A titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential, and its preparation method and application

Abstract

The present invention discloses a titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential, as well as its preparation method and application, belonging to the field of nuclear energy material technology. The titanium-based high-entropy amorphous / tungsten multilayer film comprises, from bottom to top, a first TiVZrNbTaMoB alloy layer, a W layer, and a second TiVZrNbTaMoB alloy layer. The atomic percentages of the 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%, and B: 0.1-0.3%. The preparation process mainly adopts magnetron sputtering. The resulting multilayer film has radiation resistance and low hydrogen retention potential.

Description

Technical Field

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

[0002] In nuclear fusion reactors, materials are exposed to long-term irradiation from high-energy particles (such as neutrons, hydrogen isotopes, helium ions, etc.), which causes radiation damage to the materials (such as vacancies, interstitial atoms, bubbles, etc.). Radiation damage to traditional materials (such as stainless steel, tungsten, etc.) under high-dose irradiation can easily induce problems such as hardening, embrittlement, and swelling. Inside the fusion reactor, the self-sustaining problem of hydrogen isotope "tritium" is also raised, which requires the materials inside the fusion reactor to have a low tritium retention. This allows "tritium" to be self-sustaining and reduces the problems of hydrogen embrittlement and mechanical property degradation caused by hydrogen isotope penetration and aggregation inside the material.

[0003] High-entropy metallic glasses (HEMGs) exhibit more uniform, denser, and locally more ordered atomic arrangements than conventional metallic glasses. Due to their high mixing entropy, atomic diffusion takes time and mobility is limited, thus hindering crystallization dynamics and complicating the formation and development of crystal nuclei. In addition, continuous polycrystalline phase transitions are observed in HEMGs, which allows the system to achieve structural diversity while maintaining a consistent chemical composition, thereby significantly improving thermal stability. This high thermal stability and the complexity of crystallization dynamics give HEMGs excellent radiation resistance.

[0004] However, while high-entropy metallic glass (HEMG) films have shown some potential for radiation resistance, their single structure struggles to balance radiation damage resistance with hydrogen retention control. Conventional single-element multilayer films (such as W / Ti) are prone to delamination and failure after irradiation due to weak interfacial bonding, making them unsuitable for service. Therefore, it is necessary to develop a new multilayer film material that combines high radiation resistance with low hydrogen retention and interfacial stability. Summary of the Invention

[0005] In response to the above technical problems, the present invention proposes a titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential, as well as 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 multilayer film with radiation resistance and low hydrogen retention potential, which comprises, from bottom to top, a first TiVZrNbTaMoB alloy layer, a W layer, and a second TiVZrNbTaMoB alloy layer, wherein the atomic percentage of the TiVZrNbTaMoB alloy in the first TiVZrNbTaMoB alloy layer and the second TiVZrNbTaMoB alloy layer is: Ti: 45-50%, V: 20-30%, Zr: 8-15%, Nb: 10-20%, Ta: 0.5-3%, Mo: 0.3-1%, and B: 0.1-0.3%.

[0008] The TiVZrNbTaMoB alloy comprises multiple main elements (Ti, V, Zr, Nb, Ta, Mo, and B) in specific atomic percentages to form a high-entropy alloy. The high mixing entropy of the high-entropy alloy limits atomic diffusion, hinders crystallization kinetics, and complicates nucleation and growth, resulting in excellent radiation resistance. Furthermore, its structural characteristics help absorb point defects generated by radiation. In the three-layer film structure, the upper and lower TiVZrNbTaMoB alloy layers leverage the radiation resistance of the high-entropy alloy, while the middle W layer, with its high melting point and excellent radiation resistance, enhances the overall damage resistance. This synergistic effect results in a multilayer film with superior radiation resistance compared to a single layer. Regarding hydrogen retention, the multilayer structure hinders hydrogen diffusion and aggregation, effectively reducing hydrogen retention compared to a single layer. TiVZrNbTaMoB remains amorphous within the multilayer film and does not crystallize even after irradiation, ensuring its structural stability. The tungsten layer maintains a crystalline structure within the multilayer film and develops new crystal orientations after irradiation, further enhancing the film's stability. This stable physical structure is the foundation for the excellent performance of the multilayer film. The film exhibits distinct interfaces between layers, with no significant damage or failure observed before or after irradiation. The tight interface between the high-entropy alloy TiVZrNbTaMoB layer and the tungsten layer effectively transfers stress, improving the film's overall performance and enhancing its radiation resistance 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, placing the alloy raw materials in a vacuum hot pressing sintering furnace for hot pressing sintering to obtain a TiVZrNbTaMoB alloy target.

