Preparation method and application of medium and high entropy amorphous oxide hydrogen barrier film
By preparing medium- and high-entropy amorphous oxide films on steel substrates, the problems of insufficient hardness and hydrogen barrier capacity of existing ceramic hydrogen barrier films have been solved, achieving high efficiency in hydrogen barrier and improved mechanical properties, making them suitable for key safety components in hydrogen storage and transportation systems.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANJING INST OF TECH
- Filing Date
- 2026-04-14
- Publication Date
- 2026-06-26
AI Technical Summary
Existing single-component oxide ceramic hydrogen barrier films lack sufficient hardness and hydrogen barrier capacity, making it difficult to effectively prevent hydrogen permeation and hydrogen embrittlement, thus limiting their application in hydrogen storage and transportation systems.
Medium- and high-entropy amorphous oxide films are used to deposit amorphous oxide films of metal elements such as Ti, Cr, Zr, Al, V, Nb, and Hf on steel substrates by magnetron sputtering, forming significant amorphous structures and complex diffusion channels, thereby enhancing hydrogen barrier properties and mechanical properties.
It achieves efficient hydrogen permeation prevention, improves the membrane's resistance to cracking and scratches, and provides excellent hydrogen barrier properties and mechanical properties, making it suitable for key safety components in hydrogen storage and transportation systems.
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Figure CN122279482A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing and applying medium- and high-entropy amorphous oxide hydrogen-barrier thin films, belonging to the field of materials technology. Background Technology
[0002] Hydrogen energy, due to its advantages of being pollution-free, widely available, and having a high calorific value, is hailed as one of the most promising secondary energy sources today. To address the contradiction between high costs and safety risks in hydrogen storage and transportation, and to achieve the overall goal of improving hydrogen storage and transportation efficiency and reducing costs, a solution is needed. However, structural materials such as steel are prone to hydrogen embrittlement and fatigue failure in hydrogen-exposed environments, causing safety issues and economic losses, severely restricting their large-scale application in advanced hydrogen storage and transportation technologies. To mitigate the permeation and diffusion of hydrogen in steel, preparing hydrogen-barrier coatings on the steel surface has become a long-term and reliable means to prevent or delay hydrogen penetration into its interior and prevent hydrogen embrittlement. Therefore, the research and development of novel high-hydrogen-barrier surface protective film materials has significant economic and social benefits.
[0003] Compared to metallic materials, ceramic materials have lower hydrogen permeability. Therefore, hydrogen diffusion can be blocked by depositing ceramic phase thin films on structural materials. Among them, medium- and high-entropy amorphous oxide thin films, due to their high configuration entropy and stable amorphous structure, provide a higher energy barrier and homogeneous trap for hydrogen diffusion behavior. At the same time, they are superior to traditional ceramic phase thin films in terms of mechanical properties, thus minimizing the risk of cracking under hydrogen pressure and effectively maintaining the structural integrity of the oxide film. This helps to improve its hydrogen barrier performance and has broad application potential in the field of hydrogen barrier protective coatings for critical safety components such as valves and flanges in hydrogen storage and transportation systems. Summary of the Invention
[0004] The purpose of this invention is to address the limitations of existing technologies in terms of insufficient hardness and hydrogen barrier capacity of single-component oxide ceramic hydrogen barrier films. This invention provides a method for preparing and applying medium- and high-entropy amorphous oxide hydrogen barrier films. The prepared medium- and high-entropy amorphous oxide hydrogen barrier films exhibit excellent mechanical and hydrogen barrier properties and can be used as hydrogen barrier protective coating materials for the surfaces of key safety components such as valves and flanges in hydrogen storage and transportation systems.
[0005] The technical solution of the present invention is as follows: A medium- or high-entropy amorphous oxide hydrogen barrier film with a thickness of 50 to 800 nm is provided. The high-entropy amorphous oxide hydrogen barrier film contains oxygen (O) at a content of 40 at.% to 75 at.%. Furthermore, the medium- or high-entropy amorphous oxide hydrogen barrier film contains any three to six metallic elements from Ti, Cr, Zr, Al, V, Nb, and Hf, with each metallic element having a content ranging from 5 at.% to 60 at.%.
