A method for achieving high hydrogen / deuterium / tritium permeation resistance of oxide coatings

Abstract

This invention discloses a method for achieving high hydrogen / deuterium / tritium permeation resistance in oxide coatings. By applying an electric current to an oxide coating (such as zirconium oxide, chromium oxide, titanium oxide, aluminum oxide, etc.) at a certain temperature, the lattice thermodynamic equilibrium is disrupted by the electric field, resulting in a high concentration of lattice point defects generated in situ within the coating, significantly enhancing its hydrogen / deuterium / tritium permeation resistance. Experimental results show that these lattice point defects can form deep-level traps, capturing hydrogen isotope atoms and effectively inhibiting the diffusion and permeation of hydrogen and its isotopes within the coating, thus achieving high hydrogen / deuterium / tritium permeation resistance. This process is simple, efficient, low-cost, and widely applicable, enabling the efficient preparation of oxide coatings with high hydrogen / deuterium / tritium permeation resistance. It has significant application prospects in the fields of tritium permeation protection in fusion reactor structural materials, hydrogen embrittlement protection of metals, and hydrogen permeation resistance in materials used in hydrogen-containing and hydrogen isotope-containing environments.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen-blocking / deuterium / tritium-blocking coatings for protecting material surfaces from hydrogen permeation in hydrogen-containing and hydrogen isotope environments, and specifically relates to a method for achieving high hydrogen / deuterium / tritium permeation blocking performance of oxide coatings. Background Technology

[0002] In controlled nuclear fusion reactor systems, structural materials operate under high temperature and high pressure environments for extended periods. The high flux of hydrogen / deuterium / tritium generated by the fusion reactor readily permeates into these materials, inducing hydrogen embrittlement damage and severely threatening the safe operation of the device. Oxide ceramic coatings (such as zirconium oxide, chromium oxide, titanium oxide, and alumina) have become primary candidate materials for constructing surface protective barriers and inhibiting hydrogen isotope permeation due to their high melting points and excellent thermochemical stability. Traditional oxide hydrogen barrier coatings primarily rely on increasing density to physically block hydrogen diffusion. However, with the increasing demands on hydrogen permeation resistance in fusion reactor design, the hydrogen barrier performance achieved through density has reached its theoretical limit. Furthermore, physical barriers are insufficient to address the cumulative permeation effects under long-term service. Therefore, breakthroughs in the hydrogen permeation resistance performance of coatings are urgently needed.

[0003] Existing technologies attempt to extend the hydrogen diffusion path and improve hydrogen barrier performance through elemental doping, the introduction of second-phase nanosheets, or composite structure design. However, these modification methods often come at the cost of sacrificing the structural stability of the coating. Specifically, elemental doping can easily cause lattice distortion or chemical segregation, leading to a decrease in the mechanical properties of the coating; while introducing a second phase or constructing a multilayer composite structure can extend the diffusion path, the process is complex, and due to the mismatch in thermal expansion coefficients between components, it is prone to interfacial cracking or coating peeling under high-temperature operation. Therefore, existing modification technologies cannot meet the long-term protection requirements of fusion reactors in extreme environments without sacrificing coating integrity.

[0004] The trapping mechanism based on lattice point defect theory holds promise as an effective approach to solving the aforementioned challenges. Unlike traditional physical barriers, lattice point defects, acting as deep-level traps, can strongly interact with hydrogen and its isotopes, effectively trapping and confining diffusing hydrogen atoms, thereby significantly reducing their effective diffusion coefficient in oxides. However, existing fabrication processes struggle to achieve efficient introduction and concentration control of lattice point defects while maintaining the density and integrity of the oxide coating structure. Therefore, there is an urgent need to develop a novel fabrication method that balances coating quality and defect introduction to obtain high-performance oxide coatings resistant to hydrogen / deuterium / tritium penetration. Summary of the Invention