[0010] Furthermore, the ball milling conditions are: ball mill speed 300 rpm, ball-to-material mass ratio 1:10, ball milling time 24 h; and / or,

[0011] The hot pressing sintering process is as follows: vacuuming to 1×10 -3 Pa, heating to 600-800°C at a heating rate of 10°C / min for pre-sintering, holding at that temperature for 30 minutes, then heating to 1200-1400°C at a heating rate of 5-10°C / min, applying axial pressure after reaching the target temperature, holding at the target temperature for 1-3 hours, cooling with the furnace to below 200°C, turning off the heating and pressure systems, and continuing to evacuate and cool to room temperature; the pressure is 30-50 MPa; and / or,

[0012] The TiVZrNbTaMoB alloy target has a thickness of 4 mm and a diameter of 5 cm.

[0013] Furthermore, 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: weighing the W element, ball milling, and then placing it in a vacuum hot pressing sintering furnace for hot pressing sintering to obtain the W target.

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

[0015] The hot pressing sintering process is as follows: vacuuming to 1×10 -3 Pa, heating to 600-800°C at a heating rate of 10°C / min for pre-sintering, holding at that temperature for 30 minutes, then heating to 1800-2000°C at a heating rate of 5-10°C / min, applying axial pressure after reaching the target temperature, holding at the target temperature for 1-3 hours, cooling with the furnace to below 200°C, turning off the heating and pressure systems, and continuing to evacuate and cool to room temperature; the pressure is 40-60MPa; and / or,

[0016] The W target has a thickness of 4 mm and a diameter of 5 cm.

[0017] A second object of the present invention is to provide a method for preparing a titanium-based high-entropy amorphous / tungsten multilayer film having radiation resistance and low hydrogen retention potential, comprising the following steps:

[0018] (1) TiVZrNbTaMoB alloy target and W target were placed in a vacuum chamber to 8×10 -4 Inside the magnetron sputtering chamber of pa;

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

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

[0021] (4) Turn off the RF power supply, rotate the substrate again above the TiVZrNbTaMoB alloy target, repeat the sputtering step of the TiVZrNbTaMoB alloy target, and prepare a second TiVZrNbTaMoB alloy layer. The resulting three-layer film is a titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential.

[0022] Further, 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: DC power of 50 W, argon flow rate of 60 sccm, sputtering pressure of 0.4 Pa, distance between the target and the substrate of 150 mm, and sputtering time of 20 min.

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

[0026] A third object of the present invention is to provide a titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential for use in the preparation of extreme radiation environment materials, including: nuclear reactor first wall materials, fusion reactor blanket materials or nuclear fuel cladding coating materials.

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

[0028] The present invention effectively disperses the radiation energy and reduces the concentrated area of ​​radiation damage through the multi-layer film structure design, thereby significantly improving the radiation resistance of the film.

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

[0030] Even after high-energy hydrogen ion irradiation, the multilayer film prepared by the present invention can still maintain a clear layered structure with distinct interfaces, without defects such as cracks, voids or delamination, showing excellent radiation resistance and interface stability.

