A hydrogen isotope diffusion resistant material, a preparation method and application thereof, and a first wall material and application thereof

Abstract

The application provides a hydrogen isotope diffusion resistance material and a preparation method and application thereof, and a first wall material and application thereof, and belongs to the technical field of hydrogen permeation resistance materials. The hydrogen isotope diffusion resistance material provided by the application comprises a helium-rich tungsten layer and a pure tungsten layer arranged on the surface of a tungsten base in sequence; the helium content in the helium-rich tungsten layer is greater than or equal to 1*10 5 ppm. The hydrogen isotope diffusion resistance material provided by the application has the characteristics of high film-base bonding force, good compatibility, high sputtering threshold and excellent hydrogen isotope diffusion resistance performance.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen permeation barrier materials technology, specifically relating to a hydrogen isotope diffusion barrier material and its preparation method and application, and a first wall material and its application. Background Technology

[0002] In nuclear fusion reactors, high-density deuterium-tritium plasma will directly act on the first wall material and is prone to diffusion, penetration and even leakage in the first wall and its structural materials, reducing the mechanical properties of the first wall and its structural materials, affecting the self-sufficiency of nuclear fusion fuel and causing radioactive pollution to the environment. Therefore, how to prevent or reduce the diffusion of tritium in the first wall and its structural materials of fusion reactors is a key technical challenge in the current development of fusion energy. Summary of the Invention

[0003] The purpose of this invention is to provide a hydrogen isotope diffusion barrier material, its preparation method and application, and a first wall material and its application. The hydrogen isotope diffusion barrier material provided by this invention has the characteristics of high film-substrate bonding, good compatibility, high sputtering threshold, and excellent hydrogen isotope diffusion barrier performance.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a hydrogen isotope diffusion-blocking material, comprising a helium-rich tungsten layer and a pure tungsten layer stacked on the surface of a tungsten substrate; wherein the helium-rich tungsten layer contains ≥1×10⁻⁶ helium. 5 ppm.

[0006] Preferably, the thickness of the helium-rich tungsten layer is 10–50 nm.

[0007] Preferably, the thickness of the pure tungsten layer is 50–1000 nm.

[0008] This invention provides a method for preparing the hydrogen isotope diffusion-blocking material described in the above technical solution, comprising the following steps:

[0009] Plasma irradiation is performed on the surface of a tungsten substrate, i.e., a helium-rich tungsten layer is prepared on the surface of a tungsten substrate;

[0010] Based on a pure tungsten target, a pure tungsten layer is prepared on the surface of the helium-rich tungsten layer using magnetron sputtering, thus obtaining the hydrogen-blocking isotope diffusion material on the surface of the tungsten substrate.

[0011] Preferably, the plasma irradiation conditions include: applying a bias voltage below -200V to a tungsten substrate, wherein the temperature of the tungsten substrate is 100–400°C; and a helium plasma flux of not less than 10. 19 ions / m 2 s, irradiation dose is 10 24 ~1027 ions / m 2 .

[0012] Preferably, the magnetron sputtering is performed in an argon atmosphere with a flow rate of 20–100 sccm.

[0013] Preferably, the conditions for magnetron sputtering include: applying a bias voltage of -20 to -50V to the helium-rich tungsten layer, the helium-rich tungsten layer being kept rotating at a rate of 5 to 10 r / min, and the temperature of the helium-rich tungsten layer not exceeding 40 to 60°C.

[0014] The present invention provides the application of the hydrogen-blocking isotope diffusion material described in the above technical solution or the hydrogen-blocking isotope diffusion material prepared by the preparation method described in the above technical solution in a first wall material.

[0015] The present invention provides a first wall material, including the hydrogen isotope diffusion barrier material described in the above technical solution or the hydrogen isotope diffusion barrier material prepared by the preparation method described in the above technical solution.

[0016] This invention provides the application of the first wall material in a fusion reactor.

