Titanium-based high-entropy amorphous / tungsten multilayer film with anti-irradiation and low-hydrogen retention potential and preparation method and application of titanium-based high-entropy amorphous / tungsten multilayer film

Abstract

The invention discloses a titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential and a preparation method and application thereof, and belongs to the technical field of nuclear energy materials. The titanium-based high-entropy amorphous / tungsten multilayer film sequentially comprises a first TiVZrNbTaMoB alloy layer, a W layer and a second TiVZrNbTaMoB alloy layer from bottom to top, and the atomic percent of TiVZrNbTaMoB alloy in the first TiVZrNbTaMoB alloy layer and the atomic percent of TiVZrNbTaMoB alloy in the second TiVZrNbTaMoB alloy layer are as follows: 45%-50% of Ti, 20%-30% of V, 8%-15% of Zr, 10%-20% of Nb, 0.5%-3% of Ta, 0.3%-1% of Mo and 0.1%-0.3% of B. The preparation process mainly adopts a magnetron sputtering method. The obtained multilayer film has the potential of radiation resistance and low hydrogen retention.

Description

Technical Field

[0001] The present invention belongs to the technical field of nuclear energy materials, and particularly relates to a titanium-based high-entropy amorphous / tungsten multi-layer film with anti-irradiation and low hydrogen retention potential, and a preparation method and application thereof. Background Art

[0002] In a fusion reactor, materials are irradiated by high-energy particles (such as neutrons, hydrogen isotopes, helium ions, etc.) for a long time, which leads to irradiation damage of the materials (such as vacancies, interstitial atoms, bubbles, etc.). Traditional materials (such as stainless steel, tungsten, etc.) are prone to problems such as hardening, embrittlement, and swelling of the materials under high-dose irradiation. Inside the fusion reactor, the self-sustaining problem of the hydrogen isotope "tritium" is also raised at the same time, which requires the materials inside the fusion reactor to have a low tritium retention amount. Thus, "tritium" can be self-sustaining and the problems of hydrogen embrittlement and degradation of mechanical properties caused by the penetration and aggregation of hydrogen isotopes inside the materials can be reduced.

[0003] High-entropy metallic glasses exhibit a more uniform, denser, and more locally ordered atomic arrangement than conventional metallic glasses. Due to their high mixing entropy characteristics, atomic diffusion takes a certain amount of time and the mobility is restricted, thus hindering the crystallization kinetics and complicating the formation and development of crystal nuclei. In addition, continuous polymorphic phase transitions are observed in high-entropy metallic glasses, which enables the system to achieve structural diversity while maintaining a consistent chemical composition, thereby significantly improving the thermal stability. This high thermal stability and complexity of crystallization kinetics endow high-entropy metallic glasses with good anti-irradiation performance.

[0004] However, although the high-entropy metallic glass film exhibits certain anti-irradiation potential, its single structure is difficult to balance the problems of anti-irradiation damage and hydrogen retention control; while conventional single-component multi-layer films (such as W / Ti) cannot meet the service conditions because of the weak interfacial bonding force and easy delamination failure after irradiation. Therefore, it is necessary to develop a new type of multi-layer film material with both high anti-irradiation performance, low hydrogen retention, and interfacial stability. Summary of the Invention

[0005] Aiming at the above technical problems, the present invention provides a titanium-based high-entropy amorphous / tungsten multi-layer film with anti-irradiation and low hydrogen retention potential, and a preparation method and application thereof.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] One of the objectives of the present invention is to provide a titanium-based high-entropy amorphous / tungsten multi-layer film with anti-irradiation and low hydrogen retention potential, which sequentially comprises a first TiVZrNbTaMoB alloy layer, a W layer, and a second TiVZrNbTaMoB alloy layer from bottom to top. Among them, the atomic percentages of TiVZrNbTaMoB alloy in the first TiVZrNbTaMoB alloy layer and the second TiVZrNbTaMoB alloy layer are as follows: Ti: 45-50%, V: 20-30%, Zr: 8-15%, Nb: 10-20%, Ta: 0.5-3%, Mo: 0.3-1%, B: 0.1-0.3%.

[0008] In the TiVZrNbTaMoB alloy, multiple main elements (Ti, V, Zr, Nb, Ta, Mo, B) form a high-entropy alloy with specific atomic percentages. The high mixing entropy characteristic of the high-entropy alloy restricts atomic diffusion, hinders crystallization kinetics, makes the formation and development of crystal nuclei more complex, and has good anti-irradiation performance. At the same time, its structural characteristics contribute to the absorption of point defects generated by irradiation. In the three-layer film structure, the upper and lower TiVZrNbTaMoB alloy layers exert the anti-irradiation advantages of the high-entropy alloy, and the middle W layer enhances the overall anti-damage ability by virtue of its high melting point and good anti-irradiation performance. This synergistic effect makes the anti-irradiation performance of the multi-layer film superior to that of the single-layer film. In terms of hydrogen retention, the multi-layer structure hinders the diffusion and aggregation of hydrogen, and more effectively reduces the hydrogen retention amount compared with the single-layer film. TiVZrNbTaMoB remains amorphous in the multi-layer film and does not crystallize after irradiation, ensuring its structural stability. The tungsten layer maintains a crystalline structure in the multi-layer film, and new crystal orientations appear after irradiation, further enhancing the stability of the film. This stable phase structure is the basis for the good performance of the multi-layer film. The interfaces between the layers of the multi-layer film are distinct, and no obvious damage or failure occurs before and after irradiation. The interface between the high-entropy alloy TiVZrNbTaMoB layer and the tungsten layer is tightly bonded, effectively transmitting stress, improving the overall performance of the film, and making it perform better in anti-irradiation and low hydrogen retention.