[0031] The multilayer film provided by the present invention can be applied to the first wall material of nuclear reactors, fusion reactor cladding material and nuclear fuel cladding coating material, providing a new high-performance material option for the development of nuclear energy technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The accompanying drawings, which constitute part of the present invention, are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are provided to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0033] Figure 1 The hydrogen ion irradiation damage of single-layer TiVZrNbTaMoB film, single-layer W film, and triple-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film simulated by SRIM software;

[0034] Figure 2 The hydrogen ion retention of single-layer TiVZrNbTaMoB film, single-layer W film, and triple-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film simulated using SRIM software;

[0035] Figure 3 The XRD patterns of the original state of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film of the present invention and after 100MeV and 300MeV hydrogen ion irradiation, and the original state XRD pattern of the single-layer TiVZrNbTaMoB film;

[0036] Figure 4 These are cross-sectional scans of the original state of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film of the present invention and after irradiation with 100MeV and 300MeV hydrogen ions. DETAILED DESCRIPTION

[0037] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0038] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0039] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0040] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0041] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0042] The present invention achieves the following synergistic effects by designing a three-layer structure of "amorphous HEMG / crystalline W / amorphous HEMG" and combining the radiation resistance of high-entropy amorphous alloys with the high stability of tungsten:

[0043] Radiation resistance: multi-layer energy dispersion + amorphous defect self-repair + tungsten layer resistance to high temperature;

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

[0045] The experimental data verified the potential of this design in extreme nuclear energy environments (such as the first wall of a fusion reactor) and provided new ideas for the development of high-performance radiation-resistant materials.

[0046] An embodiment of the present invention provides a method for preparing a titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential, which is prepared using a TiVZrNbTaMoB alloy target and a W target as raw materials, and specifically includes the following steps:

[0047] (1) Preparation of TiVZrNbTaMoB alloy target: Ti, V, Zr, Nb, Ta, Mo and B elements are weighed in a stoichiometric ratio, mixed and ball-milled to obtain an alloy raw material, and the alloy raw material is placed in a vacuum hot pressing sintering furnace for hot pressing sintering to obtain a TiVZrNbTaMoB alloy target;

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

[0049] (3) TiVZrNbTaMoB alloy target and W target were placed in a vacuum chamber to 8×10 -4 The invention relates to a method for preparing a titanium-based high-entropy amorphous / tungsten multilayer film having a pa structure (vacuumed by a mechanical pump and a molecular pump); taking a silicon wafer (111) crystal orientation as a substrate, sputtering a TiVZrNbTaMoB alloy target on the substrate to obtain a TiVZrNbTaMoB alloy layer; turning off a DC power supply, rotating the substrate above a W target, sputtering the W target to obtain a W layer; turning off a radio frequency power supply, rotating the substrate again above the TiVZrNbTaMoB alloy target, repeating the sputtering step of the TiVZrNbTaMoB alloy target, and obtaining a TiVZrNbTaMoB alloy layer again. The obtained three-layer film is a titanium-based high-entropy amorphous / tungsten multilayer film (note: TiVZrNbTaMoB / W / TiVZrNbTaMoB film) with radiation resistance and low hydrogen retention potential. During the entire sputtering process, the substrate is always in a rotating state to ensure that the thickness of the obtained three-layer film is uniform.

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

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

[0052] In the following preferred embodiment of the present invention, the hot pressing sintering process in step (1) is as follows: vacuuming to 1×10 - 3Pa (the purpose of vacuuming is to remove oxygen and volatile impurities), and then pre-sintering at a heating rate of 10°C / min to 600-800°C (preferably 700°C). The temperature is then held at this temperature for 30 minutes (the purpose of pre-sintering is to further degas and activate the powder surface). Subsequently, the temperature is increased to 1200-1400°C (preferably 1300°C) at a heating rate of 5-10°C / min (preferably 8°C / min). After reaching the target temperature, axial pressure is applied (maintaining constant pressure is to ensure sufficient diffusion and densification of the powder). The target temperature is then held for 1-3 hours (preferably 2 hours). The furnace is then cooled to below 200°C, the heating and pressure systems are turned off, and the vacuum is continued to cool to room temperature; the pressure is 30-50 MPa (preferably 40 MPa). After demolding, ultrasonic cleaning is used to remove residual release agent on the surface. After demolding, the sintered alloy ingot is processed to the target material design size using wire cutting.

