Titanium-based high-entropy amorphous / oxide multilayer film with characteristics of radiation resistance and low hydrogen retention as well as preparation method and application of titanium-based high-entropy amorphous / oxide multilayer film

Abstract

The invention discloses a titanium-based high-entropy amorphous / oxide multilayer film with the characteristics of radiation resistance and low hydrogen retention as well as a preparation method and application of the titanium-based high-entropy amorphous / oxide multilayer film, and belongs to the technical field of nuclear energy materials. The titanium-based high-entropy amorphous / oxide multilayer film with the anti-irradiation and low-hydrogen retention characteristics sequentially comprises a first Al2O3 layer, a TiVZrNbTaMoB alloy layer and a second Al2O3 layer from bottom to top, and the TiVZrNbTaMoB alloy layer comprises, by atomic percent, 45%-50% of Ti, 20%-25% of V, 8%-12% of Zr, 12%-16% of Nb, 1%-3% of Ta, 0.3%-0.6% of Mo and 0.1%-0.3% of B. Through the high-entropy amorphous alloy-ceramic composite structure design and precise process control, collaborative optimization of the anti-irradiation performance and the low-hydrogen retention performance of the material is achieved, and the nuclear energy extreme environment service requirement is met.

Description

Technical Field

[0001] This invention belongs to the field of nuclear energy materials technology, and more specifically relates to a titanium-based high-entropy amorphous / oxide multilayer film with radiation resistance and low hydrogen retention characteristics, its preparation method and application. Background Technology

[0002] During the operation of nuclear fusion reactor systems, core structural materials are subjected to extreme environments for extended periods, including continuous bombardment by high-energy particles. The interaction between these particles and the materials leads to the formation of point defects. These defects further evolve, causing degradation of the material's microstructure and properties, ultimately resulting in material failure. This severely shortens the service life of nuclear energy equipment and hinders the safe and efficient operation of nuclear energy systems. To address these issues, researchers have proposed a technical approach to improve radiation resistance by increasing the density of interfaces within the material. This involves using interfaces as "defect traps" to capture irradiation-induced defects and promoting the migration of interstitial atoms to the interface, as well as the emission of interstitial atoms from the interface to annihilate vacancies, thereby suppressing defect accumulation. Against this backdrop, multilayer film materials, due to their ability to construct high-density interfaces through alternating stacking of components, show promising prospects for radiation-resistant applications. Since Koehler proposed the concept of nanolayered films, related research has developed various heterogeneous stacked systems, such as metal systems (e.g., Cu / Nb, Cu / W, Cu / V, Fe / W, Al / Nb, and V / Ag), ceramic systems (e.g., AlN / TiN and TiN / MgO), and metal-ceramic composite systems (e.g., Al / B4C and FeCr / TiO2). However, existing multilayered films still have significant drawbacks: metal-metal multilayered films, although exhibiting good interfacial bonding, suffer from an imbalance in the ratio of light to heavy elements, making it difficult to simultaneously meet the dual requirements of "low hydrogen retention" and "low radiation damage"; ceramic-ceramic multilayered films possess excellent chemical stability but are brittle, with interfacial stress concentration, making them prone to cracking after irradiation; traditional metal-ceramic multilayered films, due to poor component matching, are prone to diffusion or delamination at the interface, making them unable to maintain long-term stable operation under extreme irradiation environments.

[0003] High-entropy amorphous alloys, as a cross-product of high-entropy alloys and amorphous alloys, offer a new direction for the development of radiation-resistant materials due to their unique advantages of "high chemical disorder + compact topology". Their compositional complexity limits atomic diffusion, their structural disorder avoids radiation damage caused by crystal defects such as dislocations and stacking faults, and their stable amorphous boundaries (containing a large amount of free volume) can directly absorb radiation defects, significantly improving damage tolerance and effectively preventing grain growth under irradiation from damaging interface integrity. However, a single high-entropy amorphous alloy film cannot simultaneously achieve radiation resistance and other key properties (such as low tritium (hydrogen) retention). Under long-term irradiation, high-density interfaces are prone to failure due to component diffusion or stress release, requiring the combination with a highly compatible second-phase component to optimize performance. Meanwhile, nuclear fusion reactors face another core challenge: fusion fuel (hydrogen isotopes deuterium and tritium) easily penetrates into the interior of metallic structural materials, leading to fuel loss, hydrogen embrittlement damage, and potentially radioactive contamination. To address this issue, coating the surface of structural materials with a tritium barrier coating (TPB) has become a key technical approach. Oxide coatings have become the mainstream research direction for tritium barrier coatings due to their excellent tritium barrier properties. Reported oxide coatings include Al2O3, Er2O3, SiO2, and Cr2O3, among which α-Al2O3 stands out for its extremely high tritium barrier factor (up to 10). 5 It exhibits excellent overall performance due to its high hardness and superior thermodynamic stability. Furthermore, the interface of oxide ceramics can act as an "irradiation defect trap," suppressing irradiation-induced grain coarsening and further enhancing the material's resistance to radiation damage.

[0004] In summary, current technologies present several challenges: single high-entropy amorphous alloy films cannot simultaneously achieve both radiation resistance and low tritium (hydrogen) retention; traditional multilayer films (metal-metal, ceramic-ceramic, and ordinary metal-ceramic) suffer from poor interfacial stability and limited performance characteristics; while oxide coatings can block tritium, pure oxide films are brittle and have limited radiation resistance. Therefore, developing a multilayer film system combining a high-entropy amorphous alloy and oxide ceramics, leveraging the radiation resistance of high-entropy amorphous alloys and the tritium blocking and defect trapping advantages of oxide ceramics, while optimizing component matching to improve interfacial stability, is a key requirement for addressing the issues of extreme radiation and tritium (hydrogen) retention in nuclear energy materials. Summary of the Invention

[0005] The purpose of this invention is to provide a titanium-based high-entropy amorphous / oxide multilayer film with radiation resistance and low hydrogen retention properties, its preparation method, and its applications, thereby solving the problems existing in the prior art. This invention achieves synergistic optimization of the material's radiation resistance and low hydrogen retention properties through a composite structure design of "high-entropy amorphous alloy-ceramic" and precise process control, meeting the service requirements of extreme nuclear energy environments.