[0006] The aforementioned medium- and high-entropy amorphous oxide hydrogen barrier film exhibits a trend of first increasing and then slightly decreasing with the increase of the substrate negative bias voltage.
[0007] The hydrogen barrier film of medium and high entropy amorphous oxide exhibits an overall trend of first increasing and then decreasing with the increase of substrate negative bias voltage.
[0008] The medium- and high-entropy amorphous oxide hydrogen barrier film exhibits a significant amorphous phase structure and a fully oxidized state, with good chemical stability and a total thickness of 50 to 800 nm.
[0009] A method for preparing a medium- to high-entropy amorphous oxide hydrogen barrier thin film includes the following steps: Step (1) Select a medium-entropy or high-entropy alloy target, fix the target and adjust its angle and height so that the target center is focused on the center of the sample stage, and place the ultrasonically cleaned and dried substrate in the center of the sample stage.
[0010] Step (2) Before deposition, the vacuum level in the sputtering chamber was evacuated to the baseline vacuum level. During the deposition of the thin film on the substrate using magnetron sputtering, the sample stage was kept rotating. First, the substrate surface was cleaned with Ar ions under a high negative bias to remove residual impurities. Subsequently, the sputtering power, substrate negative bias, substrate heating temperature, sputtering time, and Ar / O2 flow rate were adjusted to obtain medium- and high-entropy amorphous oxide hydrogen barrier films with the set composition and structure.
[0011] The medium- or high-entropy alloy target mentioned in step (1) contains any three to six metal elements of Ti, Cr, Zr, Al, V, Nb, and Hf, with the content of each metal element ranging from 15 at.% to 60 at.% and the purity above 99%.
[0012] The substrate mentioned in step (1) is selected from commonly used steel materials in the field, such as pure iron, ferritic steel, martensitic steel, bainitic steel and austenitic steel. When used in industry, the substrate can be selected according to the requirements, such as using industrial pure iron, carbon structural steel, pipeline steel and stainless steel as the substrate.
[0013] The substrate described in step (1) is first ground and polished, then cleaned with ultrasonic power of 20~200 kHz in alcohol or acetone solution for 10~30 min, and dried at 120~180 ℃ for 1~3 h.
[0014] In step (2), the base vacuum level of the sputtering cavity should be lower than 8 × 10⁻⁶. -4 Pa, the sample stage rotation speed is 2 ~ 10 r / min.
[0015] In step (2), a negative bias of 300 ~ 800 V is applied to the substrate before sputtering, and Ar ion cleaning is performed with an Ar flow rate of 20 ~ 50 sccm for 10 ~ 40 min.
[0016] In step (2), when depositing the thin film on the substrate by magnetron sputtering, the negative bias voltage of the substrate is 0~300V. The heating temperature of the substrate is 25 ~ 600 ℃.
[0017] In step (2), by adjusting the sputtering power, sputtering time, and Ar / O2 flow rate of the medium-entropy or high-entropy alloy target, a medium- or high-entropy amorphous oxide hydrogen barrier film of different thicknesses and compositions is obtained. Based on the composition and thickness range of a medium- or high-entropy amorphous oxide hydrogen barrier film, the sputtering power of the high-entropy oxide layer is 100 ~ 300 W, the sputtering time is 3000 ~ 30000 s, the Ar flow rate is 10 ~ 60 sccm, and the O2 flow rate is 10 ~ 50 sccm.
[0018] The amorphous oxide film, as a hydrogen permeation barrier coating, is applied to hydrogen-blocking protective coatings on the surfaces of critical safety components such as valves and flanges in hydrogen storage and transportation systems.