[0005] Based on the needs of existing technologies, this invention provides a method for achieving high hydrogen / deuterium / tritium barrier properties in oxide coatings. The method involves heating the oxide coating to a predetermined temperature and then applying a constant current. The applied current promotes the escape of lattice oxygen, generating lattice point defects, and utilizing these defects to capture hydrogen and its isotope atoms, significantly improving the coating's resistance to hydrogen permeation.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A method for achieving high hydrogen / deuterium / tritium permeation resistance in oxide coatings includes the following steps:

[0008] S1. Preparation of coating samples: An oxide coating is prepared on the surface of the substrate using a coating process or a deposition process to obtain a coating sample. The coating process includes sol-gel method, spraying method, spin coating method, and dip-coating method. The deposition process includes physical vapor deposition, chemical vapor deposition, and atomic layer deposition.

[0009] S2. Arrange conductive electrodes: Arrange conductive electrodes on the surface of the coating sample and lead them out through wires;

[0010] S3. Electric field-assisted heat treatment: The coating sample with conductive electrodes is placed in a protective atmosphere for heat treatment. During the heat treatment process, an electric current is applied to the coating sample through the conductive electrodes.

[0011] S4. Cooling treatment: After the heat treatment and energization are completed, the coating sample is cooled to room temperature to obtain an oxide hydrogen barrier coating with high hydrogen / deuterium / tritium permeation resistance.

[0012] Furthermore, in step S2, a high-temperature resistant conductive paste is applied to both ends of the coated sample, and electrode sheets are arranged as conductive electrodes, with the electrode sheets in electrical contact with the conductive paste.

[0013] Furthermore, in step S1, the oxide coating is a variety of metal oxides or composite oxides, such as zirconium oxide, chromium oxide, titanium oxide, and aluminum oxide.

[0014] Furthermore, in step S3, the heat treatment is carried out in a tube furnace, and the protective atmosphere is a vacuum environment or a mixture of one or more of inert and reducing gases, with an atmosphere flow rate of 10-500 sccm. The inert gas includes nitrogen and argon, and the reducing gas includes hydrogen.

[0015] Furthermore, in step S3, the heat treatment temperature is 300-1200°C, the heating rate is 5-30°C / min, and the holding time is 1-10 h.

[0016] Furthermore, in step S3, the applied current intensity is 0.1A-50A, and the current application time is 0.1h-5h.

[0017] Furthermore, in step S4, the coated sample is cooled to 500°C at a rate of 2-5°C / min, and then cooled to room temperature at a rate of 5-20°C / min.

[0018] An apparatus for implementing the method described above, comprising:

[0019] Heating furnace body, used to provide a heat treatment environment;

[0020] A sample carrier unit is disposed inside the heating furnace and is used to fix the coating sample and the conductive electrode electrically connected to it.

[0021] A power source, connected to the conductive electrode via a wire, is used to apply current to the coating sample during heat treatment;

[0022] The interior of the heating furnace is a vacuum or protective atmosphere environment.

[0023] An oxide hydrogen-blocking coating prepared by the method described above contains a high concentration of lattice point defects introduced by electric field-assisted heat treatment. These lattice point defects act as deep-level traps to capture hydrogen isotope atoms, enabling the coating to reduce hydrogen / deuterium / tritium permeability by 3-4 orders of magnitude.

[0024] An application of an oxide hydrogen-blocking coating as described above is used in the fields of tritium permeation protection of fusion reactor structural materials, hydrogen embrittlement protection of metals, or hydrogen permeation prevention of materials in hydrogen-containing and hydrogen isotope environments.

[0025] The beneficial effects of this invention are as follows:

[0026] (1) This invention proposes a method for achieving high hydrogen / deuterium / tritium barrier properties of oxide coatings by using an electric field to control lattice point defects. This invention has good versatility and is not limited to a single material system. It can stably and efficiently introduce lattice point defects into various oxide coatings (such as zirconium oxide, chromium oxide, titanium oxide, aluminum oxide, etc.) and composite oxides.