[0017] This invention provides a hydrogen isotope diffusion barrier material, comprising a helium-rich tungsten layer and a pure tungsten layer stacked on the surface of a tungsten substrate. In this invention, the helium-rich tungsten layer provides a channel for hydrogen isotopes to diffuse to the surface during service, thereby hindering their further diffusion into the tungsten substrate. The pure tungsten layer, as a protective layer, traps a high concentration of hydrogen at its interface with the helium-rich tungsten layer, working together to impede hydrogen diffusion. This results in a hydrogen isotope diffusion barrier material with a high sputtering threshold and low sputtering yield. Simultaneously, the pure tungsten layer effectively delays damage to the helium-rich tungsten layer after plasma sputtering during service, ensuring the service life of the hydrogen isotope diffusion barrier material. Furthermore, the pure tungsten layer has the same composition as the substrate, exhibiting excellent compatibility and adhesion, ensuring the structural stability of the resulting hydrogen isotope diffusion barrier material at high temperatures and solving the problem of film peeling under high-temperature conditions. The embodiments show that the present invention utilizes the barrier effect of the helium-rich tungsten layer and the pure tungsten layer / tungsten matrix interface on the diffusion of hydrogen isotopes to reduce the amount of deuterium retained in the tungsten matrix after deuterium plasma irradiation to the original 5% to 20%.

[0018] Furthermore, based on the inhibitory effect of the helium-rich tungsten layer and the tungsten matrix interface on hydrogen isotope diffusion, this invention constructs a hydrogen isotope diffusion-blocking material with hydrogen isotope diffusion-blocking function on the surface of the first wall material of the fusion reactor, thereby achieving effective control of hydrogen isotope permeation in the fusion reactor. The preparation method of the hydrogen isotope diffusion-blocking material can be used to prepare fusion reactor structural materials and hydrogen storage industrial materials with hydrogen isotope diffusion-blocking properties.

[0019] Furthermore, the present invention constructs a hydrogen isotope diffusion barrier material on the surface of the first wall material, enabling it to hinder tritium permeation, thereby greatly reducing the service pressure of the hydrogen isotope diffusion barrier material, effectively controlling tritium leakage after the hydrogen isotope diffusion barrier material fails under irradiation, thermal environment or mechanical deformation, and reducing tritium recovery costs and technical difficulties. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments 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.

[0021] Figure 1 This is a schematic diagram of the structure of the hydrogen isotope diffusion barrier material obtained in Example 1;

[0022] Figure 2 This is a surface morphology diagram of the pure tungsten layer on the hydrogen-blocking isotope diffusion material obtained in Example 1;

[0023] Figure 3 This is a schematic diagram showing the cross-section and thickness of the pure tungsten layer on the hydrogen-blocking isotope diffusion material obtained in Example 1;

[0024] Figure 4 The graph shows the test results of the bonding force between the pure tungsten layer and the tungsten substrate on the hydrogen isotope diffusion barrier material obtained in Example 1.

[0025] Figure 5 The hydrogen-deuterium depth distribution maps are shown for the tungsten matrix and the tungsten matrix containing hydrogen isotope diffusion barrier material obtained in Example 1 after deuterium plasma irradiation.

[0026] Figure 6 The deuterium thermal desorption spectra of the tungsten matrix and the tungsten matrix containing the hydrogen isotope diffusion barrier material obtained in Example 1 after deuterium plasma irradiation are shown.

[0027] Figure 7 The graph shows the total amount of deuterium retained in the tungsten matrix and the tungsten matrix containing hydrogen isotope diffusion barrier material obtained in Example 1 after deuterium plasma irradiation. Detailed Implementation

[0028] This invention provides a hydrogen isotope diffusion-blocking material, comprising a helium-rich tungsten layer and a pure tungsten layer stacked on the surface of a tungsten substrate; wherein the helium-rich tungsten layer contains ≥1×10⁻⁶ helium. 5 ppm, preferably ≥2×10 5 ppm.

[0029] In this invention, the thickness of the helium-rich tungsten layer is preferably 10-50 nm, more preferably 20-40 nm.

[0030] In this invention, the thickness of the pure tungsten layer is preferably 50-1000 nm, more preferably 100-500 nm.

[0031] The hydrogen isotope diffusion barrier material of this invention can reduce the amount of hydrogen isotopes entering the tungsten matrix to 5% to 20% of the original amount. In this invention, the bonding force between the pure tungsten layer and the tungsten matrix is ​​preferably greater than 10N.

[0032] This invention provides a method for preparing the hydrogen isotope diffusion-blocking material described in the above technical solution, comprising the following steps:

[0033] Plasma irradiation is performed on the surface of a tungsten substrate, i.e., a helium-rich tungsten layer is prepared on the surface of a tungsten substrate;

[0034] Based on a pure tungsten target, a pure tungsten layer is prepared on the surface of the helium-rich tungsten layer using magnetron sputtering, thus obtaining the hydrogen-blocking isotope diffusion material on the surface of the tungsten substrate.