[0019] Compared with traditional methods for preparing high-entropy oxide thin films, this invention has the following characteristics: This invention relates to a medium- and high-entropy amorphous oxide hydrogen barrier film, which is dominated by a fully oxidized medium- and high-entropy oxide amorphous phase. The film exhibits severe atomic misalignment and a significant amorphous structure, providing complex and tortuous diffusion channels to inhibit hydrogen permeation. Macroscopically, this results in a lower hydrogen diffusion coefficient. It effectively prevents hydrogen diffusion, thus exhibiting optimal hydrogen barrier performance. Furthermore, the amorphous structure and medium- and high-entropy effect contribute to excellent overall mechanical properties, significantly improving the film's crack and scratch resistance.
[0020] This invention discloses a method for preparing medium- and high-entropy amorphous oxide hydrogen barrier films. The method utilizes DC magnetron sputtering, which is simple to operate, easy to control the preparation conditions, and has good repeatability. It can be used in practical applications and also provides guidance for the design and preparation of other oxide hydrogen barrier films. Attached Figure Description
[0021] Figure 1 XPS results for the high-entropy amorphous oxide hydrogen barrier thin film prepared in step 2; Figure 2 The cross-sectional SEM image of the high-entropy amorphous oxide hydrogen barrier film prepared in step 2 is shown. Figure 3 XRD results of the high-entropy amorphous oxide hydrogen barrier thin film prepared in step 2; Figure 4 The curves showing the change in hardness of the high-entropy amorphous oxide hydrogen barrier film prepared in steps 1-4 as a function of the negative bias voltage of the substrate are shown. Figure 5 Hydrogen permeation curves of the high-entropy amorphous oxide hydrogen barrier films prepared in steps 1-4 are shown. Figure 6 The hydrogen permeation curves of the alumina hydrogen barrier film prepared for Comparative Example 1 and industrial pure iron for Comparative Example 2 are shown. Detailed Implementation
[0022] The invention will now be further described with reference to the accompanying drawings. Example 1
[0023] The target material was selected as a high-entropy alloy target with a purity of 99% (Ti 25 at.%, Cr 25 at.%, Al 25 at.%, Zr 25 at.%), and industrial pure iron as the substrate. The substrate was first ground and polished, then cleaned in an alcohol solution with 50 kHz ultrasonic power for 15 min, and dried at 150℃ for 2 h. After that, it was placed in the center of the sample stage.
[0024] Before deposition, the vacuum level in the sputtering chamber is evacuated to a background vacuum of 5 × 10⁻⁶. -4 When depositing thin films on a substrate using magnetron sputtering, the sample stage was kept rotating at a speed of 8 r / min. First, a negative bias of 400 V was applied to the substrate before sputtering, and Ar ion cleaning was performed at a flow rate of 30 sccm for 20 min. When depositing thin films on industrial pure iron using magnetron sputtering, the negative bias of the substrate was 0 V, and the substrate heating temperature was 300 ℃. The sputtering power of the medium-entropy alloy target was adjusted to 200 W, the sputtering time to 18000 s, the Ar flow rate to 20 sccm, and the O2 flow rate to 20 sccm. The resulting high-entropy amorphous oxide thin film had the following elemental contents: O 50.7 at.%, Ti 10.9 at.%, Cr 10.1 at.%, Al 14.2 at.%, and Zr 14.1 at.%. The film exhibited a fully oxidized state with a total thickness of 490 nm. Example 2
[0025] The target material was selected as a high-entropy alloy target with a purity of 99% (Ti 25 at.%, Cr 25 at.%, Al 25 at.%, Zr 25 at.%), and industrial pure iron was used as the substrate. The substrate was first ground and polished, then cleaned in an alcohol solution with 50 kHz ultrasonic power for 15 min, and dried at 150 ℃ for 2 h. After that, it was placed in the center of the sample stage.
