CN112813399B - 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
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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 condition of the cladding material used by the current nuclear reactor is 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 station is 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 H 2 Resulting 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. Research proves that the Zr alloy cladding material is in a high-temperature environment of more than 800 DEG CThe defects of oxidation resistance, mechanical property and the like are exposed, so that the accident-resistant cladding material needs to be developed. Under the accident condition, a larger safety margin is provided as far as possible, 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. A polycrystal or an amorphous may be formed depending on deposition conditions; the high-temperature oxidation resistance can be improved by optimizing the deposition condition; 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. The matching of the physicochemical properties between the coating and the substrate is also of critical importance.
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 and SiC coating 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 infinite diffusion in the oxidation process of the coating, reduction of a protection effect and the like. In addition, the reactive dissolution of alumina-based and silica-based coatings in high temperature, high pressure water is also a problem.
It has been found that the properties of the material can be improved by blending different components and that 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. While the amorphous phase will exist 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 -4 And (4) below Pa, depositing the high-entropy metal glass coating by adopting a co-sputtering method after pre-sputtering.
In the step (1), the zirconium-based multi-element target material also 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 and the aluminum target material are 3 inches, and the components of the target material are 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 -4 And 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 baffle 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 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 2-4cm 2 。
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 1-3um.
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 beneficial effects of the invention are: 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, the metal glass coating can be used for surface protection of a nuclear fuel cladding or other anti-oxidation fields, the entropy value of the coating is increased through element screening combination, the disadvantages of a single element coating are avoided, element diffusion and enrichment occur in oxidation at high temperature, especially, an inner alumina barrier layer is formed by aluminum diffusion and oxidation, and the inner diffusion of oxygen can be well blocked so as to slow down the oxidation corrosion rate. 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 embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a TEM image of an 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 cm 2 Al target material of monocrystalline silicon piece, sticking area is 2 cm 2 Of monocrystalline silicon wafersTaking a Zr-Fe-Nb-Cr combined target as a sputtering target, taking a 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 cm 2 The 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 cm 2 The 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 -4 When 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 a 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 cm 2 The 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 cm 2 The DC 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 cm 2 Al target material of monocrystalline silicon piece, pasted area is 3 cm 2 Taking 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 x 10 -4 mbar around startAnd (6) depositing. The area of the paste is 3 cm 2 The 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 cm 2 The 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 -4 When 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 a 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 material, starting the Radio Frequency (RF) power supply, adjusting power, after the Zr-Ta-Nb-Cr combined target material is started, adjusting a molecular pump gate valve, and adjusting 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 be 0.08A, the voltage at the moment to be 62.5V, and the power of the DC power supply to be 5W; and opening the substrate shielding plate to carry out co-sputtering.
The control pasting area is 3 cm 2 The 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 attached area is 3 cm 2 The DC power supply power of the Al target of the monocrystalline silicon piece is 5W. Under 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 sputtered for 4.5 hours.
Example 3
The selected adhesive area is 4cm 2 Al target material of monocrystalline silicon piece, sticking area is 4cm 2 Taking 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 4cm 2 An Al target of a single crystal silicon wafer is connected to a target position connected with a Direct Current (DC) power supply. The area of the paste is 4cm 2 The Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is connected with a Radio Frequency (RF) power supplyIs detected at the target site.
The air pressure of the chamber reaches 5 x 10 -4 When 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 be 0.09A, the voltage at the moment to be 66.7V, and the power of the DC power supply to be 6W; and opening the substrate shielding plate to carry out co-sputtering.