[0027] (2) This invention utilizes an external electric field to introduce lattice point defects in the oxide coating, which significantly improves the coating's resistance to hydrogen permeation. Experimental results show that after treatment by this method, the hydrogen permeability of the coating is reduced by 3 to 4 orders of magnitude, significantly enhancing the coating's hydrogen / deuterium / tritium permeation resistance, and meeting the technical requirements for high-performance hydrogen-blocking coatings in extreme environments such as nuclear fusion reactors. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 These are surface scanning electron microscope (SEM) images of the ZrO2 coating, Cr2O3 coating, TiO2 coating, and Al2O3 coating prepared in Examples 1-4 of this invention, as well as macroscopic images of the corresponding coating surfaces.

[0030] Figure 2 These are the X-ray diffraction (XRD) patterns of the four oxide coatings in Examples 1-4 of this invention;

[0031] Figure 3 These are the X-ray photoelectron spectroscopy (XPSO1s) spectra of oxygen on the surfaces of the four oxide coatings in Examples 1-4 of this invention.

[0032] Figure 4 These are hydrogen / deuterium / tritium isotope permeability diagrams of the four oxide coatings in Examples 1-4 of this invention;

[0033] Figure 5 The images show the scanning electron microscope (SEM) image of the ZrO2 coating prepared in Comparative Example 1 of this invention, the corresponding macroscopic surface image of the coating, the X-ray diffraction (XRD) pattern, the X-ray photoelectron spectroscopy (XPS) O1s spectrum of the surface oxygen element, and the hydrogen / deuterium / tritium isotope permeability diagram.

[0034] Figure 6 The images show the scanning electron microscope (SEM) image of the Cr2O3 coating prepared in Comparative Example 1 of this invention, the corresponding macroscopic surface image of the coating, the X-ray diffraction (XRD) pattern, the X-ray photoelectron spectroscopy (XPS) O1s spectrum of the surface oxygen element, and the hydrogen / deuterium / tritium isotope permeability diagram. Detailed Implementation

[0035] The specific embodiments of the present invention are described below to facilitate understanding of the invention by those skilled in the art. However, it should be understood that the present invention is not limited to the scope of the specific embodiments. For those skilled in the art, various modifications are obvious as long as they fall within the spirit and scope of the invention as defined and determined by the appended claims. All inventions utilizing the concept of the present invention are protected.

[0036] Example 1

[0037] (1) Preparation of coating by sol-gel method: Zirconium acetate is dissolved in an appropriate amount of alcohol solvent and stirred until completely dissolved to obtain zirconium sol. The concentration of zirconium source in the sol can be controlled between 0.05 and 5 mol / L. The zirconium sol is coated on the surface of the metal substrate by dip-coating method. After preheating at 50 to 500°C for 0.5 to 1 h, a ZrO2 coating sample with a thickness of 0.05 to 5 μm is obtained.

[0038] (2) Apply a high-temperature sintering conductive metal paste to both sides of the upper surface of the ZrO2 coated sample, and set a platinum electrode sheet in contact with the conductive metal paste and lead it out through a wire;

[0039] (3) The coated sample was placed in a tube furnace and heat treatment was carried out in a vacuum environment. The temperature was increased to 300°C at a rate of 5°C / min and held for 2 hours. After the temperature reached the preset temperature, the power supply and wires were connected. Current control was used and the current intensity was set to 10A. The power was turned off after 2 hours.

[0040] (4) The coating sample was cooled to 500°C at a rate of 2°C / min in the furnace, and then cooled to room temperature at a rate of 5°C / min to obtain a ZrO2 coating with high hydrogen / deuterium / tritium permeation resistance.

[0041] The scanning electron microscope (SEM) image, surface macroscopic image, X-ray diffraction (XRD) pattern, X-ray photoelectron spectroscopy (XPS) O1s spectrum, and hydrogen / deuterium / tritium isotope permeability diagram of the ZrO2 coating prepared in this embodiment are shown below. Figure 1-4 As shown.

[0042] Example 2

[0043] (1) Preparation of coating by sol-gel method: Chromium acetate is dissolved in an appropriate amount of alcohol solvent and stirred until completely dissolved to obtain chromium sol. The concentration of chromium source in the sol can be controlled between 0.05 and 5 mol / L. The chromium sol is coated on the surface of the metal substrate by dip-coating method. After preheating at 50 to 500°C for 0.5 to 1 h, a Cr2O3 coating sample with a thickness of 0.05 to 5 μm is obtained.