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

[0054] In the following preferred embodiment of the present invention, the hot pressing sintering process in step (2) is as follows: vacuuming to 1×10 - 3 Pa (the purpose of vacuuming is to remove oxygen and volatile impurities), heat to 600-800℃ (more preferably 700℃) at a heating rate of 10℃ / min for pre-sintering, keep warm for 30min (the purpose of pre-sintering is to further degas and activate the powder surface), then heat to 1800-2000℃ (more preferably 2000℃) at a heating rate of 5-10℃ / min (more preferably 8℃ / min), apply axial pressure after reaching the target temperature (the pressure is constant, the purpose of maintaining constant pressure is to ensure sufficient diffusion and densification of the powder), and keep warm at the target temperature for 1-3h (more preferably 2h), cool to below 200℃ with the furnace, turn off the heating and pressure system, and continue to vacuum cool to room temperature; the pressure is 40-60MPa (more preferably 50MPa). After demolding, ultrasonic cleaning is used to remove residual release agent on the surface. After demolding, wire cutting is used to process the sintered W to the target design size.

[0055] In the following preferred embodiment of the present invention, the W target material in step (2) has a thickness of 4 mm and a diameter of 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: DC power 50 W, argon flow rate 60 sccm, sputtering pressure 0.4 Pa, distance between the target and the substrate 150 mm, and sputtering time 20 min.

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

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

[0061] The raw materials used in the present invention are all purchased from the market.

[0062] The technical solution of the present invention is further illustrated by the following examples.

[0063] Example 1

[0064] A method for preparing a titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential, specifically comprising the following steps:

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

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

[0067] (3) The interior of the magnetron sputtering chamber was evacuated to 8×10 -4 pa, then place the TiVZrNbTaMoB alloy target and the W target in the magnetron sputtering chamber respectively; take the silicon wafer (111) crystal orientation as the substrate, and sputter the TiVZrNbTaMoB alloy target on the substrate, and the sputtering parameters are: DC power 50W, argon flow rate 60sccm, sputtering pressure 0.4pa, the distance between the target and the substrate is 150mm, and the sputtering time is 20min, to obtain a TiVZrNbTaMoB alloy layer with a thickness of 468nm; turn off the DC power supply, rotate the substrate containing the TiVZrNbTaMoB alloy layer to the top of the W target, and sputter the W target, and the sputtering parameters are: sputtering power is The RF was 80W, the argon flow rate was 60sccm, the sputtering pressure was 1.0Pa, the distance between the target and the substrate was 150mm, and the sputtering time was 2h to obtain a W layer with a thickness of 273nm; the RF power was turned off, and the substrate containing the two thin films was rotated again above the TiVZrNbTaMoB alloy target, and the sputtering step of the TiVZrNbTaMoB alloy target was repeated to obtain a TiVZrNbTaMoB alloy layer with a thickness of 463nm again. The obtained three-layer thin film is a titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential (i.e., a three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film).

[0068] Comparative Example 1

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

[0070] Comparative Example 2

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

[0072] Performance testing:

[0073] 1. The films prepared in Example 1, Comparative Example 1 and Comparative Example 2 were subjected to ion irradiation experiments in an ion irradiation experimental platform. The experimental sample size was 10×6×0.5 mm, the irradiation ion source was hydrogen ion, and the ion acceleration energy was 100 MeV and 300 MeV. The irradiation doses were 4.4×10 11 ions / cm 2 and 1.4×10 12 ions / cm 2 All irradiation experiments were performed at room temperature.

[0074] Figure 1 This simulation uses SRIM software to simulate hydrogen ion irradiation damage in a single-layer TiVZrNbTaMoB film (HEMC), a single-layer W film (W), and a three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film (HEMC-WHEMC). Analysis of the irradiation damage path lengths reveals that, at the same irradiation energy, the three films exhibit irradiation damage paths of 2.18, 3.64, and 2.82 μm, respectively. Longer irradiation damage paths indicate more dispersed irradiation energy, making it less likely that significant damage will be concentrated in a single area within the irradiated material. Therefore, it can be seen that the present invention improves the film's radiation resistance through the design of a multilayer film structure.

[0075] Figure 2 The hydrogen ion retention of a single-layer TiVZrNbTaMoB film, a single-layer W film, and a triple-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film simulated using SRIM software is shown in Table 1. The retention results are summarized in Table 1.

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

[0077]

[0078] Note: “HEMG” means “single-layer TiVZrNbTaMoB thin film”, “W” means “single-layer W thin film”, and “HEMG-W-HEMG” means “triple-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB thin film”.

