time, the higher the temperature, the thicker the oxide film thickness.
FIG. 5 is a diagram of an optical mirror showing the difference between the thickness of an oxide film formed by steam oxidation at 1000 ℃ for 1 hour in a zirconium alloy position with or without a high-entropy metallic glass coating protection and a zirconium alloy position without a coating protection, and a plan view of the zirconium alloy position with or without a high-entropy coating protection.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a high-entropy metal glass protective coating for a nuclear reactor is characterized by comprising the following steps:
(1) cutting a zirconium-based multi-element target material to form a sputtering target material, and respectively attaching monocrystalline silicon to the sputtering target material and an aluminum target material;
(2) connecting an aluminum target material attached with monocrystalline silicon to a target position connected with a direct-current power supply, connecting a sputtering target material attached with monocrystalline silicon to the target position connected with a radio-frequency power supply, and depositing a high-entropy metal glass coating by adopting a co-sputtering method after pre-sputtering.
2. The method of claim 1, wherein: the zirconium-based multi-element target material in the step (1) also comprises at least three of Fe, Nb, Cr, Mo, Ti or Ta, and the thickness of the sputtering target material and the aluminum target material is 3-10mm, and the diameter of the sputtering target material and the aluminum target material is 3 inches.
3. The method of manufacturing layer of claim 1, wherein: and (2) taking the monocrystalline silicon wafer or the zirconium alloy as a coating substrate in the step (1).
4. The method according to claim 1, wherein the pre-sputtering in the step (2) comprises the steps of: pumping the air pressure in the chamber to 5 × 10-4And introducing Ar gas below Pa, adjusting the working air pressure in the chamber to 3-5 Pa, starting a radio frequency power supply to preheat, after preheating is finished, opening a target head baffle plate of the sputtering target material, starting the radio frequency power supply, after the sputtering target material is started to glow, adjusting the air pressure in the chamber to 0.32-1.5 Pa, opening the target head baffle plate of the aluminum target material, starting a direct current power supply, and adjusting the voltage and the current of the direct current power supply.
5. The method of claim 4, wherein: and after the radio frequency power supply is turned on, the sputtering power of the radio frequency power supply is adjusted to 70-120W, after the direct current power supply is turned on, the voltage of the direct current power supply is adjusted to 50-80V, the current is adjusted to 0.06-0.1A, and the sputtering power of the direct current power supply is adjusted to 3-8W.
6. The method of claim 1, wherein: the co-sputtering condition in the step (2) is as follows: after the pre-sputtering, opening a substrate shielding plate, carrying out co-sputtering, setting the gas flow of Ar to be 20-30 sccm, adjusting the air pressure in the vacuum chamber to be 0.32-1.5 Pa, and adjusting the sputtering power of a direct-current power supply to be 3-8W and the sputtering power of a radio-frequency power supply to be 70-120W.
7. The method of claim 1, wherein: the area of the monocrystalline silicon in the step (1) is 2-4cm2。
8. A high-entropy metallic glass protective coating produced by the production method described in any one of claims 1 to 7, characterized in that: the thickness of the high-entropy metal glass protective coating is 1-3 um.
9. Use of the high-entropy metallic glass protective coating of claim 8 in the field of oxidation resistance.
10. Use of the high entropy metallic glass protective coating of claim 8 for surface protection of nuclear fuel enclosures.
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