[0009] Furthermore, the raw materials of the first TiVZrNbTaMoB alloy layer and the second TiVZrNbTaMoB alloy layer are TiVZrNbTaMoB alloy targets, and the specific preparation method includes the following steps: weighing Ti, V, Zr, Nb, Ta, Mo, and B elements according to the stoichiometric ratio, mixing and ball-milling to obtain alloy raw materials, and placing the alloy raw materials in a vacuum hot-pressing sintering furnace for hot-pressing sintering to obtain TiVZrNbTaMoB alloy targets.

[0010] Even further, the conditions for the ball-milling are: the rotation speed of the ball mill is 300 rpm, the mass ratio of balls to materials is 1:10, and the ball-milling time is 24 h; and / or,

[0011] The process of hot pressing and sintering is as follows: evacuate to 1×10 -3 Pa, heat up at a heating rate of 10 °C / min to 600 - 800 °C for pre-sintering, hold for 30 min, then heat up at a heating rate of 5 - 10 °C / min to 1200 - 1400 °C, apply axial pressure after reaching the target temperature, and hold at the target temperature for 1 - 3 h, cool with the furnace to below 200 °C, turn off the heating and pressure systems, and continue to evacuate and cool to room temperature; the pressure is 30 - 50 MPa; and / or,

[0012] The thickness of the TiVZrNbTaMoB alloy target is 4 mm, and the diameter is 5 cm.

[0013] Further, the raw material of the W layer is a W target (the purity of the W target is 99.99%), and the specific preparation method includes the following steps: weigh W element, ball mill, and then place it in a vacuum hot pressing and sintering furnace for hot pressing and sintering to obtain a W target.

[0014] Furthermore, the conditions of the ball milling are: the rotation speed of the ball mill is 300 rpm, the mass ratio of the ball to the material is 1∶10, and the ball milling time is 24 h; and / or,

[0015] The process of hot pressing and sintering is as follows: evacuate to 1×10 -3 Pa, heat up at a heating rate of 10 °C / min to 600 - 800 °C for pre-sintering, hold for 30 min, then heat up at a heating rate of 5 - 10 °C / min to 1800 - 2000 °C, apply axial pressure after reaching the target temperature, and hold at the target temperature for 1 - 3 h, cool with the furnace to below 200 °C, turn off the heating and pressure systems, and continue to evacuate and cool to room temperature; the pressure is 40 - 60 MPa; and / or,

[0016] The thickness of the W target is 4 mm, and the diameter is 5 cm.

[0017] The second object of the present invention is to provide a preparation method of a titanium-based high-entropy amorphous / tungsten multi-layer film with anti-irradiation and low hydrogen retention potential, including the following steps:

[0018] (1) Place the TiVZrNbTaMoB alloy target and the W target respectively inside a magnetron sputtering cavity evacuated to 8×10 -4 Pa;

[0019] (2) Using the (111) crystal orientation of a silicon wafer as the substrate, sputter the TiVZrNbTaMoB alloy target on the substrate to obtain a first TiVZrNbTaMoB alloy layer;

[0020] (3) Turn off the DC power supply, rotate the substrate above the W target, and sputter the W target to obtain a W layer;

[0021] (4) Turn off the radio frequency power supply, rotate the substrate above the TiVZrNbTaMoB alloy target again, and repeat the sputtering step of the TiVZrNbTaMoB alloy target to prepare the second TiVZrNbTaMoB alloy layer. The obtained three-layer thin film is a titanium-based high-entropy amorphous / tungsten multi-layer thin film with the potential of anti-irradiation and low hydrogen retention.

[0022] Furthermore, the thickness of the first TiVZrNbTaMoB alloy layer and the second TiVZrNbTaMoB alloy layer is 400 - 500 nm; and / or,

[0023] the thickness of the W layer is 200 - 300 nm.

[0024] Furthermore, the sputtering conditions of the TiVZrNbTaMoB alloy target are all: the power is 50 W DC, the argon gas flow rate is 60 sccm, the sputtering gas pressure is 0.4 pa, the distance between the target and the substrate is 150 mm, and the sputtering time is 20 min.