[0026] Before deposition, the vacuum level in the sputtering chamber is evacuated to a background vacuum of 5 × 10⁻⁶. -4When depositing thin films on a substrate using magnetron sputtering, the sample stage was kept rotating at a speed of 8 r / min. Before sputtering, a negative bias of 400 V was applied to the substrate, and Ar ion cleaning was performed at a flow rate of 30 sccm for 20 min. When depositing thin films on industrial pure iron using magnetron sputtering, the negative bias of the substrate was 100 V, and the substrate heating temperature was 300 ℃. The sputtering power of the medium-entropy alloy target was adjusted to 200 W, the sputtering time to 18000 s, the Ar flow rate to 20 sccm, and the O2 flow rate to 20 sccm. The resulting high-entropy amorphous oxide thin film contained the following elemental compositions: O 56.1 at.%, Ti 10.7 at.%, Cr 9.7 at.%, Al 14.5 at.%, and Zr 9.0 at.%. The film exhibited a fully oxidized state with a total thickness of 465 nm. Example 3
[0027] The target material was selected as a high-entropy alloy target with a purity of 99% (Ti 25 at.%, Cr 25 at.%, Al 25 at.%, Zr 25 at.%), and industrial pure iron was used as the substrate. The substrate was first ground and polished, then cleaned in an alcohol solution with 50 kHz ultrasonic power for 15 min, and dried at 150 ℃ for 2 h. After that, it was placed in the center of the sample stage.
[0028] Before deposition, the vacuum level in the sputtering chamber is evacuated to a background vacuum of 5 × 10⁻⁶. -4 When depositing thin films on a substrate using magnetron sputtering, the sample stage was kept rotating at a speed of 8 r / min. Before sputtering, a negative bias of 400 V was applied to the substrate, and Ar ion cleaning was performed at a flow rate of 30 sccm for 20 min. When depositing thin films on industrial pure iron using magnetron sputtering, the negative bias of the substrate was 200 V, and the substrate heating temperature was 300 ℃. The sputtering power of the medium-entropy alloy target was adjusted to 200 W, the sputtering time to 18000 s, and the Ar and O2 flow rates to be 20 sccm and 20 sccm respectively. The resulting high-entropy amorphous oxide thin film contained the following elemental compositions: O 48.9 at.%, Ti 12.2 at.%, Cr 10.6 at.%, Al 14.1 at.%, and Zr 14.2 at.%. The film exhibited a fully oxidized state with a total thickness of 425 nm. Example 4
[0029] The target material was selected as a high-entropy alloy target with a purity of 99% (Ti 25 at.%, Cr 25 at.%, Al 25 at.%, Zr 25 at.%), and industrial pure iron was used as the substrate. The substrate was first ground and polished, then cleaned in an alcohol solution with 50 kHz ultrasonic power for 15 min, and dried at 150 ℃ for 2 h. After that, it was placed in the center of the sample stage.
[0030] Before deposition, the vacuum level in the sputtering chamber is evacuated to a background vacuum of 5 × 10⁻⁶. -4 When depositing thin films on a substrate using magnetron sputtering, the sample stage was kept rotating at a speed of 8 r / min. Before sputtering, a negative bias of 400 V was applied to the substrate, and Ar ion cleaning was performed at a flow rate of 30 sccm for 20 min. When depositing thin films on industrial pure iron using magnetron sputtering, the negative bias of the substrate was 300 V, and the substrate heating temperature was 300 ℃. The sputtering power of the medium-entropy alloy target was controlled at 200 W, the sputtering time at 18000 s, the Ar flow rate at 20 sccm, and the O2 flow rate at 20 sccm. The resulting high-entropy amorphous oxide thin film contained the following elemental compositions: O 46.4 at.%, Ti 12.9 at.%, Cr 10.5 at.%, Al 14.9 at.%, and Zr 15.3 at.%. The film exhibited a fully oxidized state with a total thickness of 411 nm.
[0031] Comparative Example 1
[0032] The target material was selected as 99% pure Al target, and the substrate was industrial pure iron. The substrate was first ground and polished, then cleaned in alcohol solution with 50 kHz ultrasonic power for 15 min, and dried at 150 ℃ for 2 h. After that, it was placed in the center of the sample stage.