[0006] To achieve the above objectives, the present invention provides the following solution: One of the technical solutions of this invention is to provide a titanium-based high-entropy amorphous / oxide multilayer film with radiation resistance and low hydrogen retention characteristics, comprising, from bottom to top, a first Al2O3 layer, a TiVZrNbTaMoB alloy layer, and a second Al2O3 layer, wherein the atomic percentage of the TiVZrNbTaMoB alloy layer is: Ti: 45~50%, V: 20~25%, Zr: 8~12%, Nb: 12~16%, Ta: 1~3%, Mo: 0.3~0.6%, B: 0.1~0.3%.

[0007] The membrane described in this invention has a symmetrical three-layer composite structure, which is a "ceramic-high-entropy amorphous-ceramic" functional complementary system formed by the first Al2O3 layer, the TiVZrNbTaMoB alloy layer, and the second Al2O3 layer.

[0008] The TiVZrNbTaMoB alloy layer comprises multiple components—Ti, V, Zr, Nb, Ta, Mo, and B—forming a high-entropy amorphous alloy with specific atomic percentages. This alloy's high mixing entropy significantly restricts atomic diffusion rates, slows down crystallization kinetics, and increases the energy barrier for nucleation and growth, thus endowing the alloy with excellent intrinsic radiation resistance. Simultaneously, its disordered atomic packing structure provides numerous defect trapping sites, effectively absorbing defects generated during irradiation and reducing performance degradation caused by defect accumulation.

[0009] As a functional reinforcement layer, the Al2O3 layer, on the one hand, leverages the inherent high melting point and structural stability of ceramic materials to further enhance the overall radiation resistance of multilayer films; on the other hand, its dense crystalline structure can construct a physical barrier for hydrogen isotope diffusion, significantly reducing the penetration and aggregation of hydrogen atoms inside the film, while also helping to disperse irradiation energy through interfacial interactions, avoiding localized damage concentration.

[0010] This invention employs an alternating composite structure of "high-entropy amorphous alloy / ceramic (α-Al2O3)" to significantly reduce hydrogen retention in the material through the high density and excellent hydrogen barrier properties of the α-Al2O3 ceramic layer, while also maintaining radiation resistance. CN120291038A discloses a titanium-based high-entropy amorphous / tungsten multilayer thin film with radiation resistance and low hydrogen retention potential, its preparation method, and applications. This constructs a "high-entropy amorphous alloy / metal (W)" multilayer system, focusing more on utilizing the high melting point and radiation resistance of the tungsten layer to enhance overall radiation resistance; its hydrogen barrier properties are relatively weaker. Moreover, tungsten, as a high-melting-point metal, is itself an excellent radiation-resistant material. The structural design of the "high-entropy amorphous alloy / metal (W)" multilayer system aims to attract and recombine point defects generated by radiation through multilayer interfaces, extending the damage path. Alumina ceramics are recognized as highly efficient hydrogen barriers with extremely low permeability to hydrogen isotopes. The alternating composite structure design of the "high-entropy amorphous alloy / ceramic (α-Al2O3)" in this invention aims to use the ceramic layer as a physical barrier to fundamentally prevent the inward diffusion and retention of hydrogen isotopes.

[0011] Preferably, the thickness of the first Al2O3 layer and the second Al2O3 layer are independently 200~300nm; the thickness of the TiVZrNbTaMoB alloy layer is 300~350nm.

[0012] Preferably, the raw material for the first Al2O3 layer and the second Al2O3 layer is an Al2O3 target material; The Al2O3 target material has a thickness of 4 mm and a diameter of 5 cm; The preparation steps of the Al2O3 target are as follows: α-Al2O3 powder is sequentially ball-milled and vacuum hot-pressed to obtain the Al2O3 target; the purity of the α-Al2O3 powder is ≥99.99%.

[0013] Furthermore, the process before ball milling α-Al2O3 powder includes a raw material pretreatment process, specifically: after soaking α-Al2O3 powder in anhydrous ethanol for 2 hours, it is cleaned with ultrasonic waves to remove surface impurities, and then dried in a vacuum drying oven to constant weight.

[0014] Preferably, the ball milling process involves placing the pretreated α-Al2O3 powder in anhydrous ethanol, adding 0.3 wt% ammonium polyacrylate, mixing it with high-purity alumina balls, and then loading it into a ball mill. The ball milling conditions are: rotation speed 300 rpm, ball-to-material mass ratio 1:10, and time 12 h.

[0015] Preferably, the vacuum hot pressing sintering includes: evacuating to a vacuum level of 1×10⁻⁶. -3The furnace is preheated to 600-700℃ at a heating rate of 10℃ / min, then heated to 1200℃ at a heating rate of 5-8℃ / min, and then to 1600-1700℃ at a heating rate of 2-5℃ / min. After reaching the target temperature, an axial pressure of 30-50MPa is applied, and the furnace is held at the target temperature for 4-6 hours. After the holding period, heating is stopped, and the furnace is cooled to below 200℃. The pressure system is then turned off, and the furnace is evacuated and cooled to room temperature.

[0016] Furthermore, the vacuum hot pressing sintering process also includes a post-processing step, specifically: grinding and polishing the surface of the product obtained by vacuum hot pressing sintering to ensure that the target material surface is flat and smooth.

[0017] Preferably, the raw material for the TiVZrNbTaMoB alloy layer is a TiVZrNbTaMoB alloy target. The TiVZrNbTaMoB alloy target has a thickness of 4 mm and a diameter of 5 cm. The preparation steps of the TiVZrNbTaMoB alloy target are as follows: the materials are prepared according to the specified atomic percentage, and then the materials are sequentially mixed, ball-milled and hot-pressed to obtain the TiVZrNbTaMoB alloy target.