[0025] Furthermore, the sputtering parameters of the W target are: the sputtering power is 80 W RF, the argon gas flow rate is 60 sccm, the sputtering gas pressure is 1.0 pa, the distance between the target and the substrate is 150 mm, and the sputtering time is 2 h.

[0026] The third object of the present invention is to provide an application of a titanium-based high-entropy amorphous / tungsten multi-layer thin film with the potential of anti-irradiation and low hydrogen retention in the preparation of materials for extreme irradiation environments, and the materials for extreme irradiation environments include: the first wall material of a nuclear reactor, the blanket material of a fusion reactor, or the coating material of a nuclear fuel cladding.

[0027] Compared with the prior art, the present invention has the following advantages and technical effects:

[0028] Through the design of the multi-layer thin film structure, the present invention effectively disperses the irradiation energy and reduces the concentrated area of irradiation damage, thereby significantly improving the anti-irradiation performance of the thin film.

[0029] Compared with a single-layer pure tungsten thin film, the hydrogen retention amount of the multi-layer thin film structure prepared by the present invention is only 10.65% of that of the single-layer pure tungsten thin film, effectively solving the problems of hydrogen embrittlement and degradation of mechanical properties caused by hydrogen retention inside the material.

[0030] Even after high-energy hydrogen ion irradiation, the multi-layer thin film prepared by the present invention can still maintain a clear layered structure with distinct interfaces, and no defects such as cracks, voids or delamination appear, showing excellent anti-irradiation stability and interface stability.

[0031] The multi-layer film provided by the present invention can be applied to the first wall material of a nuclear reactor, the blanket material of a fusion reactor, and the coating material of a nuclear fuel cladding, providing new high-performance material options for the development of nuclear energy technology. Description of the Drawings

[0032] The drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments and descriptions thereof of the present invention are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0033] Figure 1 Shows the hydrogen ion irradiation damage of a single-layer TiVZrNbTaMoB film, a single-layer W film, and a three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film simulated using SRIM software;

[0034] Figure 2 Shows the hydrogen ion retention of a single-layer TiVZrNbTaMoB film, a single-layer W film, and a three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film simulated using SRIM software;

[0035] Figure 3 Shows the XRD patterns of the original state of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film of the present invention and after being irradiated with 100 MeV and 300 MeV hydrogen ions, and the XRD pattern of the original state of the single-layer TiVZrNbTaMoB film;

[0036] Figure 4 Shows the cross-sectional scanning diagrams of the original state (Primitive state) of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film of the present invention and after being irradiated with 100 MeV and 300 MeV hydrogen ions. Detailed Description of the Invention

[0037] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation to the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention.

[0038] It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0039] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although this invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of this invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the said documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0040] Without departing from the scope or spirit of this invention, various improvements and changes can be made to the specific embodiments of this invention's specification, which are obvious to those skilled in the art. Other embodiments obtained from this invention's specification are obvious to those skilled in the art. This invention's specification and examples are merely exemplary.

[0041] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0042] By designing a three-layer structure of "amorphous HEMG / crystalline W / amorphous HEMG" and combining the anti-irradiation advantage of high-entropy amorphous alloys with the high stability of tungsten, the following synergistic effects are achieved:

[0043] Anti-irradiation: multi-layer energy dispersion + amorphous defect self-repair + high-temperature resistance of tungsten layer;

[0044] Low hydrogen retention: amorphous diffusion inhibition + physical barrier of tungsten layer + interface maze effect.

[0045] Experimental data verify the potential of this design in the extreme nuclear environment (such as the first wall of a fusion reactor), providing a new idea for the development of high-performance anti-irradiation materials.

[0046] An embodiment of this invention provides a preparation method for a titanium-based high-entropy amorphous / tungsten multi-layer thin film with the potential of anti-irradiation and low hydrogen retention, which is prepared from a TiVZrNbTaMoB alloy target and a W target as raw materials, and specifically includes the following steps:

[0047] (1) Preparation of the TiVZrNbTaMoB alloy target: Weigh the elements of Ti, V, Zr, Nb, Ta, Mo, and B according to the stoichiometric ratio, mix and ball-mill them to obtain alloy raw materials, and place the alloy raw materials in a vacuum hot-pressing sintering furnace for hot-pressing sintering to obtain the TiVZrNbTaMoB alloy target;

[0048] (2) Preparation of the W target: Weigh the element W, ball-mill it, and then place it in a vacuum hot-pressing sintering furnace for hot-pressing sintering to obtain the W target;

[0049] (3) Place the TiVZrNbTaMoB alloy target and the W target respectively inside the magnetron sputtering cavity evacuated to 8×10 -4 Pa (evacuated by a mechanical pump and a molecular pump); using the (111) crystal orientation of the silicon wafer as the substrate, sputter the TiVZrNbTaMoB alloy target on the substrate to obtain a TiVZrNbTaMoB alloy layer; turn off the DC power supply, rotate the substrate above the W target, sputter the W target to obtain a W layer; turn off the RF power supply, rotate the substrate above the TiVZrNbTaMoB alloy target again, repeat the sputtering step of the TiVZrNbTaMoB alloy target, and obtain a TiVZrNbTaMoB alloy layer again. The three-layer thin film obtained is a titanium-based high-entropy amorphous / tungsten multi-layer thin film with the potential of anti-irradiation and low hydrogen retention (denoted as: TiVZrNbTaMoB / W / TiVZrNbTaMoB thin film). During the entire sputtering process, the substrate is always in a self-rotating state to ensure that the thickness of the three-layer thin film obtained is uniform.