[0033] Before deposition, the vacuum level in the sputtering chamber is evacuated to a background vacuum of 5 × 10⁻⁶. -4 When depositing thin films on a substrate using magnetron sputtering, the sample stage was kept rotating at a speed of 8 r / min. Before sputtering, a negative bias of 400 V was applied to the substrate, and Ar ion cleaning was performed at a flow rate of 30 sccm for 20 min. When depositing thin films on industrial pure iron using magnetron sputtering, the negative bias of the substrate was 100 V, and the substrate heating temperature was 300 ℃. The sputtering power of the medium-entropy alloy target was controlled at 200 W, the sputtering time at 18000 s, and the Ar and O2 flow rates were both 20 sccm. The resulting alumina thin film contained 62.2 at.% O and 37.8 at.% Al. The film exhibited a fully oxidized state with a total thickness of 398 nm.
[0034] Comparative Example 2
[0035] The substrate was first ground and polished, then cleaned in an alcohol solution with 50 kHz ultrasonic power for 15 min, and dried at 150 ℃ for 2 h. Hydrogen-barrier films were prepared on the surface by non-magnetic sputtering.
[0036] The average hardness and hydrogen barrier parameters of the six high-entropy amorphous oxide hydrogen barrier films of Examples 1-4, Comparative Example 1 alumina oxide film, and Comparative Example 2 industrial pure iron are listed in Table 1.
[0037] Table 1 shows the average hardness and hydrogen barrier parameters of Examples 1-4 and Comparative Examples 1-2. Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Hardness (GPa) 5.8 7.1 12.8 12.7 9.7 1.3 <![CDATA[Hydrogen diffusion coefficient (10 -8 cm 2 / s)]]> 16.3 7.7 18.1 15.2 704 12100 Depend on Figure 1 It can be seen that the high-entropy amorphous oxide hydrogen barrier film prepared in Example 2 exhibits a fully oxidized state. Figure 2 It can be seen that the high-entropy oxide film prepared in Example 2 has good adhesion to the substrate, with no significant cracks or peeling. Figure 3 It can be seen that the high-entropy oxide film prepared in Example 2 exhibits significant amorphous structural characteristics overall. Figure 4 It can be seen that with the increase of the substrate negative bias voltage, the hardness of the high-entropy amorphous oxide hydrogen barrier films prepared in Examples 1-4 first increases and then slightly decreases. Through Figure 5 Hydrogen permeation curves of the high-entropy amorphous oxide hydrogen barrier films prepared in steps 1-4, and Figure 6 The hydrogen permeation curves of the alumina hydrogen barrier film prepared in Comparative Example 1 and the industrial pure iron in Comparative Example 2, combined with the results in Table 1, show that compared with the traditional alumina hydrogen barrier coating prepared in Comparative Example 1, the high-entropy amorphous oxide hydrogen barrier films prepared in Examples 1-4 have a complex and tortuous diffusion channel provided by their internal amorphous structure, thereby inhibiting the diffusion and permeation of hydrogen atoms, exhibiting a lower hydrogen diffusion coefficient and showing excellent hydrogen barrier performance.
[0038] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A medium- or high-entropy amorphous oxide hydrogen barrier film according to claim 1, characterized in that: The medium- or high-entropy amorphous oxide hydrogen barrier film has a thickness of 50 to 800 nm and contains oxygen (O) at a content of 40 at.% to 75 at.%. Furthermore, the medium- or high-entropy amorphous oxide hydrogen barrier film contains any three to six metal elements from Ti, Cr, Zr, Al, V, Nb, and Hf, with each metal element having a content ranging from 5 at.% to 60 at.%.