[0079] From the perspective of hydrogen retention, it can be found that the hydrogen retention of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film at 1 dpa, 3 dpa and 5 dpa is 0.08%, 0.24% and 0.399%, respectively, while the retention of pure W under the same radiation damage is 0.751%, 2.292% and 3.82%. The hydrogen retention of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film is only 10.65% of that of the single-layer pure W film, which shows that the present invention can effectively reduce the problem of hydrogen retention inside the material through the specific three-layer film structure design.

[0080] 2. In order to study the phase evolution behavior of TiVZrNbTaMoB / W / TiVZrNbTaMoB multilayer films before and after hydrogen ion irradiation, the present invention performed X-ray diffraction (XRD) phase analysis on pure amorphous TiVZrNbTaMoB films, unirradiated multilayer films, and multilayer films irradiated with 100MeV and 300MeV hydrogen ions. The present invention uses the grazing incidence mode of the RigakuSmartLab X-ray diffractometer to perform X-ray diffraction analysis (XRD) on the multilayer film samples before and after irradiation to obtain GIXRD diffraction patterns. The equipment uses Cu target material, the operating voltage is 40KV, the operating current is 150mA, and the maximum power is 9KW. The grazing angle is adjusted to 0.8°, the scanning range is 20°-80°, the scanning speed is 5° / min, and a sample signal point is collected every 0.02 degrees.

[0081] Figure 3The XRD patterns of the original state of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film of the present invention and after 100MeV and 300MeV hydrogen ion irradiation, as well as the original state XRD pattern of the single-layer TiVZrNbTaMoB film, are shown. As can be seen from the XRD spectrum, the pure amorphous TiVZrNbTaMoB film does not show obvious diffraction peaks within the diffraction angle range of 2θ, indicating that its structure is amorphous. In the multilayer film, it can be found that TiVZrNbTaMoB remains amorphous within 35-45°. After 100MeV and 300MeV hydrogen ion irradiation, the TiVZrNbTaMoB amorphous layer does not crystallize and still maintains an amorphous structure. In contrast, for the unirradiated TiVZrNbTaMoB / W / TiVZrNbTaMoB multilayer film, a clear tungsten (W) diffraction peak appears in the XRD spectrum, indicating that the tungsten layer maintains a crystalline structure in the multilayer film. Comparison with standard PDF cards reveals that unirradiated tungsten exhibits two crystal orientations: (110) and (211). Furthermore, after 100MeV and 300MeV hydrogen ion irradiation, the tungsten diffraction peaks in the multilayer film at the (110) and (211) directions still persist. Furthermore, when the irradiation energy is increased to 300MeV, a new (200) crystal orientation emerges in the multilayer film.

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

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

[0084] In summary, the present invention alters the radiation damage path through multilayer thin film design. Under the same radiation energy, the radiation damage path length of the three-layer TiVZrNbTaMoB / W / TiVZrNbTaMoB film is 3.64μm, compared to 2.82μm for a single-layer TiVZrNbTaMoB film and 2.18μm for a single-layer W film. This makes the radiation energy more dispersed, making it less likely to cause significant damage concentrated in a single area within the material, effectively improving the film's radiation resistance.

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

[0086] After irradiation with 100MeV and 300MeV hydrogen ions, the TiVZrNbTaMoB amorphous layer still maintains an amorphous structure, the tungsten layer maintains a crystalline structure and shows new crystal orientations. The overall film does not show obvious defects such as cracks, voids or delamination. The interfaces between the layers are clear, maintaining good structural integrity and interface bonding strength.

[0087] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential, characterized in that: From bottom to top, there are a first TiVZrNbTaMoB alloy layer, a W layer and a second TiVZrNbTaMoB alloy layer, wherein 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%, and B: 0.1-0.3%.

2. The titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential according to claim 1, characterized in that: 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: weighing Ti, V, Zr, Nb, Ta, Mo and B elements according to the stoichiometric ratio, mixing and ball milling to obtain alloy raw materials, placing the alloy raw materials in a vacuum hot pressing sintering furnace for hot pressing sintering to obtain the TiVZrNbTaMoB alloy target.