[0018] Furthermore, the ingredients are specifically selected as follows: high-purity Ti powder, V powder, Zr powder, Nb powder, Ta powder, Mo powder, and B powder by atomic percentage. Each powder must first be dried in a vacuum drying oven for 4 hours to remove surface-adsorbed moisture and impurities, and then weighed in an argon-protected glove box to avoid powder oxidation.

[0019] Preferably, the ball milling conditions are: rotation speed 300 rpm, ball-to-material mass ratio 1:10, and time 12 h.

[0020] Preferably, the hot pressing sintering includes: evacuating to a vacuum of 1×10⁻⁶. -3 Pre-fire at 600-800℃ with a heating rate of 10℃ / min, hold for 30min, then heat to 1200-1400℃ with a heating rate of 5-10℃ / min. After reaching the target temperature, apply 30-50MPa axial pressure and hold at the target temperature for 1-3h. After holding, stop heating, cool with the furnace to below 200℃, shut off the pressure system, and continue vacuum cooling to room temperature.

[0021] Furthermore, the hot pressing sintering process also includes a post-processing step, specifically: after demolding, the sintered alloy ingot is machined to the designed size using wire cutting, the target surface is polished step by step (400 grit, 800 grit, 1200 grit, 1500 grit diamond grinding wheels), then polished with diamond polishing paste, the polished target is placed in anhydrous ethanol for ultrasonic cleaning for 15 minutes to remove surface debris, and finally vacuum dried to obtain the final product.

[0022] The second technical solution of the present invention provides a method for preparing the above-mentioned titanium-based high-entropy amorphous / oxide multilayer film with radiation resistance and low hydrogen retention characteristics, comprising the following steps: TiVZrNbTaMoB alloy target and Al2O3 target were placed in a vacuum chamber evacuated to 8×10⁻⁶ m / s. -4 Inside the magnetron sputtering cavity of PA; Using a silicon wafer with a (111) crystal orientation as a substrate, an Al2O3 target is sputtered on the substrate to obtain the first Al2O3 layer; Sputtering of TiVZrNbTaMoB alloy target material onto the obtained first Al2O3 alloy layer yields a TiVZrNbTaMoB alloy layer. The sputtering steps of the Al2O3 target were repeated on the obtained TiVZrNbTaMoB alloy layer to prepare a second Al2O3 layer, thus obtaining the titanium-based high-entropy amorphous / oxide multilayer film with radiation resistance and low hydrogen retention characteristics.

[0023] Preferably, the sputtering conditions for the TiVZrNbTaMoB alloy target are: DC power of 50W, argon flow rate of 60sccm, sputtering pressure of 0.9pa, distance between the target and the substrate of 150mm, and sputtering time of 20min.

[0024] Preferably, the sputtering conditions of the Al2O3 target are as follows: sputtering power of 80W (RF), argon flow rate of 60sccm, sputtering pressure of 0.9pa, distance between the target and the substrate of 150mm, and sputtering time of 2h.

[0025] The third technical solution of the present invention provides the application of the above-mentioned titanium-based high-entropy amorphous / oxide multilayer film with radiation resistance and low hydrogen retention characteristics in the preparation of materials for extreme radiation environments, wherein the materials for extreme radiation environments include nuclear reactor first wall materials, fusion reactor blanket materials or nuclear fuel cladding coating materials.

[0026] Leveraging the excellent radiation resistance and low hydrogen retention characteristics of titanium-based high-entropy amorphous / oxide multilayer films, these multilayer films can serve as core protective components or functional coatings, adapting to key structural components in nuclear energy systems that withstand high-energy particle bombardment and hydrogen isotope infiltration, thus meeting service requirements.

[0027] The present invention discloses the following technical effects: This invention achieves synergistic optimization of radiation resistance and low hydrogen retention performance through a composite structure design of "TiVZrNbTaMoB high-entropy amorphous-Al2O3 layer". The TiVZrNbTaMoB high-entropy amorphous material possesses excellent intrinsic radiation resistance due to its disordered atomic structure and high mixing entropy. The interlayer interfaces of the multilayer film act as "defect traps," efficiently capturing irradiation-induced defects and inhibiting defect accumulation. The Al2O3 layer, relying on its dense crystalline structure, significantly reduces the retention of hydrogen isotopes within the film, solving the problem that existing single-functional materials cannot simultaneously meet multiple performance requirements.

[0028] Verified by high-energy hydrogen ion irradiation testing, the multilayer thin film prepared by this invention still maintains a clear layered structure with distinct interlayer boundaries, and no typical irradiation damage defects such as cracks, voids, or delamination are observed. This characteristic indicates that the multilayer thin film can not only resist the damage to the microstructure by high-energy particles, but also maintain a good interfacial bonding state, effectively avoiding sudden performance degradation caused by irradiation, and exhibiting excellent radiation resistance stability and structural integrity.