[0035] In this invention, unless otherwise specified, all raw materials used are commercially available products well known to those skilled in the art or prepared using methods well known to those skilled in the art.

[0036] Before plasma irradiation, the tungsten substrate is preferably washed with anhydrous ethanol. In this invention, the washing is preferably performed 2 to 4 times, more preferably 3 times; the washing time for each wash is preferably 15 to 25 minutes, more preferably 20 minutes.

[0037] This invention involves plasma irradiation of a tungsten substrate surface to prepare a helium-rich tungsten layer. Before plasma irradiation, the helium flow rate is preferably 20–100 sccm, more preferably 40 sccm; the cavity pressure is preferably 0.1–5 Pa, more preferably 0.1–0.3 Pa. This invention preferably employs a high-density helium plasma irradiation method to prepare the helium-rich tungsten layer on the tungsten substrate surface. During plasma irradiation, the microwave ECR ion source power during plasma discharge is preferably 100–1000 W, more preferably 500 W; the helium plasma flux is preferably not less than 10... 19 ions / m 2 s, more preferably 10 19 ~10 22 ions / m 2 s; the preferred irradiation dose is 10 24 ~10 27 ions / m 2 More preferably 1.0×10 25ions / m 2 The chamber vacuum is preferably ≤1.0×10⁻⁶. -4 Pa, more preferably ≤5.0×10 -5 Pa. During plasma irradiation, the present invention preferably applies a bias voltage of -200V or less (preferably -50 to -200V) to the tungsten substrate, and preferably heats the tungsten substrate to 100 to 400°C (preferably 200 to 300°C). In embodiments of the present invention, specifically in the plasma irradiation apparatus, the temperature of the tungsten substrate is controlled by a cooling device and a heating device attached to the back of the tungsten substrate. After the plasma irradiation is completed, the present invention preferably cools the obtained material to room temperature under vacuum conditions to obtain a helium-rich tungsten layer.

[0038] After obtaining the helium-rich tungsten layer, this invention uses a pure tungsten target and magnetron sputtering to prepare a pure tungsten layer on the surface of the helium-rich tungsten layer, i.e., to obtain the hydrogen isotope diffusion barrier material on the surface of the tungsten substrate. In this invention, the purity of the tungsten target is preferably >99.99%. When preparing the pure tungsten layer, this invention preferably uses a DC power supply to sputter the tungsten target. In this invention, the DC power supply power of the tungsten target is preferably 100–300 W, more preferably 200 W; the sputtering time of the tungsten target is preferably 10–60 min, more preferably 20–50 min. The magnetron sputtering of this invention is preferably carried out in an argon atmosphere, and the flow rate of the argon gas is preferably 20–100 sccm, more preferably 40 sccm. When preparing the pure tungsten layer, the gas pressure in the magnetron sputtering chamber is preferably 0.6–0.8 Pa, more preferably 0.65–0.75 Pa. During magnetron sputtering, the present invention preferably applies a bias voltage of -20 to -50V (preferably -30 to 40V) to the tungsten substrate. During magnetron sputtering, the helium-rich tungsten layer is preferably kept rotating at a rotation speed of 5 to 10 r / min, more preferably 6 to 8 r / min. During magnetron sputtering, the helium-rich tungsten layer is preferably not heated, and its temperature is preferably not higher than 60°C, more preferably 40 to 60°C. After magnetron sputtering, the resulting material is preferably cooled to room temperature under vacuum conditions to obtain the hydrogen isotope diffusion barrier material on the tungsten substrate surface.

[0039] The hydrogen isotope diffusion barrier material of this invention has excellent hydrogen isotope diffusion barrier performance, good bonding force between the pure tungsten layer and the tungsten substrate, and a high plasma sputtering threshold. Its preparation method is simple, and the helium concentration of the helium-rich tungsten layer and the thickness of the pure tungsten layer can be precisely controlled.

[0040] The present invention also provides the application of the hydrogen-blocking isotope diffusion material described in the above technical solution or the hydrogen-blocking isotope diffusion material prepared by the preparation method described in the above technical solution in the first wall material.

[0041] The present invention also provides a first wall material, including the hydrogen isotope diffusion barrier material described in the above technical solution or the hydrogen isotope diffusion barrier material prepared by the preparation method described in the above technical solution.

[0042] This invention provides the application of the first wall material in a fusion reactor.