[0044] (2) Apply a high-temperature resistant sintering conductive metal paste to both sides of the upper surface of the Cr2O3 coated sample, and set a platinum electrode sheet in contact with the conductive metal paste as a conductive electrode, and lead it out through a wire.

[0045] (3) The coated sample was placed in a tube furnace and heat-treated under a nitrogen protective atmosphere. The temperature was increased to 600°C at a rate of 10°C / min and held for 4 hours. After the temperature reached the preset temperature, the power supply and wires were connected. Current control was used and the current intensity was set to 25A. The power was turned off after 3 hours.

[0046] (4) The coating sample was cooled to 500°C at a rate of 3°C / min in the furnace, and then cooled to room temperature at a rate of 10°C / min to obtain a Cr2O3 coating with high hydrogen / deuterium / tritium penetration resistance.

[0047] The scanning electron microscope (SEM) image, surface macroscopic image, X-ray diffraction (XRD) pattern, X-ray photoelectron spectroscopy (XPS) O1s spectrum, and hydrogen / deuterium / tritium isotope permeability diagram of the Cr2O3 coating prepared in this embodiment are shown below. Figure 1-4 As shown.

[0048] Example 3

[0049] (1) Preparation of coating by sol-gel method: Titanium sulfate is dissolved in an appropriate amount of alcohol solvent and stirred until completely dissolved to obtain titanium sol. The concentration of titanium source in the sol can be controlled between 0.05 and 5 mol / L. The titanium sol is coated on the surface of the metal substrate by dip-coating method. After preheating at 50 to 500°C for 0.5 to 1 h, a TiO2 coating sample with a thickness of 0.05 to 5 μm is obtained.

[0050] (2) Apply a high-temperature sintering conductive metal paste to both sides of the upper surface of the TiO2 coated sample, and set a platinum electrode sheet in contact with the conductive metal paste as a conductive electrode, and lead it out through a wire.

[0051] (3) The coated sample was placed in a tube furnace and heat-treated under an argon protective atmosphere. The temperature was increased to 900°C at a rate of 20°C / min and held for 8 hours. After the temperature reached the preset temperature, the power supply and wires were connected. Current control was used, and the current intensity was set to 40A. The power was turned off after 4 hours.

[0052] (4) The coating sample was cooled to 500°C at a rate of 4°C / min in the furnace, and then cooled to room temperature at a rate of 15°C / min to obtain a TiO2 coating with high hydrogen / deuterium / tritium penetration resistance.

[0053] The scanning electron microscope (SEM) image, surface macroscopic image, X-ray diffraction (XRD) pattern, X-ray photoelectron spectroscopy (XPS) O1s spectrum, and hydrogen / deuterium / tritium isotope permeability diagram of the TiO2 coating prepared in this embodiment are shown below. Figure 1-4 As shown.

[0054] Example 4

[0055] (1) Preparation of coating by sol-gel method: aluminum nitrate is dissolved in an appropriate amount of alcohol solvent and stirred until completely dissolved to obtain aluminum sol. The concentration of aluminum source in the sol can be controlled between 0.05 and 5 mol / L. The aluminum sol is coated on the surface of the metal substrate by dip-coating method. After preheating at 50 to 500°C for 0.5 to 1 h, an Al2O3 coating sample with a thickness of 0.05 to 5 μm is obtained.

[0056] (2) Apply a high-temperature resistant sintering conductive metal paste to both sides of the upper surface of the Al2O3 coated sample, and set a platinum electrode sheet in contact with the conductive metal paste as a conductive electrode, and lead it out through a wire.

[0057] (3) The coated sample was placed in a tube furnace and heat-treated in a hydrogen atmosphere. The temperature was increased to 1200°C at a rate of 30°C / min and held for 10 hours. After the temperature reached the preset temperature, the power supply and wires were connected. Current control was used and the current intensity was set to 50A. The power was turned off after 5 hours.