[0029] The TiVZrNbTaMoB high-entropy amorphous multilayer film provided by this invention can be applied to the protection or preparation of key components such as the first wall material of nuclear reactors, fusion reactor blanket, and nuclear fuel cladding, providing a new high-performance material option with better performance and stronger adaptability in the field of nuclear energy technology. Attached Figure Description

[0030] Figure 1 Hydrogen ion irradiation damage was simulated using SRIM software for monolayer Al2O3 film (a), monolayer TiVZrNbTaMoB film (b), and three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 film (c), as well as the hydrogen ion irradiation damage pathways for monolayer Al2O3 film (d), monolayer TiVZrNbTaMoB film (e), and three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 film (f). Figure 2 The hydrogen ion retention is calculated using SRIM software for monolayer Al2O3 film (a), monolayer TiVZrNbTaMoB film (b), and three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 film (c). Figure 3 XRD patterns of the original state of the monolayer TiVZrNbTaMoB film and the monolayer Al2O3 film (a), and the original state and XRD patterns of the three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 film of the present invention after 40MeV hydrogen ion irradiation (b). Figure 4The images show the surface morphology scans of the three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 thin film of the present invention in its original state (a) and after 40MeV hydrogen ion irradiation (b). Figure 5 The images show the original state (a) and the cross-sectional bright-field diagrams (b) of the three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 thin film of the present invention after 40MeV hydrogen ion irradiation. Detailed Implementation

[0031] This invention designs a three-layer composite structure of "crystalline Al2O3 / high-entropy amorphous HEMG / crystalline Al2O3", combining the radiation resistance of high-entropy amorphous alloys with the low hydrogen retention characteristics of alumina ceramics, to achieve a highly efficient synergistic effect at the material functional level, specifically manifested in: Radiation resistance: Multi-layer structure disperses radiation energy + amorphous phase enables self-healing of defects + alumina layer enhances high-temperature radiation resistance; Low hydrogen retention characteristics: Amorphous phase inhibits hydrogen diffusion + alumina layer constructs a physical barrier.

[0032] This invention provides a method for preparing a TiVZrNbTaMoB high-entropy amorphous alumina ceramic multilayer film with radiation resistance and low hydrogen retention properties. The film is prepared using TiVZrNbTaMoB alloy target and Al2O3 target as raw materials, and specifically includes the following steps: (1) Preparation of TiVZrNbTaMoB alloy target: weigh high-purity metal powders of Ti, V, Zr, Nb, Ta, Mo and B according to stoichiometric ratio, pre-treat the raw materials, mix and ball mill to obtain alloy raw materials, place the alloy raw materials in a vacuum hot pressing sintering furnace for hot pressing sintering to obtain TiVZrNbTaMoB alloy sintered billet, and post-process to obtain TiVZrNbTaMoB alloy target.

[0033] (2) Preparation of Al2O3 target material: The raw material is high-purity α-Al2O3 powder. The raw material is pretreated, ball-milled, and then placed in a vacuum hot-pressing sintering furnace for hot pressing sintering. The Al2O3 alloy target material is obtained after post-treatment.

[0034] (3) Place the TiVZrNbTaMoB alloy target and the Al2O3 target respectively in a vacuum of 8×10 -4Inside a magnetron sputtering chamber with vacuum pumped by a mechanical pump and a molecular pump (pa), an Al2O3 target is sputtered onto a silicon wafer (111) as the substrate to obtain the first Al2O3 layer. The RF power supply is then turned off, and the substrate is rotated above a TiVZrNbTaMoB target for further sputtering to obtain a TiVZrNbTaMoB alloy layer. The DC power supply is then turned off, and the substrate is rotated again above the Al2O3 target to repeat the sputtering process, resulting in the second Al2O3 layer. This results in a three-layer film, which is a high-entropy amorphous alumina ceramic multilayer film of TiVZrNbTaMoB with radiation resistance and low hydrogen retention characteristics (denoted as Al2O3 / TiVZrNbTaMoB / Al2O3 film). Throughout the sputtering process, the substrate remains in a rotating state to ensure that the thickness of the three-layer film is uniform.

[0035] In this invention, the atomic percentages of Ti, V, Zr, Nb, Ta, Mo, and B in step (1) are as follows: Ti: 45-50%, V: 20-25%, Zr: 8-12%, Nb: 12-16%, Ta: 1-3%, Mo: 0.3-0.6%, 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%.

[0036] In this invention, the conditions for the raw material pretreatment in step (1) are as follows: each powder is placed in a vacuum drying oven (temperature 80°C, vacuum degree 1×10⁻⁶). -2 Dry the powder for 4 hours to remove adsorbed moisture and impurities; then weigh it in an argon-protected glove box to prevent powder oxidation.

[0037] In this invention, the ball milling conditions in step (1) are as follows: the mixed powder and cemented carbide balls are loaded into a ball mill jar, the air inside the jar is replaced with argon gas (replaced 3 times), the ball mill speed is 300 rpm, the ball-to-material mass ratio is 1:10, the ball milling medium is anhydrous ethanol (solid-to-liquid volume ratio 1:1.5), and the ball milling time is 24 h. After ball milling, the powder is vacuum dried (temperature 70℃, vacuum degree 1×10⁻⁶). -2 Pa) to obtain composite powder.

[0038] In this invention, the hot pressing sintering process in step (1) is as follows: the composite powder is loaded into a graphite mold and placed in a vacuum hot pressing sintering furnace, and the furnace is first evacuated to 1×10⁻⁶. -3Pa, to remove air and prevent powder oxidation. Pre-fire at 600-800℃ (more preferably 700℃) at a heating rate of 10℃ / min, holding for 30min (pre-fire and holding remove residual ethanol vapor and adsorbed gases from the powder to prevent porosity during sintering). After pre-fire, heat to 1200-1400℃ (more preferably 1300℃) at a heating rate of 5-10℃ / min (more preferably 8℃ / min). Once the target temperature is reached, apply axial pressure (maintaining constant pressure ensures powder densification under high temperature and pressure), and hold at the target temperature for 1-3h (more preferably 2h). After holding, stop heating, cool with the furnace to below 200℃, shut off the pressure system, and continue vacuum cooling to room temperature. The pressure is 30-50MPa (more preferably 40MPa).

[0039] In this invention, the post-processing process described in step (1) is as follows: after demolding, the sintered alloy ingot is processed to the design size of the target material by wire cutting, and the surface of the target material is polished step by step (400 mesh, 800 mesh, 1200 mesh, 1500 mesh diamond grinding wheels), then polished with diamond polishing paste, and the polished target material is placed in anhydrous ethanol and ultrasonically cleaned for 15 minutes to remove surface debris, and then vacuum dried (60℃, 2h) to obtain TiVZrNbTaMoB alloy target material.