[0050] In the following preferred embodiments of the present invention, the atomic percentages of the Ti, V, Zr, Nb, Ta, Mo, and B elements in step (1) are: Ti: 45 - 50%, V: 20 - 30%, Zr: 8 - 15%, Nb: 10 - 20%, Ta: 0.5 - 3%, Mo: 0.3 - 1%, B: 0.1 - 0.3%. More preferably: Ti: 47.3%, V: 25%, Zr: 11%, Nb: 14%, Ta: 2%, Mo: 0.5%, B: 0.2%.

[0051] In the following preferred embodiments of the present invention, the conditions of the ball milling in step (1) are: the rotational speed of the ball mill is 300 rpm, the mass ratio of balls to materials is 1:10, and the ball milling time is 24 h. Alcohol is added to the materials during ball milling, and the alcohol is removed by drying after ball milling.

[0052] In the following preferred embodiments of the present invention, the process of hot pressing and sintering in step (1) is: evacuate to 1×10 - 3Pa (The purpose of vacuum pumping is to remove oxygen and volatile impurities). Heat up to 600 - 800 °C (more preferably 700 °C) at a heating rate of 10 °C / min for pre-sintering, and keep it for 30 min (the purpose of pre-sintering is to further degas and activate the powder surface). Then, heat up to 1200 - 1400 °C (more preferably 1300 °C) at a heating rate of 5 - 10 °C / min (more preferably 8 °C / min). After reaching the target temperature, apply axial pressure (the purpose of maintaining a constant pressure is to ensure sufficient powder diffusion and densification), and keep it at the target temperature for 1 - 3 h (more preferably 2 h). Cool it in the furnace to below 200 °C, turn off the heating and pressure systems, and continue to cool it to room temperature under vacuum; the pressure is 30 - 50 MPa (more preferably 40 MPa). After demolding, use ultrasonic cleaning to remove the residual mold release agent on the surface. After demolding, use wire cutting to process the sintered alloy ingot into the designed size of the target.

[0053] In the following preferred embodiments of the present invention, the conditions of the ball milling in step (2) are: the rotation speed of the ball mill is 300 rpm, the mass ratio of balls to materials is 1:10, and the ball milling time is 24 h. Alcohol is added to the materials during ball milling, and the alcohol is removed by drying after ball milling.

[0054] In the following preferred embodiments of the present invention, the process of hot press sintering in step (2) is: vacuum pump to 1×10 - 3 Pa (The purpose of vacuum pumping is to remove oxygen and volatile impurities). Heat up to 600 - 800 °C (more preferably 700 °C) at a heating rate of 10 °C / min for pre-sintering, and keep it for 30 min (the purpose of pre-sintering is to further degas and activate the powder surface). Then, heat up to 1800 - 2000 °C (more preferably 2000 °C) at a heating rate of 5 - 10 °C / min (more preferably 8 °C / min). After reaching the target temperature, apply axial pressure (the pressure is constant, and the purpose of maintaining a constant pressure is to ensure sufficient powder diffusion and densification), and keep it at the target temperature for 1 - 3 h (more preferably 2 h). Cool it in the furnace to below 200 °C, turn off the heating and pressure systems, and continue to cool it to room temperature under vacuum; the pressure is 40 - 60 MPa (more preferably 50 MPa). After demolding, use ultrasonic cleaning to remove the residual mold release agent on the surface. After demolding, use wire cutting to process the sintered W into the designed size of the target.

[0055] In the following preferred embodiments of the present invention, the thickness of the W target in step (2) is 4 mm, and the diameter is 5 cm.

[0056] In the following preferred embodiments of the present invention, the thickness of the TiVZrNbTaMoB alloy layer in step (3) is 400 - 500 nm, more preferably 468 nm or 463 nm.

[0057] In the following preferred embodiments of the present invention, the thickness of the W layer in step (3) is 200 - 300 nm, more preferably 273 nm.

[0058] In the following preferred embodiments of the present invention, the sputtering parameters of the TiVZrNbTaMoB alloy target in step (3) are as follows: the power is 50 W DC, the argon flow rate is 60 sccm, the sputtering gas pressure is 0.4 Pa, the distance between the target and the substrate is 150 mm, and the sputtering time is 20 min.

[0059] In the following preferred embodiments of the present invention, the sputtering parameters of the W target in step (3) are: the sputtering power is 80 W RF, the argon flow rate is 60 sccm, the sputtering gas pressure is 1.0 Pa, the distance between the target and the substrate is 150 mm, and the sputtering time is 2 h.