[0058] (4) The coating sample was cooled to 500°C at a rate of 5°C / min in the furnace, and then cooled to room temperature at a rate of 20°C / min to obtain an Al2O3 coating with high hydrogen / deuterium / tritium penetration resistance.

[0059] The scanning electron microscope (SEM) image, surface macroscopic image, X-ray diffraction (XRD) pattern, X-ray photoelectron spectroscopy (XPS) O1s spectrum, and hydrogen / deuterium / tritium isotope permeability diagram of the Al2O3 coating prepared in this embodiment are shown below. Figure 1-4 As shown.

[0060] Comparative Example 1

[0061] (1) Preparation of coating by sol-gel method: Zirconium acetate is dissolved in an appropriate amount of alcohol solvent and stirred until completely dissolved to obtain zirconium sol. The concentration of zirconium source in the sol can be controlled between 0.05 and 5 mol / L. The zirconium sol is coated on the surface of the metal substrate by dip-coating method. After preheating at 50 to 500°C for 0.5 to 1 h, a ZrO2 coating sample with a thickness of 0.05 to 5 μm is obtained.

[0062] (2) The coated sample was placed in a tube furnace and heat treatment was carried out in an atmosphere of nitrogen and argon with a volume ratio of 1:1. The temperature was increased to 300°C at a rate of 5°C / min and held for 2 hours.

[0063] (3) The coating sample was cooled to 500°C in the furnace at a cooling rate of 2°C / min, and then cooled to room temperature at a cooling rate of 5°C / min to obtain the ZrO2 coating.

[0064] The scanning electron microscope (SEM) image, surface macroscopic image, X-ray diffraction (XRD) pattern, X-ray photoelectron spectroscopy (XPS) O1s spectrum, and hydrogen / deuterium / tritium isotope permeability diagram of the ZrO2 coating prepared in this embodiment are shown below. Figure 5 As shown.

[0065] Comparative Example 2

[0066] (1) Preparation of coating by sol-gel method: Chromium acetate is dissolved in an appropriate amount of alcohol solvent and stirred until completely dissolved to obtain chromium sol. The concentration of chromium source in the sol can be controlled between 0.05 and 5 mol / L. The chromium sol is coated on the surface of the metal substrate by dip-coating method. After preheating at 50 to 500°C for 0.5 to 1 h, a ZrO2 coating sample with a thickness of 0.05 to 5 μm is obtained.

[0067] (2) The coated sample was placed in a tube furnace and heat treatment was carried out in an atmosphere of argon and hydrogen with a volume ratio of 5:1. The temperature was increased to 600°C at a rate of 10°C / min and held for 4 hours.

[0068] (3) The coating sample was cooled to 500°C at a rate of 3°C / min in the furnace, and then cooled to room temperature at a rate of 10°C / min to obtain the Cr2O3 coating.

[0069] The scanning electron microscope (SEM) image, surface macroscopic image, X-ray diffraction (XRD) pattern, X-ray photoelectron spectroscopy (XPS) O1s spectrum, and hydrogen / deuterium / tritium isotope permeability diagram of the Cr2O3 coating prepared in this embodiment are shown below. Figure 6 As shown.

[0070] refer to Figure 1 Macroscopic photographs and scanning electron microscope (SEM) images of the four oxide coatings (ZrO2, Cr2O3, TiO2, and Al2O3) show that all coating surfaces exhibit a dense, smooth, and uniform microstructure. Observations revealed no obvious macroscopic defects such as cracks, pores, pinholes, or peeling on the surfaces of any of the four coatings. This fully demonstrates that the electric field-assisted preparation process described in this invention has excellent film quality and versatility; the applied electric field treatment alters the microstructure of the material without compromising the structural integrity of the coating, which retains its excellent density.