[0040] In this invention, the TiVZrNbTaMoB target material described in step (1) has a thickness of 4 mm and a diameter of 5 cm.

[0041] In this invention, the conditions for selecting raw materials in step (2) are as follows: high-purity α-Al2O3 powder (purity ≥99.99%) is selected as raw material. α-Al2O3 is a stable crystal form of Al2O3, with high melting point, high hardness and excellent chemical stability.

[0042] In this invention, the pretreatment conditions for the raw materials in step (2) are as follows: α-Al2O3 powder is soaked in anhydrous ethanol for 2 hours, then ultrasonically cleaned to remove surface impurities, and subsequently placed in a vacuum drying oven (temperature 80℃, vacuum degree 1×10⁻⁶). - 2 (Pa) Dry to constant weight.

[0043] In this invention, the ball milling conditions in step (2) are as follows: the pretreated α-Al2O3 powder is placed in anhydrous ethanol, 0.3wt% of ammonium polyacrylate is added, and wet ball milling is performed using a planetary ball mill. The powder is mixed with high-purity alumina balls and placed in the ball mill. The ball mill speed is 300 rpm, the ball-to-material mass ratio is 1:10, the ball milling medium is anhydrous ethanol (solid-to-liquid ratio 1:2), the ball milling time is 12 h, and after ball milling, it is vacuum dried (temperature 60℃, time 4 h) to obtain uniformly dispersed Al2O3 powder.

[0044] In this invention, the hot pressing sintering process in step (2) is as follows: Al2O3 powder is loaded into a graphite mold, placed in a vacuum hot pressing sintering furnace, and vacuumed to 1×10⁻⁶. -3 The pressure is increased to 600-700°C (more preferably 600°C) at a rate of 10°C / min to remove residual moisture and dispersant decomposition products. Then, the temperature is increased to 1200°C at a rate of 5-8°C / min (more preferably 5°C / min), at which point the particles begin initial sintering. The temperature is then increased to 1600-1700°C (more preferably 1700°C) at a rate of 2-5°C / min (more preferably 2°C / min) to enter the high-temperature densification stage, and held at the target temperature for 4-6 hours (more preferably 5 hours). After holding, heating is stopped, and the furnace is cooled to below 200°C. The pressure system is then shut off, and vacuum cooling continues until room temperature. The pressure is 30-50 MPa (more preferably 40 MPa).

[0045] In this invention, the Al2O3 target material in step (2) has a thickness of 4 mm and a diameter of 5 cm.

[0046] In this invention, the thickness of the TiVZrNbTaMoB alloy layer in step (3) is 300~350nm, and more preferably 314.4nm.

[0047] In this invention, the thickness of the first Al2O3 layer and the second Al2O3 layer in step (3) is independently 200~300nm, and more preferably 265.8nm or 245.4nm.

[0048] In this invention, the sputtering parameters of the TiVZrNbTaMoB alloy target in step (3) are as follows: power is DC 50W, argon flow rate is 60sccm, sputtering pressure is 0.9pa, distance between target and substrate is 150mm, and sputtering time is 20min.

[0049] In this invention, the sputtering parameters of the Al2O3 target in step (3) are: sputtering power of 80W radio frequency, argon flow rate of 60sccm, sputtering pressure of 0.9pa, distance between the target and the substrate of 150mm, and sputtering time of 2h.

[0050] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0051] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0052] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0053] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0054] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0055] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0056] Unless otherwise specified, the room temperature involved in this invention is 25±5℃.

[0057] Unless otherwise specified, all raw materials used in the following embodiments are commercially available products, and the source of commercially available products does not affect the technical effect of the present invention.