2. The medium- and high-entropy amorphous oxide hydrogen barrier film according to claim 1, characterized in that: The aforementioned medium- and high-entropy amorphous oxide hydrogen barrier film exhibits a trend of first increasing and then slightly decreasing with the increase of substrate negative bias voltage; The hydrogen barrier film of medium and high entropy amorphous oxide exhibits an overall trend of first increasing and then decreasing with the increase of substrate negative bias voltage.
3. The medium- and high-entropy amorphous oxide hydrogen barrier film according to claim 1, characterized in that: The medium- and high-entropy amorphous oxide hydrogen barrier film exhibits a significant amorphous phase structure and a fully oxidized state, with good chemical stability and a total thickness of 50 to 800 nm.
4. A method for preparing a medium- or high-entropy amorphous oxide hydrogen-barrier thin film as described in any one of claims 1 to 3, characterized in that: Includes the following steps: Step (1): Select a medium-entropy or high-entropy alloy target, fix the target and adjust the angle and height of the target so that the target center is focused on the center of the sample stage, and place the ultrasonically cleaned and dried substrate in the center of the sample stage. Step (2): Before deposition, the vacuum level in the sputtering chamber is evacuated to the baseline vacuum level. When depositing the thin film on the substrate by magnetron sputtering, the sample stage is kept rotating. First, the substrate surface is cleaned with Ar ions under a high negative bias to remove residual impurities. Subsequently, the sputtering power, substrate negative bias, substrate heating temperature, sputtering time, and Ar / O2 flow rate are adjusted to obtain medium- and high-entropy amorphous oxide hydrogen barrier films with the set composition and structure.
5. The method for preparing a medium- or high-entropy amorphous oxide hydrogen barrier thin film according to claim 4, characterized in that: The medium-entropy or high-entropy alloy target mentioned in step (1) contains any three to six metallic elements of Ti, Cr, Zr, Al, V, Nb, and Hf, with the content of each metallic element ranging from 15 at.% to 60 at.% and the purity above 99%. The substrate mentioned in step (1) is selected from commonly used steel materials in the field, such as pure iron, ferritic steel, martensitic steel, bainitic steel and austenitic steel. When used in industry, the substrate can be selected according to the requirements, such as using industrial pure iron, carbon structural steel, pipeline steel and stainless steel as the substrate. The substrate described in step (1) is first ground and polished, then cleaned with ultrasonic power of 20~200 kHz in alcohol or acetone solution for 10~30 min, and dried at 120~180 ℃ for 1~3 h.
6. The method for preparing a medium- or high-entropy amorphous oxide hydrogen-barrier thin film according to claim 4, characterized in that: In step (2), the base vacuum level of the sputtering cavity should be lower than 8 × 10⁻⁶. -4 Pa, the sample stage rotation speed is 2 ~ 10 r / min; In step (2), a negative bias of 300 ~ 800 V is applied to the substrate before sputtering, and Ar ion cleaning is performed with an Ar flow rate of 20 ~ 50 sccm for 10 ~ 40 min. In step (2), when depositing the thin film on the substrate by magnetron sputtering, the negative bias voltage of the substrate is 0~300V. The heating temperature of the substrate is 25 ~ 600 ℃; In step (2), by adjusting the sputtering power, sputtering time and Ar / O2 flow rate of the medium-entropy or high-entropy alloy target, a medium- or high-entropy amorphous oxide hydrogen barrier film with different thicknesses and compositions can be obtained. According to the composition and thickness range of a medium- and high-entropy amorphous oxide hydrogen barrier film, the sputtering power of the medium- and high-entropy amorphous oxide film is 100 ~ 300 W, the sputtering time is 3000 ~ 30000 s, the Ar flow rate is 10 ~ 60 sccm, and the O2 flow rate is 10 ~ 50 sccm.
7. An application of a medium- or high-entropy amorphous oxide hydrogen barrier thin film as described in any one of claims 1-3, characterized in that, include: The amorphous oxide film, as a hydrogen permeation barrier coating, is applied to hydrogen-blocking protective coatings on the surfaces of critical safety components such as valves and flanges in hydrogen storage and transportation systems.