[0060] In the present invention, "room temperature" refers to 20 - 30 °C unless otherwise specified.

[0061] All raw materials used in the present invention are obtained by purchasing on the market.

[0062] The technical solution of the present invention is further described below through examples.

[0063] Example 1

[0064] A preparation method of a titanium-based high-entropy amorphous / tungsten multi-layer film with anti-irradiation and low hydrogen retention potential specifically includes the following steps:

[0065] (1) Preparation of the TiVZrNbTaMoB alloy target: Weigh Ti: 47.3%, V: 25%, Zr: 11%, Nb: 14%, Ta: 2%, Mo: 0.5%, B: 0.2% and mix to obtain a mixed material. Ball mill the mixed material under the conditions of: the ball mill rotation speed is 300 rpm, the ball-to-material mass ratio is 1∶10, and the ball milling time is 24 h. Put the obtained alloy raw material into a vacuum hot-pressing sintering furnace, evacuate to 1×10 -3 Pa, then put in the obtained alloy raw material, heat it at a heating rate of 10 °C / min to 700 °C for pre-sintering, keep it warm for 30 min, then heat it at a heating rate of 8 °C / min to 1300 °C. After reaching the target temperature, apply an axial pressure of 40 MPa and keep it warm at the target temperature for 2 h. Cool it in the furnace to below 200 °C, turn off the heating and pressure systems, and continue to evacuate and cool to room temperature; after demolding, use ultrasonic cleaning to remove the residual demolding agent on the surface. After demolding, use wire cutting to process the sintered alloy ingot to the designed size of the target to obtain a TiVZrNbTaMoB alloy target with a thickness of 4 mm and a diameter of 5 cm.

[0066] (2) Preparation of W target: Weigh W element, ball mill it, and then place it in a vacuum hot pressing sintering furnace for hot pressing sintering. The conditions for ball milling are as follows: the rotation speed of the ball mill is 300 rpm, the mass ratio of balls to materials is 1:10, and the ball milling time is 24 h. Put the obtained W raw material into the vacuum hot pressing sintering furnace, evacuate to 1×10 -3 Pa, then put in the obtained W raw material, heat it to 700 °C at a heating rate of 10 °C / min for pre-sintering, hold for 30 min, then heat it to 2000 °C at a heating rate of 8 °C / min. After reaching the target temperature, apply an axial pressure of 50 MPa and hold at the target temperature for 2 h. Cool with the furnace to below 200 °C, turn off the heating and pressure systems, and continue to evacuate and cool to room temperature; after demolding, use ultrasonic cleaning to remove the residual mold release agent on the surface. After demolding, use wire cutting to process the sintered alloy ingot into the designed size of the target, and obtain a W target with a thickness of 4 mm and a diameter of 5 cm;

[0067] (3) Use a mechanical pump and a molecular pump to evacuate the inside of the magnetron sputtering chamber to 8×10 -4 Pa, and then place the TiVZrNbTaMoB alloy target and the W target inside the magnetron sputtering chamber respectively; use the (111) crystal orientation of the silicon wafer as the substrate, and sputter the TiVZrNbTaMoB alloy target on the substrate. The sputtering parameters are all: the power is 50 W DC, the argon flow rate is 60 sccm, the sputtering gas pressure is 0.4 Pa, the distance between the target and the substrate is 150 mm, and the sputtering time is 20 min to obtain a TiVZrNbTaMoB alloy layer with a thickness of 468 nm; turn off the DC power supply, rotate the substrate with the TiVZrNbTaMoB alloy layer above the W target, and perform sputtering of the W target. The sputtering parameters are: the sputtering power is 80 W RF, the argon flow rate is 60 sccm, the sputtering gas pressure is 1.0 Pa, the distance between the target and the substrate is 150 mm, and the sputtering time is 2 h to obtain a W layer with a thickness of 273 nm; turn off the RF power supply, rotate the substrate with the two-layer film above the TiVZrNbTaMoB alloy target again, and repeat the sputtering step of the TiVZrNbTaMoB alloy target to obtain a TiVZrNbTaMoB alloy layer with a thickness of 463 nm again. The obtained three-layer film is a titanium-based high-entropy amorphous / tungsten multi-layer film with the potential of anti-irradiation and low hydrogen retention (i.e., three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film).

[0068] Comparative Example 1

[0069] Same as Example 1, the difference is that the specific steps of step (3) are: Use a mechanical pump and a molecular pump to evacuate the inside of the magnetron sputtering chamber to 8×10 -4pa, and then place the TiVZrNbTaMoB alloy target inside the magnetron sputtering chamber; using the (111) crystal orientation of the silicon wafer as the substrate, sputter the TiVZrNbTaMoB alloy target on the substrate. The sputtering parameters are as follows: the power is 50 W DC, the argon gas flow rate is 60 sccm, the sputtering gas pressure is 0.4 pa, the distance between the target and the substrate is 150 mm, and the sputtering time is 20 min, to obtain a TiVZrNbTaMoB alloy layer with a thickness of 468 nm. The obtained single-layer film is the single-layer TiVZrNbTaMoB film.