[0058] Example 1 A method for preparing a TiVZrNbTaMoB high-entropy amorphous alumina ceramic multilayer film with radiation resistance and low hydrogen retention properties, specifically including the following steps: (1) Preparation of TiVZrNbTaMoB alloy target: Weigh Ti: 47.3%, V: 25%, Zr: 11%, Nb: 14%, Ta: 2%, Mo: 0.5%, B: 0.2% and mix them to obtain a mixture. The mixture is then ball-milled under the following conditions: ball mill speed 300 rpm, ball-to-material mass ratio 1:10, and ball milling time 24 h. The obtained alloy raw material is then placed in a vacuum hot pressing sintering furnace and vacuumed to 1×10⁻⁶. -3 The alloy ingot was pre-fired at 700℃ with a heating rate of 10℃ / min and held for 30 min. Then, it was heated to 1300℃ with a heating rate of 8℃ / min. After reaching the target temperature, an axial pressure of 40MPa was applied and held at the target temperature for 2 h. The ingot was then cooled to below 200℃ in the furnace. The heating and pressure systems were turned off, and the ingot was further cooled to room temperature under vacuum. After demolding, the residual release agent on the surface was removed by ultrasonic cleaning. The sintered alloy ingot was then machined to the design size of the target material by wire cutting to obtain a TiVZrNbTaMoB alloy target material with a thickness of 4 mm and a diameter of 5 cm. (2) Preparation of Al2O3 target material: α-Al2O3 powder with a purity ≥99.99% was selected as raw material. After soaking in anhydrous ethanol for 2 hours, surface impurities were removed by ultrasonic cleaning. Then, it was placed in a vacuum drying oven (temperature 80℃, vacuum degree 1×10²Pa) and dried to constant weight. The pretreated α-Al2O3 powder was placed in anhydrous ethanol, and 0.3wt% of ammonium polyacrylate was added. After mixing with high-purity alumina balls, wet ball milling was performed using a planetary ball mill at a speed of 300 rpm, a ball-to-material mass ratio of 1:10, and a milling time of 12 hours. After milling, it was vacuum dried (temperature 60℃, time 4 hours) to obtain uniformly dispersed Al2O3 powder. The Al2O3 powder was loaded into a graphite mold and placed in a vacuum hot pressing sintering furnace. The vacuum was evacuated to 1×10³Pa. The temperature was first raised to 600℃ at a heating rate of 10℃ / min, and then at a heating rate of 5℃ / min. The temperature is increased to 1200℃ at a rate of 2℃ / min to induce initial sintering of the particles. Then, the temperature is increased to 1700℃ at a rate of 2℃ / min to enter the high-temperature densification stage. The temperature is held at the target temperature for 5 hours, and then cooled to below 200℃ in the furnace. The heating and pressure systems are then turned off, and the furnace is further evacuated to room temperature. After demolding, the residual release agent on the surface is removed by ultrasonic cleaning. After demolding, the sintered alloy ingot is machined to the design size of the target material using wire cutting to obtain an Al2O3 target material with a thickness of 4mm and a diameter of 5cm. (3) The inside of the magnetron sputtering chamber is evacuated to 8×10 using a mechanical pump and a molecular pump. -4Then, the TiVZrNbTaMoB alloy target and the Al2O3 target were placed inside the magnetron sputtering cavity. Using a silicon wafer with a (111) crystal orientation as the substrate, Al2O3 target sputtering was performed on the substrate. The sputtering parameters were: RF power of 80W, argon flow rate of 60sccm, sputtering pressure of 0.9pa, distance between target and substrate of 150mm, and sputtering time of 2h, resulting in an Al2O3 layer with a thickness of 265.8nm. The RF power was turned off, and the substrate containing the Al2O3 layer was rotated above the TiVZrNbTaMoB target for sputtering. The sputtering parameters were: sputtering power of 80W, argon flow rate of 60sccm, sputtering pressure of 0.9pa, distance between target and substrate of 150mm, and sputtering time of 2h, resulting in an Al2O3 layer with a thickness of 265.8nm. Sputtering was performed at 50W, with an argon flow rate of 60 sccm, a sputtering pressure of 0.9 Pa, a target-substrate distance of 150 mm, and a sputtering time of 20 min, resulting in a TiVZrNbTaMoB layer with a thickness of 314.4 nm. The DC power was then turned off, and the substrate containing the two thin films was rotated again above the Al2O3 target. The sputtering process with the Al2O3 target was repeated, resulting in another Al2O3 layer with a thickness of 245.4 nm. The resulting three-layer film is a high-entropy amorphous alumina ceramic multilayer film of TiVZrNbTaMoB with radiation resistance and low hydrogen retention characteristics (i.e., a three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 film).

[0059] Comparative Example 1 Same as in Example 1, except that the specific steps of step (3) are as follows: the inside of the magnetron sputtering cavity is evacuated to 8×10 using a mechanical pump and a molecular pump. -4 Pa, and then the TiVZrNbTaMoB alloy target was placed inside the magnetron sputtering cavity; using a silicon wafer with (111) crystal orientation as the substrate, the TiVZrNbTaMoB alloy target was sputtered on the substrate. The sputtering parameters were: power of DC 50W, argon flow rate of 60sccm, sputtering pressure of 0.9pa, distance between target and substrate of 150mm, sputtering time of 20min, and a TiVZrNbTaMoB alloy layer with a thickness of 314.4nm was obtained. The obtained single-layer film is the single-layer TiVZrNbTaMoB film.

[0060] Comparative Example 2 Same as in Example 1, except that the specific steps of step (3) are as follows: the inside of the magnetron sputtering cavity is evacuated to 8×10 using a mechanical pump and a molecular pump. -4Pa, and then the Al2O3 target is placed inside the magnetron sputtering cavity; using the silicon wafer (111) crystal orientation as the substrate, the Al2O3 target is sputtered on the substrate. The sputtering parameters are: sputtering power of RF 80W, argon flow rate of 60sccm, sputtering pressure of 0.9pa, distance between target and substrate of 150mm, sputtering time of 2h, and an Al2O3 layer with a thickness of 260nm is obtained. The obtained single-layer film is the single-layer Al2O3 film.

[0061] Performance testing: 1. The thin films prepared in Example 1, Comparative Example 1, and Comparative Example 2 were subjected to ion irradiation experiments on an ion irradiation experimental platform. The experimental sample size was 10 × 6 × 0.5 mm, the ion source was hydrogen ions, and the ion acceleration energy was 40 MeV. The irradiation dose was 1.9 × 10⁻⁶ times, respectively. 12 ions / cm 2 3.7×10 12 ions / cm 2 7.5×10 12 ions / cm 2 1.5×10 13 ions / cm 2 All irradiation experiments were conducted at room temperature.

[0062] Figure 1 The hydrogen ion irradiation damage was simulated using SRIM software for three films: a) a single-layer Al2O3 film (Al2O3), b) a single-layer TiVZrNbTaMoB film (HEMG), c) a three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 film (Al2O3-HEMG-Al2O3), and d) a single-layer Al2O3 film (Al2O3), e) a single-layer TiVZrNbTaMoB film (HEMG), and f) a three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 film (Al2O3-HEMG-Al2O3). Analysis of the irradiation damage path length shows that, under the same irradiation energy, the three films have irradiation damage paths of 1.18, 0.63, and 0.91 μm, respectively. A longer irradiation damage path indicates a more dispersed irradiation energy, making it less likely for large damage to concentrate in a specific region within the irradiated material. Simulation results show that the design of the multilayer thin film structure effectively extends the energy deposition path of hydrogen ions, thereby improving the overall radiation resistance of the film.

[0063] Figure 2The hydrogen ion retention is simulated using SRIM software for monolayer Al2O3 thin films (Al2O3) (a), monolayer TiVZrNbTaMoB thin films (HEMG) (b), and three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 thin films (Al2O3-HEMG-Al2O3) (c). The maximum irradiation dose is 1.5 × 10⁻⁶. 13 atom / cm 2 Below, the hydrogen retention capacity of a single layer of pure Al2O3 is 1.33 × 10⁻⁶. -5 The hydrogen retention of the three-layer Al2O3-HEMG-Al2O3 film decreased to 1.14 × 10⁻⁶. -5 This result demonstrates that through multi-layer synergy of "ceramic Al2O3-high-entropy amorphous", the hydrogen retention effect can be further optimized while retaining the high hydrogen resistance of ceramic Al2O3.