The control pasting area is 4cm 2 The RF power supply power of the Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is 100W, and the sticking area is 4cm 2 The DC power supply power of the Al target of the monocrystalline silicon piece 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 cm 2 Al target material of monocrystalline silicon piece, and adhered area of 2 cm 2 Taking 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 x 10 -4 Deposition starts around mbar. The area of the paste is 2 cm 2 The 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 2 cm 2 The Zr-Fe-Nb-Cr combined target 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 -4 When below Pa, opening a process gas valve, introducing Ar, passingThe gas flow of Ar is set to be 20sccm by the gas flow meter, and the air pressure in the vacuum chamber is adjusted to be 3 Pa (+ -0.01 Pa) by 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, after the Zr-Fe-Nb-Cr combined target material is ignited, adjusting a molecular pump gate valve, and 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 cm 2 The 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 cm 2 The DC 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 cm 2 Al target material of monocrystalline silicon piece, sticking area is 3 cm 2 Taking 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 cm 2 The 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 cm 2 The 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 -4 When 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; turning on Radio Frequency (RF) power supplyPreheating, after the preheating of a Radio Frequency (RF) power supply is finished, opening a target head baffle plate of the Zr-Ta-Nb-Cr combined target material, opening the Radio Frequency (RF) power supply, adjusting power, after the Zr-Ta-Nb-Cr combined target material glows, 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 cm 2 The 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 attached area is 3 cm 2 The 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 4cm 2 Al target material of monocrystalline silicon piece, pasting area is 4cm 2 Taking 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 surface for 20 minutes by using acetone, alcohol and deionized water, 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 4cm 2 The 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 4cm 2 The 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 -4 When 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 material, starting the Radio Frequency (RF) power supply, adjusting power,after the Zr-Fe-Nb-Cr combined target material 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 4cm 2 The RF power of the Zr-Fe-Nb-Cr combined target material of the monocrystalline silicon piece is 100W, and the pasting area is 4cm 2 The 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 cm 2 Al target material of monocrystalline silicon piece, pasted area is 3 cm 2 Taking 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 x 10 -4 Deposition starts around mbar. The area of the paste is 3 cm 2 The 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 cm 2 The 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 -4 When 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 material, starting the Radio Frequency (RF) power supply, adjusting power, after the Zr-Ta-Nb-Cr combined target material is started, adjusting a molecular pump gate valve, and adjusting the air pressure in the vacuum chamber to 1.5 Pa; opening the target head baffle plate of the Al target material, and beatingOpening 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 be 0.1A, the voltage at the moment to be 80V, and the power of the DC power supply to be 8W; and opening the substrate shielding plate to carry out co-sputtering.
The control pasting area is 3 cm 2 The 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 attached area is 3 cm 2 The 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 prepared coating of example 3 was tested and the results are as follows;
1. coating quality characterization
Using a transmission electron microscope (TEM, FEI TecnaiG) 2 F20 The component distribution and the crystal structure of a coating section sample are analyzed, and the surface morphology and the section morphology characteristics of the Zr-Fe-Nb-Cr-Al-Si high-entropy metal glass film are characterized by a JEOL field emission scanning electron microscope (FE-SEM).
2. Oxidation resistance test of 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) 2 F20 Comparing the component change before and after oxidation, EDX line scanning and 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 then judging the product after oxidation by combining the component analysis. And (4) utilizing a scanning electron microscope (FE-SEM) to characterize the surface morphology change of the coating before and after oxidation.
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 in the Zr-Fe-Nb-Cr-Al-Si high-entropy metal glass film, the element diffusion gradually tends to be stable, and the high-entropy coating crystallizes. 800. EDS (electric Desorption deposition) scanning and component analysis of a section of the coating subjected to oxidation at the temperature of 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 a 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. 1000. EDS (electric Desorption deposition) scanning and composition analysis of a section of the Zr-Fe-Nb-Cr-Al-Si high-entropy coating layer after being oxidized for 2 hours at the temperature of DEG C show that the layering trend appears in the Zr-Fe-Nb-Cr-Al-Si high-entropy coating layer, 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 layer.
And (3) utilizing a scanning electron microscope (FE-SEM) to represent 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 unprotected by the coating, and the changes of the thickness of the oxide film along with the prolonging of the oxidation time of the high-entropy coating position and the non-coating protection position.
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 metal glass coating is oxidized in air 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, an alumina oxygen barrier layer is gradually formed through the diffusion of a large amount of elements and tends 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 should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (9)
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;
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.
2. The production method according to claim 1, characterized in that: 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 piece 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 -4 And 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 manufacturing according to claim 4, characterized in that: 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 area of the monocrystalline silicon in the step (1) is 2-4cm 2 。
7. A high-entropy metallic glass protective coating produced by the production method described in any one of claims 1 to 6, characterized in that: the thickness of the high-entropy metal glass protective coating is 1-3um.
8. Use of the high-entropy metallic glass protective coating of claim 7 in the field of oxidation resistance.
9. Use of the high entropy metallic glass protective coating of claim 7 for surface protection of nuclear fuel cladding.
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