[0071] refer to Figure 2Analysis of the X-ray diffraction (XRD) patterns of the four oxide coatings revealed that all samples exhibited sharp and high-intensity diffraction peaks, with peak positions closely matching the characteristic peak positions of standard cards PDF#88-1007, PDF#38-1479, PDF#21-1276, and PDF#46-1131. This indicates that the ZrO2, Cr2O3, TiO2, and Al2O3 coatings, after processing according to the present invention, all possess good crystallinity and purity. No obvious impurity peaks were detected in the patterns, indicating that the precursors were completely converted into the target oxide phase, resulting in the corresponding oxide coatings.

[0072] refer to Figure 3 XPS 1s high-resolution energy dispersive spectroscopy analysis of the four coating samples revealed significant fitting peaks at the characteristic binding energy positions of lattice defects and oxygen vacancies in the ZrO2, Cr2O3, TiO2, and Al2O3 coatings, with high peak intensities. This result directly confirms the effectiveness of the external electric field-assisted treatment, indicating that the process successfully introduced a high concentration of lattice defects into various oxide coating systems, providing abundant sites for subsequent hydrogen isotope capture.

[0073] refer to Figure 4 Hydrogen isotope permeation experiments showed that, compared to uncoated metal substrates, samples coated with ZrO2, Cr2O3, TiO2, and Al2O3 showed a 3-4 order of magnitude reduction in hydrogen permeability, demonstrating excellent hydrogen / deuterium / tritium permeation blocking performance. Combined with... Figure 3 XPS analysis results show that the high concentration of lattice point defects induced by the electric field in the coating acts as an effective hydrogen trap, significantly hindering the diffusion behavior of hydrogen isotopes in the coating, thereby greatly improving the hydrogen / deuterium / tritium permeation resistance of the oxide hydrogen barrier coating.

[0074] refer to Figure 5 For the ZrO2 coating prepared solely by heat treatment (Comparative Example 1), macroscopic photographs and scanning electron microscope (SEM) images of its surface were observed. The coating surface was dense, with no macroscopic defects such as voids. The X-ray diffraction (XRD) pattern was consistent with the crystal structure of the coating obtained by external electric field assisted treatment in Example 1 of this invention. XPS O 1s spectrum analysis showed that the characteristic peak intensity corresponding to the lattice oxygen vacancies in this sample was extremely weak, indicating that a single heat treatment method is unlikely to introduce lattice point defects into the ZrO2 coating. Hydrogen isotope permeation experiments showed that the hydrogen permeability of this coating was almost the same as that of the metal substrate, failing to play a hydrogen barrier role. By comparing with Example 1 of this invention, it is shown that external electric field assistance can introduce lattice point defects into the coating, thereby significantly improving the coating's resistance to hydrogen / deuterium / tritium permeation.

[0075] refer to Figure 6 Macroscopic photographs and scanning electron microscope (SEM) images of the Cr2O3 coating obtained solely through heat treatment (Comparative Example 2) were observed. The coating surface was smooth and free of macroscopic defects such as cracks. The X-ray diffraction (XRD) pattern was consistent with the crystal structure of the coating obtained by external electric field assisted treatment in Example 2 of this invention. XPS O 1s spectrum analysis showed that the Cr2O3 coating obtained solely through heat treatment lacked lattice oxygen vacancy signals. Hydrogen isotope permeation experiments showed that the hydrogen permeability of this coating was very close to that of the metal substrate, indicating that the coating did not have an effective hydrogen barrier effect. By comparing with Example 2 of this invention, it is shown that external electric field assistance can introduce lattice point defects into the coating, thereby significantly improving the coating's resistance to hydrogen / deuterium / tritium permeation.

[0076] This invention proposes a general method for achieving high hydrogen / deuterium / tritium permeation resistance in oxide coatings. Verification using four different oxide systems in the examples confirms that an external electric field-assisted treatment technique can efficiently introduce high concentrations of lattice point defects into various oxide coatings. Experimental data shows that this method is not limited to specific material systems but has significant universality, successfully constructing lattice defect traps through electric field manipulation, thereby endowing the coating with excellent resistance to hydrogen isotope permeation. The resulting oxide coating not only has a dense structure but also possesses extremely high hydrogen / deuterium / tritium permeation resistance. This invention has significant application prospects in the fields of tritium permeation protection of fusion reactor structural materials, hydrogen embrittlement protection of metals, and hydrogen permeation resistance in other hydrogen-containing and hydrogen isotope environments.