[0064] 2. To investigate the phase changes of Al2O3 / TiVZrNbTaMoB / Al2O3 multilayer films after hydrogen ion irradiation, this invention conducted X-ray diffraction (XRD) phase analysis on magnetron sputtered single-layer TiVZrNbTaMoB films, single-layer Al2O3 films, and Al2O3 / TiVZrNbTaMoB / Al2O3 multilayer films before and after 40 MeV hydrogen ion irradiation. A Rigaku SmartLab X-ray diffractometer was used to acquire the GIXRD diffraction patterns of the multilayer film samples before and after irradiation in grazing incidence mode. The diffractometer used a Cu target, with an operating voltage of 40 kV, an operating current of 150 mA, and a maximum power of 9 kW. During testing, the grazing angle was adjusted to 0.6°, the scanning range was controlled between 20 and 80°, the scanning speed was set to 3° / min, and sample signal points were acquired every 0.02 degrees.

[0065] Figure 3 This image shows the XRD patterns of the three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 thin film of this invention in its original state and after 40 MeV hydrogen ion irradiation. The XRD patterns show that the single-layer TiVZrNbTaMoB film exhibits a "bun peak" in the 30–40° range, indicating its amorphous structure. Comparison with standard PDF cards reveals that the sputtered alumina in the single-layer Al2O3 film is crystalline α-Al2O3. In the multilayer film, TiVZrNbTaMoB remains amorphous within the 30–40° range. After 40 MeV hydrogen ion irradiation, the amorphous TiVZrNbTaMoB layer does not crystallize and retains its amorphous structure. The Al2O3 layer maintains a crystalline structure in the multilayer film. Even after 40 MeV hydrogen ion irradiation, the alumina (α-Al2O3) diffraction peaks in the multilayer film are still present.

[0066] 3. The surface morphology of multilayer thin films was observed using a Zeiss G300 high-resolution field emission scanning electron microscope (SEM). This instrument has an accelerating voltage range of 20–30 kV, enabling the acquisition of high-resolution images suitable for characterizing micro- and nanoscale structures. During the experiment, the samples were fixed to the sample stage with conductive adhesive to ensure good electrical contact and reduce the impact of charge accumulation on image quality. In secondary electron (SE) signal mode, due to its high sensitivity to surface morphology, it can clearly reveal microstructural details such as grains, cracks, and pores.

[0067] Figure 4 This paper presents SEM images of the pristine state of the three-layer Al₂O₃ / TiVZrNbTaMoB / Al₂O₃ thin film prepared according to this invention, as well as its surface morphology after 40 MeV hydrogen ion irradiation. Comparing the images before and after irradiation, it is clearly observed that the film surface remains intact and dense, without any irradiation-induced micro-defects such as cracks, peeling, voids, or bubbles. This result demonstrates that the multilayer thin film structure exhibits excellent structural integrity and irradiation stability even after high-energy particle bombardment.

[0068] 4. Using a high-resolution transmission electron microscope (FEI Talos F200X, ThermoFisher Scientific, America) operating at 200kV, the alternating layered structure of the three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 thin film was observed in scanning transmission electron microscope mode. The imaging process of this device is as follows: the electron beam emitted by the electron gun is focused by the condenser lens system and penetrates the sample. After elastic / inelastic scattering with the atoms in the sample, the image is magnified by the objective lens and projection lens system.

[0069] Figure 5 These are bright-field TEM images of the three-layer Al₂O₃ / TiVZrNbTaMoB / Al₂O₃ thin film before and after hydrogen ion irradiation. The results show that both the film and the irradiation images exhibit a clear, alternating layered structure with distinct interfaces between layers. No obvious cracks, voids, or interlayer delamination were observed, indicating that the multilayer film maintains excellent interfacial bonding and structural integrity after hydrogen ion irradiation. Specifically, the interface between the TiVZrNbTaMoB intermediate layer and the two Al₂O₃ layers did not undergo significant degradation or structural abrupt changes after irradiation, demonstrating that the composite structure has good resistance to irradiation-induced interfacial damage. This excellent irradiation stability is likely closely related to its unique interfacial structure, the high phase stability of the high-entropy alloy intermediate layer, and the well-matched thermal expansion coefficients and chemical compatibility between the layers.

[0070] In summary, this invention successfully achieved effective control over the irradiation damage path through a multilayer thin film structure design. Specifically, in the three-layer Al2O3 / TiVZrNbTaMoB / Al2O3 structure, the different layered interfaces act as additional defect traps, significantly extending the energy deposition and dissipation path of high-energy particles within the material. Experimental results show that, under the same irradiation conditions, the equivalent damage path length of this multilayer thin film reaches 0.91 μm. This value is significantly higher than the 0.63 μm of the single-layer TiVZrNbTaMoB film, indicating that the multilayer design disperses and absorbs irradiation energy through interface effects, thereby improving the overall damage resistance.

[0071] A specific three-layer thin-film structure design reduces hydrogen retention within the material. At 40 MeV, 1.5 × 10⁻⁶ 13 ions / cm 2 At the irradiation dose, the hydrogen retention of the three-layer structure is 1.14 × 10⁻⁶. -5 This is lower than the 1.33 × 10⁻⁶ for a single-layer Al₂O₃ film. -5 This study demonstrates that the multilayer synergistic design of "ceramic-high-entropy amorphous metal-ceramic" further optimizes hydrogen retention behavior while maintaining high hydrogen barrier performance.