[0070] Comparative Example 2

[0071] Same as Example 1, the difference is that the specific steps of step (3) are: evacuate the inside of the magnetron sputtering chamber to 8×10 -4 pa by a mechanical pump and a molecular pump, and then place the W target inside the magnetron sputtering chamber; using the (111) crystal orientation of the silicon wafer as the substrate, sputter the W target on the substrate. The sputtering parameters are: the sputtering power is 80 W RF, the argon gas flow rate is 60 sccm, the sputtering gas pressure is 1.0 pa, the distance between the target and the substrate is 150 mm, and the sputtering time is 2 h, to obtain a W layer with a thickness of 273 nm. The obtained single-layer film is the single-layer W film.

[0072] Performance test:

[0073] 1. Perform ion irradiation experiments on the films prepared in Example 1, Comparative Example 1, and Comparative Example 2 on an ion irradiation experiment platform. The size of the experimental sample is 10×6×0.5 mm. The irradiation ion source is selected as hydrogen ions, and the ion acceleration energies are 100 MeV and 300 MeV. The irradiation doses are 4.4×10 11 ions / cm 2 and 1.4×10 12 ions / cm 2 . All irradiation experiments are carried out at room temperature.

[0074] Figure 1 The hydrogen ion irradiation damage of the single-layer TiVZrNbTaMoB film (HEMC), single-layer W film (W), and three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film (HEMC-WHEMC) simulated by SRIM software. Analyzing from the irradiation damage path length, it can be seen that at the same irradiation energy, the three films have irradiation damage paths of 2.18, 3.64, and 2.82 μm respectively. The longer the irradiation damage path, the more dispersed the irradiation energy, and thus it is not easy to concentrate a large amount of damage in a certain area inside the irradiated material. Therefore, it can be found that through the design of the multi-layer film structure in the present invention, the anti-irradiation performance of the film is improved.

[0075] Figure 2 The hydrogen ion retention amounts of the single-layer TiVZrNbTaMoB thin film, single-layer W thin film, and three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB thin film simulated by SRIM software. Table 1 shows the summary results of all retention amounts.

[0076] Table 1 Hydrogen ion retention amounts of different thin films at irradiation doses of 1 dpa, 3 dpa, and 5 dpa

[0077]

[0078] Note: "HEMG" represents "single-layer TiVZrNbTaMoB thin film", "W" represents "single-layer W thin film", and "HEMG-W-HEMG" represents "three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB thin film".

[0079] Analysis from the perspective of hydrogen retention amount shows that the hydrogen retention amounts of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB thin film at 1 dpa, 3 dpa, and 5 dpa are 0.08%, 0.24%, and 0.399% respectively. While for pure W under the same irradiation damage, the retention amounts are 0.751%, 2.292%, and 3.82%. The hydrogen retention amount of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB thin film is only 10.65% of that of the single-layer pure W thin film, which indicates that through the specific design of the three-layer thin film structure in the present invention, the problem of hydrogen retention inside the material can be effectively reduced.

[0080] 2. To study the phase evolution behavior of the TiVZrNbTaMoB / W / TiVZrNbTaMoB multi-layer thin film before and after hydrogen ion irradiation, the present invention carried out X-ray diffraction (XRD) phase analysis on the pure amorphous TiVZrNbTaMoB thin film, unirradiated multi-layer thin film, and multi-layer thin film after being irradiated with 100 MeV and 300 MeV hydrogen ions. The present invention used the grazing incidence mode of a Rigaku SmartLab X-ray diffractometer to perform X-ray diffraction analysis (X-Ray Diffraction, XRD) on the multi-layer thin film samples before and after irradiation, and obtained GIXRD diffraction patterns. The equipment selected a Cu target, with a working voltage of 40 KV, a working current of 150 mA, and a maximum power of 9 KW. The grazing angle was adjusted to 0.8°, the scanning range was 20° - 80°, the scanning speed was 5° / min, and a sample signal point was collected every 0.02 degrees.