3. The titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential according to claim 2, characterized in that: The ball milling conditions are: ball mill speed 300 rpm, ball to material mass ratio 1:10, ball milling time 24 h; and / or, The hot pressing sintering process is as follows: vacuuming to 1×10 -3 Pa, heating to 600-800°C at a heating rate of 10°C / min for pre-sintering, holding at that temperature for 30 minutes, then heating to 1200-1400°C at a heating rate of 5-10°C / min, applying axial pressure after reaching the target temperature, holding at the target temperature for 1-3 hours, cooling with the furnace to below 200°C, turning off the heating and pressure systems, and continuing to evacuate and cool to room temperature; the pressure is 30-50 MPa; and / or, The TiVZrNbTaMoB alloy target has a thickness of 4 mm and a diameter of 5 cm.

4. The titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential according to claim 1, characterized in that: The raw material of the W layer is a W target material, and the specific preparation method includes the following steps: weighing W element, ball milling, and then placing it in a vacuum hot pressing sintering furnace for hot pressing sintering to obtain the W target material.

5. The titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential according to claim 4, characterized in that: The ball milling conditions are: ball mill speed 300 rpm, ball to material mass ratio 1:10, ball milling time 24 h; and / or, The hot pressing sintering process is as follows: vacuuming to 1×10 -3 Pa, heating to 600-800°C at a heating rate of 10°C / min for pre-sintering, holding at that temperature for 30 minutes, then heating to 1800-2000°C at a heating rate of 5-10°C / min, applying axial pressure after reaching the target temperature, holding at the target temperature for 1-3 hours, cooling with the furnace to below 200°C, turning off the heating and pressure systems, and continuing to evacuate and cool to room temperature; the pressure is 40-60MPa; and / or, The W target has a thickness of 4 mm and a diameter of 5 cm.

6. A method for preparing a titanium-based high-entropy amorphous / tungsten multilayer film having radiation resistance and low hydrogen retention potential according to any one of claims 1 to 5, characterized in that: The following steps are involved: The TiVZrNbTaMoB alloy target and W target were placed in a vacuum chamber at 8×10 -4 Inside the magnetron sputtering chamber of pa; Using a silicon wafer (111) in the crystal orientation as a substrate, sputtering a TiVZrNbTaMoB alloy target material on the substrate to obtain a first TiVZrNbTaMoB alloy layer; Turn off the DC power supply, rotate the substrate above the W target, and sputter the W target to obtain a W layer; The RF power supply is turned off, and the substrate is rotated again above the TiVZrNbTaMoB alloy target. The sputtering step of the TiVZrNbTaMoB alloy target is repeated to prepare a second TiVZrNbTaMoB alloy layer. The resulting three-layer film is a titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential.

7. The method for preparing a titanium-based high-entropy amorphous / tungsten multilayer film having radiation resistance and low hydrogen retention potential according to claim 6, characterized in that: The thickness of the first TiVZrNbTaMoB alloy layer and the second TiVZrNbTaMoB alloy layer is 400-500 nm; and / or, The thickness of the W layer is 200-300 nm.

8. The method for preparing a titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential according to claim 6, characterized in that: The sputtering conditions of the TiVZrNbTaMoB alloy target are: DC power of 50 W, argon flow rate of 60 sccm, sputtering pressure of 0.4 Pa, distance between the target and the substrate of 150 mm, and sputtering time of 20 min.

9. The method for preparing a titanium-based high-entropy amorphous / tungsten multilayer film having radiation resistance and low hydrogen retention potential according to claim 6, characterized in that: The sputtering conditions of the W target are as follows: sputtering power of 80 W RF, argon flow rate of 60 sccm, sputtering pressure of 1.0 Pa, distance between the target and substrate of 150 mm, and sputtering time of 2 h.

10. Use of the titanium-based high-entropy amorphous / tungsten multilayer film with radiation resistance and low hydrogen retention potential according to any one of claims 1 to 5 in the preparation of materials for extreme radiation environments, characterized in that: The extreme radiation environment material includes a nuclear reactor first wall material, a fusion reactor blanket material or a nuclear fuel cladding coating material.

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