[0072] After irradiation with 40 MeV hydrogen ions, the TiVZrNbTaMoB layer in the multilayer film remained amorphous and did not crystallize; the Al2O3 layer also maintained its crystalline structure without phase transition or lattice degradation, indicating that this multilayer system exhibits excellent phase stability under 40 MeV hydrogen ion irradiation. Furthermore, no cracks, peeling, or pores appeared on the film surface after irradiation; the interlayer interfaces were clear and tightly bonded. This demonstrates that the multilayer structure maintains good microstructural integrity and interfacial bonding strength under irradiation conditions.

[0073] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.

[0074] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A titanium-based high-entropy amorphous / oxide multilayer film with anti-irradiation and low hydrogen retention characteristics, characterized in that, From bottom to top are a first Al2O3 layer, a TiVZrNbTaMoB alloy layer, and a second Al2O3 layer, wherein the TiVZrNbTaMoB alloy layer has an atomic percentage of Ti: 45-50%, V: 20-25%, Zr: 8-12%, Nb: 12-16%, Ta: 1-3%, Mo: 0.3-0.6%, and B: 0.1-0.3%.

2. The titanium-based high-entropy amorphous / oxide multilayer film with anti- radiation and low hydrogen retention characteristics of claim 1, wherein, The first Al2O3 layer and the second Al2O3 layer independently have a thickness of 200-300 nm, and the TiVZrNbTaMoB alloy layer has a thickness of 300-350 nm.

3. The titanium-based high-entropy amorphous / oxide multilayer film with anti-irradiation and low hydrogen retention characteristics of claim 1, wherein, The first Al2O3 layer and the second Al2O3 layer are made of an Al2O3 target material. The Al2O3 target material has a thickness of 4 mm and a diameter of 5 cm. The Al2O3 target material is prepared by sequentially subjecting α-Al2O3 powder to ball milling and vacuum hot-press sintering, and the α-Al2O3 powder has a purity of ≥ 99.99%.

4. The titanium-based high-entropy amorphous / oxide multilayer film with anti- radiation and low hydrogen retention characteristics of claim 3, wherein, The ball milling is performed at a speed of 300 rpm, a ball-to-material mass ratio of 1:10, and for 12 h. The vacuum hot-press sintering comprises: vacuumizing to 1×10 -3 Pa, pre-sintering at 600~700℃ with a temperature increasing rate of 10℃ / min, then increasing the temperature to 1200℃ with a temperature increasing rate of 5~8℃ / min, and then increasing the temperature to 1600~1700℃ with a temperature increasing rate of 2~5℃ / min, applying an axial pressure of 30~50MPa after reaching the target temperature, and keeping the temperature for 4~6h, stopping heating after the keeping, cooling down to below 200℃ with the furnace, closing the pressure system, and continuing vacuumizing and cooling to room temperature.

5. The titanium-based high-entropy amorphous / oxide multilayer film with anti-irradiation and low hydrogen retention characteristics of claim 1, wherein, The TiVZrNbTaMoB alloy layer is made of a TiVZrNbTaMoB alloy target material. The TiVZrNbTaMoB alloy target material has a thickness of 4 mm and a diameter of 5 cm. The TiVZrNbTaMoB alloy target material is prepared by dosing according to the specified atomic percentage, and then sequentially mixing, ball milling, and hot-press sintering to obtain the TiVZrNbTaMoB alloy target material.

6. The titanium-based high-entropy amorphous / oxide multilayer film with anti- radiation and low hydrogen retention characteristics of claim 5, wherein, The ball milling is performed at a speed of 300 rpm, a ball-to-material mass ratio of 1:10, and for 12 h. The hot-press sintering comprises: vacuumizing to 1x10 -3 Pa, pre-sintering at 600~800℃ with a temperature increasing rate of 10℃ / min, holding for 30min, then increasing the temperature to 1200~1400℃ with a temperature increasing rate of 5~10℃ / min, applying an axial pressure of 30~50MPa after reaching the target temperature, holding for 1~3h at the target temperature, stopping heating after the holding, cooling down to below 200℃ with the furnace, closing the pressure system, and continuing vacuumizing and cooling to room temperature.

7. The method of producing a titanium-based high-entropy amorphous / oxide multilayer film having anti-radiation and low hydrogen retention characteristics according to any one of claims 1 to 6, characterized by, The method comprises the following steps: The TiVZrNbTaMoB alloy target and the Al2O3 target were placed in the magnetron sputtering chamber of the vacuum coater, respectively, which was pumped to 8 x 10 -4 pa; and the Al2O3 target was placed in the magnetron sputtering chamber of the vacuum coater, which was pumped to 8 x 10 Sputtering of the Al2O3 target material on a silicon wafer (111) substrate to obtain the first Al2O3 layer; Sputtering of the TiVZrNbTaMoB alloy target material on the obtained first Al2O3 alloy layer to obtain the TiVZrNbTaMoB alloy layer; Repeating the sputtering step of the Al2O3 target material on the obtained TiVZrNbTaMoB alloy layer to prepare the second Al2O3 layer, thereby obtaining the titanium-based high-entropy amorphous / oxide multilayer film with anti-radiation and low hydrogen retention characteristics.

8. The preparation method according to claim 7, characterized in that, The sputtering conditions of the TiVZrNbTaMoB alloy target material are as follows: a direct current power of 50 W, an argon flow rate of 60 sccm, a sputtering pressure of 0.9 Pa, a distance between the target material and the substrate of 150 mm, and a sputtering time of 20 min.

9. The preparation method according to claim 7, characterized in that, The sputtering conditions of the Al2O3 target material are as follows: a radio frequency power of 80 W, an argon flow rate of 60 sccm, a sputtering pressure of 0.9 Pa, a distance between the target material and the substrate of 150 mm, and a sputtering time of 2 h.

10. Use of the titanium-based high-entropy amorphous / oxide multilayer film with anti-radiation and low hydrogen retention characteristics according to any one of claims 1 to 6 for 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 cladding material, or a nuclear fuel cladding coating material.

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