[0081] Figure 3This is the XRD pattern of the as - deposited state of the three - layer TiVZrNbTaMoB / W / TiVZrNbTaMoB thin film of the present invention, as well as the XRD patterns after being irradiated by 100 MeV and 300 MeV hydrogen ions, and the XRD pattern of the as - deposited state of the single - layer TiVZrNbTaMoB thin film. It can be seen from the XRD spectra that there are no obvious diffraction peaks in the diffraction angle 2θ range for the pure amorphous TiVZrNbTaMoB thin film, indicating that its structure is amorphous. In the multi - layer thin film, it can be found that TiVZrNbTaMoB remains amorphous within 35 - 45°. After being irradiated by 100 MeV and 300 MeV hydrogen ions, the amorphous TiVZrNbTaMoB layer does not crystallize and still maintains an amorphous structure. For the un - irradiated TiVZrNbTaMoB / W / TiVZrNbTaMoB multi - layer thin film, obvious tungsten (W) diffraction peaks appear in the XRD pattern, indicating that the tungsten layer maintains a crystalline structure in the multi - layer thin film. By comparing with the standard PDF card, it can be known that there are two crystal orientations for the un - irradiated tungsten, which are the (110) crystal orientation and the (211) crystal orientation. In addition, after being irradiated by 100 MeV and 300 MeV hydrogen ions, the (110) crystal orientation and the (211) crystal orientation of the tungsten diffraction peaks in the multi - layer thin film still exist, and when the irradiation energy increases to 300 MeV, a new (200) crystal orientation appears in the multi - layer thin film.

[0082] 3. The cross - sectional morphology of the multi - layer thin film was observed using a Zeiss high - resolution field - emission scanning electron microscope (SEM) G300. This device has an acceleration voltage range of 20 - 30 kV, can provide high - resolution surface morphology images, and is suitable for the characterization of micro - and nano - scale structures. During the experiment, the sample was fixed on the sample stage, and good electrical contact was ensured through conductive glue to avoid the influence of charge accumulation on the imaging quality. The signal mode was selected as the secondary electron mode (SE), which has a high sensitivity to the morphological features of the sample surface and can clearly present the microscopic structural details of the sample surface, such as grains, cracks, holes, etc.

[0083] Figure 4This is the cross-sectional scanning image of the original state of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film of the present invention and after being irradiated by 100 MeV and 300 MeV hydrogen ions. It can be seen from the SEM cross-sectional image that the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film shows a clear layered structure before and after irradiation, the interfaces between layers are distinct, and no obvious defects such as cracks, voids or delamination are observed. And the tungsten layer is brighter, which is due to the relatively large atomic number of tungsten itself. The multi-layer film still maintains good structural integrity and interfacial bonding strength after hydrogen ion irradiation. Specifically, the interface between the TiVZrNbTaMoB layer and the W layer has not changed significantly before and after irradiation, indicating that the irradiation does not cause obvious damage or failure in the interfacial region. This phenomenon may be related to the high radiation resistance of the TiVZrNbTaMoB / W multi-layer film. Due to its multi-principal element design, the high-entropy alloy TiVZrNbTaMoB layer can effectively absorb the point defects generated by irradiation, while the tungsten (W) layer further enhances the overall damage resistance of the multi-layer film due to its high melting point and good radiation resistance.

[0084] In summary, through the design of the multi-layer film structure, the present invention changes the irradiation damage path. At the same irradiation energy, the irradiation damage path length of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film is 3.64 μm, compared with 2.82 μm of the single-layer TiVZrNbTaMoB film and 2.18 μm of the single-layer W film, which makes the irradiation energy more dispersed and not easy to concentrate and cause large damage in a certain area inside the material, effectively improving the radiation resistance of the film.

[0085] The specific design of the three-layer film structure significantly reduces the hydrogen retention amount inside the material. At the irradiation doses of 1 dpa, 3 dpa and 5 dpa, the hydrogen retention amounts of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film are 0.08%, 0.24% and 0.399% respectively, which is only 10.65% of the hydrogen retention amount of the single-layer pure W film, effectively solving the problem of hydrogen retention.

[0086] After being irradiated by 100 MeV and 300 MeV hydrogen ions, the TiVZrNbTaMoB amorphous layer still maintains the amorphous structure, the tungsten layer maintains the crystalline structure and new crystal orientations appear, and no obvious defects such as cracks, voids or delamination are observed in the overall film, the interfaces between layers are distinct, and good structural integrity and interfacial bonding strength are maintained.

[0087] The above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A titanium-based high-entropy amorphous / tungsten multilayer film with anti-irradiation and low hydrogen retention potential, characterized in that, It successively includes a first TiVZrNbTaMoB alloy layer, a W layer, and a second TiVZrNbTaMoB alloy layer from bottom to top. Among them, the atomic percentages of the TiVZrNbTaMoB alloy in the first TiVZrNbTaMoB alloy layer and the second TiVZrNbTaMoB alloy layer are: Ti: 45 - 50%, V: 20 - 30%, Zr: 8 - 15%, Nb: 10 - 20%, Ta: 0.5 - 3%, Mo: 0.3 - 1%, B: 0.1 - 0.3%.

2. The titanium-based high-entropy amorphous / tungsten multi-layer thin film with anti-irradiation and low hydrogen retention potential according to claim 1, wherein, The raw materials of the first TiVZrNbTaMoB alloy layer and the second TiVZrNbTaMoB alloy layer are TiVZrNbTaMoB alloy targets. The specific preparation method includes the following steps: Weigh elements Ti, V, Zr, Nb, Ta, Mo, and B according to the stoichiometric ratio, mix and ball-mill them to obtain alloy raw materials, and place the alloy raw materials in a vacuum hot-pressing sintering furnace for hot-pressing sintering to obtain TiVZrNbTaMoB alloy targets.