[0043] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0044] The plasma irradiation equipment used in this embodiment is a linear plasma irradiation device equipped with active cooling and heating devices. The plasma is excited using a microwave ECR ion source and confined by a ring excitation coil. The device is equipped with a Langmuir probe (capable of measuring parameters such as ion flux and plasma density). During irradiation, the material is clamped on a sample tray; the device is equipped with thermocouples to monitor the material temperature in real time during irradiation; the device is also equipped with a bias power supply connected to the sample tray. During plasma irradiation, the helium flow rate is fixed, the helium purity is >99.99%, and the cavity pressure is regulated using a turbomolecular pump valve.

[0045] The parameters of the magnetron sputtering equipment used in this embodiment are as follows: equipment ultimate vacuum <1×10 -4 The equipment has a heating temperature range of 10–300℃ and features temperature control. A strong magnetic target head is mounted on top of the equipment for attaching the target material, and the target head is equipped with a DC sputtering power supply. During magnetron sputtering, the substrate is placed on a rotatable sample tray at the bottom of the equipment. The equipment is equipped with a bias power supply connected to the sample tray. In the process of preparing pure tungsten layers using magnetron sputtering, the argon gas flow rate is fixed, the argon gas purity is >99.999%, and the chamber pressure is regulated using a turbomolecular pump valve.

[0046] Example 1

[0047] The tungsten substrate was cleaned and wiped in anhydrous ethanol using an ultrasonic cleaner. This process was repeated three times, each time for 20 minutes. After cleaning, the tungsten substrate was removed and dried.

[0048] A helium-rich tungsten layer was prepared on the surface of a tungsten substrate by plasma irradiation under a helium atmosphere. The specific process is as follows: (1) The tungsten substrate was tightly clamped on the sample plate, and the plasma irradiation equipment was evacuated until the pressure in the cavity was less than 1×10⁻⁶. -4When Pa, set the heating temperature of the sample plate to 200℃ and turn on the heating; (2) When the temperature of the sample plate reaches 200℃, introduce 40 sccm of helium gas, adjust the chamber pressure to 0.13 Pa, turn on the microwave ECR ion source and set the output power to 500W, apply a -100V bias voltage to the tungsten substrate on the sample plate using a bias power supply, and excite the helium plasma to irradiate the surface of the tungsten substrate; (3) Measure the hydrogen ion flux using a Langmuir probe and determine the irradiation time according to the irradiation dose; (4) When the irradiation dose reaches the set value (the helium plasma flux is 1.5×10), 21 ions / m 2 s, the irradiation dose is 1.0 × 10 25 ions / m 2 (5) After the helium plasma irradiation is completed, the tungsten substrate with a helium-rich tungsten layer on its surface is placed in a vacuum environment and cooled to room temperature before being taken out.

[0049] Based on a pure tungsten target, a pure tungsten layer was prepared on the surface of the helium-rich tungsten layer using magnetron sputtering. The specific process is as follows: (1) The helium-rich tungsten layer was placed on the sample tray at the bottom of the magnetron sputtering equipment, and the magnetron sputtering equipment was evacuated; (2) The gas pressure in the chamber of the magnetron sputtering equipment was <1.5×10⁻⁶. -3 When Pa, 40 sccm of argon gas is introduced, the chamber pressure is adjusted to 5 Pa, the sample disk is turned on (rotation speed is 5 r / min), the bias power supply (-500V) is turned on, and argon plasma surface cleaning is performed; (3) Keep 40 sccm of argon gas introduced, adjust the chamber pressure to 0.65 Pa, apply 200W power to the tungsten target using DC power supply, apply -50V bias to the helium-rich tungsten layer on the sample disk using bias power supply, and start depositing a pure tungsten layer on the helium-rich tungsten layer. The deposition time is 10 min. After the deposition, a pure tungsten layer can be obtained on the surface of the helium-rich tungsten layer, that is, a hydrogen isotope diffusion barrier material is formed on the surface of the tungsten substrate (the thickness of the pure tungsten layer is 50-60 nm).

[0050] A schematic diagram of the hydrogen isotope diffusion barrier material prepared in Example 1 is shown below. Figure 1 As shown. By Figure 1 As can be seen, the hydrogen isotope diffusion barrier material prepared in this embodiment comprises a helium-rich tungsten layer and a pure tungsten layer sequentially disposed on the surface of a tungsten substrate, wherein the thickness of the helium-rich tungsten layer is 20-30 nm and the thickness of the pure tungsten layer is 50-60 nm.