[0077] The experimental results of four different oxide systems in this invention consistently confirm the universality of the method. For different types of oxide coatings in the embodiments, lattice point defects can be introduced into the oxide coating using an applied electric field. Experimental data show that the process described in this invention can effectively construct lattice point defects using an applied electric field for different types of oxide coatings, thereby achieving excellent hydrogen permeation resistance. This universality greatly expands the application scope of this technology, making it of significant value for promotion in the fields of fusion reactor blankets, hydrogen storage containers, and hydrogen pipeline protection.

[0078] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed herein should be included within the scope of protection of the present invention. Therefore, the present invention will not 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 method for achieving high hydrogen / deuterium / tritium permeation resistance in oxide coatings, characterized in that, Includes the following steps: S1. Preparation of coating samples: An oxide coating is prepared on the surface of the substrate using a coating process or a deposition process to obtain a coating sample. The coating process includes sol-gel method, spraying method, spin coating method, and dip-coating method. The deposition process includes physical vapor deposition, chemical vapor deposition, and atomic layer deposition. S2. Arrange conductive electrodes: Arrange conductive electrodes on the surface of the coating sample and lead them out through wires; S3. Electric field-assisted heat treatment: The coating sample with conductive electrodes is placed in a protective atmosphere for heat treatment. During the heat treatment process, an electric current is applied to the coating sample through the conductive electrodes. S4. Cooling treatment: After the heat treatment and energization are completed, the coating sample is cooled to room temperature to obtain an oxide hydrogen barrier coating with high hydrogen / deuterium / tritium permeation resistance.

2. The method according to claim 1, characterized in that, In step S2, a high-temperature resistant conductive paste is applied to both ends of the coated sample, and electrode sheets are arranged as conductive electrodes, with the electrode sheets in electrical contact with the conductive paste.

3. The method according to claim 1, characterized in that, In step S1, the oxide coating is a variety of metal oxides or composite oxides, such as zirconium oxide, chromium oxide, titanium oxide, and aluminum oxide.

4. The method according to claim 1, characterized in that, In step S3, the heat treatment is carried out in a tube furnace. The protective atmosphere is a vacuum environment or a mixture of one or more of inert and reducing gases. The atmosphere flow rate is 10-500 sccm. The inert gas includes nitrogen and argon, and the reducing gas includes hydrogen.

5. The method according to claim 1, characterized in that, In step S3, the heat treatment temperature is 300-1200°C, the heating rate is 5-30°C / min, and the holding time is 1-10 h.

6. The method according to claim 1, characterized in that, In step S3, the applied current intensity is 0.1A-50A, and the current application time is 0.1h-5h.

7. The method according to claim 1, characterized in that, In step S4, the coated sample is cooled to 500°C at a rate of 2-5°C / min, and then cooled to room temperature at a rate of 5-20°C / min.

8. An apparatus for implementing the method according to any one of claims 1-7, characterized in that, include: Heating furnace body, used to provide a heat treatment environment; A sample carrier unit is disposed inside the heating furnace and is used to fix the coating sample and the conductive electrode electrically connected to it. A power source, connected to the conductive electrode via a wire, is used to apply current to the coating sample during heat treatment; The interior of the heating furnace is a vacuum or protective atmosphere environment.

9. An oxide hydrogen-barrier coating prepared by the method according to any one of claims 1-7, characterized in that, The coating contains a high concentration of lattice point defects introduced through electric field-assisted heat treatment. These lattice point defects act as deep-level traps to capture hydrogen isotope atoms, enabling the coating to reduce hydrogen / deuterium / tritium permeability by 3-4 orders of magnitude.

10. An application of the oxide hydrogen-barrier coating as described in claim 9, characterized in that, Applications include tritium permeation protection in fusion reactor structural materials, hydrogen embrittlement protection in metals, and hydrogen permeation prevention in other hydrogen-containing and hydrogen isotope environments.

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