3. The titanium-based high-entropy amorphous / tungsten multi-layer film with anti-irradiation and low hydrogen retention potential according to claim 2, characterized in that The conditions for the ball-milling are: the rotational speed of the ball mill is 300 rpm, the mass ratio of balls to materials is 1:10, and the ball-milling time is 24 h; and / or The process of hot pressing sintering is as follows: evacuate to 1×10 -3 Pa, heat up to 600 - 800 °C at a heating rate of 10 °C / min for pre-sintering, keep warm for 30 min, then heat up to 1200 - 1400 °C at a heating rate of 5 - 10 °C / min, apply axial pressure after reaching the target temperature, and keep warm at the target temperature for 1 - 3 h, cool down with the furnace to below 200 °C, turn off the heating and pressure systems, and continue to evacuate and cool down to room temperature; the pressure is 30 - 50 MPa; and / or, The thickness of the TiVZrNbTaMoB alloy target is 4 mm, and the diameter is 5 cm.

4. The titanium-based high-entropy amorphous / tungsten multi-layer thin film with anti-irradiation and low hydrogen retention potential according to claim 1, wherein The raw material of the W layer is a W target. The specific preparation method includes the following steps: Weigh element W, ball-mill it, and then place it in a vacuum hot-pressing sintering furnace for hot-pressing sintering to obtain a W target.

5. The titanium-based high-entropy amorphous / tungsten multi-layer film with anti-irradiation and low hydrogen retention potential according to claim 4, characterized in that The conditions for the ball-milling are: the rotational speed of the ball mill is 300 rpm, the mass ratio of balls to materials is 1:10, and the ball-milling time is 24 h; and / or The process of hot pressing and sintering is as follows: evacuate to 1×10 -3 Pa, heat up to 600 - 800 °C at a heating rate of 10 °C / min for pre-sintering, hold for 30 min, then heat up to 1800 - 2000 °C at a heating rate of 5 - 10 °C / min, apply axial pressure after reaching the target temperature, and hold at the target temperature for 1 - 3 h, cool in the furnace to below 200 °C, turn off the heating and pressure systems, and continue to evacuate and cool to room temperature; the pressure is 40 - 60 MPa; and / or, The thickness of the W target is 4 mm, and the diameter is 5 cm.

6. A method for preparing a titanium-based high-entropy amorphous / tungsten multilayer film with anti-irradiation and low hydrogen retention potential as described in any one of claims 1-5, characterized in that, It includes the following steps Place the TiVZrNbTaMoB alloy target and the W target respectively inside the magnetron sputtering cavity evacuated to 8×10 -4 Pa. Using the (111) crystal orientation of a silicon wafer as the substrate, sputter the TiVZrNbTaMoB alloy target on the substrate to obtain the first TiVZrNbTaMoB alloy layer; Turn off the DC power supply, rotate the substrate above the W target, and sputter the W target to obtain the W layer; Turn off the RF power supply, rotate the substrate above the TiVZrNbTaMoB alloy target again, and repeat the sputtering step of the TiVZrNbTaMoB alloy target to prepare the second TiVZrNbTaMoB alloy layer. The obtained three-layer film is the titanium-based high-entropy amorphous / tungsten multi-layer film with anti-irradiation and low hydrogen retention potential.

7. The preparation method of the titanium-based high-entropy amorphous / tungsten multi-layer film with anti-irradiation and low hydrogen retention potential according to claim 6, characterized in that The thicknesses of the first TiVZrNbTaMoB alloy layer and the second TiVZrNbTaMoB alloy layer are 400 - 500 nm; and / or The thickness of the W layer is 200 - 300 nm.

8. The preparation method of the titanium-based high-entropy amorphous / tungsten multi-layer thin film with anti-irradiation and low hydrogen retention potential according to claim 6, characterized in that, The sputtering conditions of the TiVZrNbTaMoB alloy target are as follows: the power is 50 W DC, the argon flow rate is 60 sccm, the sputtering gas pressure is 0.4 Pa, the distance between the target and the substrate is 150 mm, and the sputtering time is 20 min.

9. The preparation method of the titanium-based high-entropy amorphous / tungsten multi-layer thin film with anti-irradiation and low hydrogen retention potential according to claim 6, characterized in that, The sputtering conditions of the W target are: the sputtering power is 80 W RF, the argon flow rate is 60 sccm, the sputtering gas pressure is 1.0 Pa, the distance between the target and the substrate is 150 mm, and the sputtering time is 2 h.

10. Use of a titanium-based high-entropy amorphous / tungsten multilayer thin film having anti-irradiation and low hydrogen retention potential as described in any one of claims 1-5 in the preparation of materials for extreme irradiation environments, characterized in that The extreme irradiation environment materials include nuclear reactor first wall materials, fusion reactor blanket materials, or nuclear fuel cladding coating materials.

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