[0051] The surface morphology of the pure tungsten layer of the hydrogen isotope diffusion barrier material prepared in Example 1 is as follows: Figure 2 As shown, the cross-section and thickness are as follows Figure 3 As shown. By Figures 2-3 It can be seen that the pure tungsten layer prepared in Example 1 has good compactness.

[0052] The binding force and deuterium retention of the hydrogen isotope diffusion barrier material prepared in Example 1 were tested, and the specific procedures are as follows:

[0053] (1) Bonding strength test

[0054] The bonding force between the pure tungsten layer and the tungsten substrate on the hydrogen-blocking isotope diffusion material obtained in Example 1 was tested using a scratch tester, and the results are as follows: Figure 4 As shown. By Figure 4 It can be seen that the bonding force between the pure tungsten layer and the tungsten substrate is 13 N.

[0055] (2) Deuterium retention test

[0056] The tungsten matrix and the tungsten matrix containing hydrogen isotope diffusion-blocking material obtained in Example 1 were irradiated using deuterium plasma at a dose of 1 × 10⁻⁶. 25 ions / m 2 The incident energy of deuterium ions was 38 eV / D, and the irradiation temperature was 400 K. After deuterium plasma irradiation, the concentration distribution of deuterium on a tungsten substrate and a tungsten substrate containing hydrogen isotope diffusion-restricting materials was measured using glow discharge spectroscopy. The results are as follows: Figure 5 As shown. By Figure 5 It can be seen that on a tungsten substrate containing hydrogen isotope diffusion barrier material, deuterium is distributed at a depth of 500 nm on the surface of both the hydrogen isotope diffusion barrier material and the tungsten substrate (including the pure tungsten layer and the helium-rich tungsten layer); while on a tungsten substrate without any coating, deuterium is distributed at a depth of 5 μm on the surface of the tungsten substrate.

[0057] After deuterium plasma irradiation, the desorption curves of deuterium on the surface of the tungsten substrate and the tungsten substrate containing hydrogen isotope diffusion-blocking material obtained in Example 1 were measured using thermal desorption spectroscopy. The results are as follows: Figure 6 As shown. The total amount of tungsten substrate and the tungsten substrate surface containing hydrogen isotope diffusion-blocking material obtained in Example 1 are as follows. Figure 7 As shown; by Figure 7 It can be seen that the total deuterium retention on the tungsten matrix containing hydrogen isotope diffusion-impeding material is 1.9 × 10⁻⁶. 19 D / m 2 On a tungsten substrate without any coating, the total deuterium retention was 2.2 × 10⁻⁶. 20 D / m 2 .

[0058] It can be seen that the deuterium distribution depth on the tungsten matrix is ​​significantly greater than that on the tungsten matrix containing the hydrogen isotope diffusion barrier material obtained in Example 1, and the deuterium desorption signal intensity and the total amount of deuterium retention on the tungsten matrix are both an order of magnitude higher than those in Example 1.

[0059] The test results above show that the hydrogen-blocking isotope diffusion material set on the surface of the tungsten material in this invention can reduce the amount of deuterium retention in the tungsten material to 8.8% of that without the hydrogen-blocking isotope diffusion material. This demonstrates that the hydrogen-blocking isotope diffusion effect of the hydrogen-blocking isotope diffusion material is significant.

[0060] 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 hydrogen isotope diffusion-blocking material, characterized in that, This includes a helium-rich tungsten layer and a pure tungsten layer sequentially stacked on the surface of a tungsten substrate; the helium-rich tungsten layer contains a helium content ≥1×10⁻⁶. 5 ppm; The thickness of the helium-rich tungsten layer is 10~50 nm; the thickness of the pure tungsten layer is 50~1000 nm. The preparation method of the hydrogen isotope diffusion barrier material includes the following steps: Plasma irradiation is performed on the surface of a tungsten substrate, i.e., a helium-rich tungsten layer is prepared on the surface of a tungsten substrate; Based on a pure tungsten target, a pure tungsten layer is prepared on the surface of the helium-rich tungsten layer using magnetron sputtering, thus obtaining the hydrogen-blocking isotope diffusion material on the surface of the tungsten substrate.

2. The method for preparing the hydrogen-blocking isotope diffusion material according to claim 1, comprising the following steps: Plasma irradiation is performed on the surface of a tungsten substrate, i.e., a helium-rich tungsten layer is prepared on the surface of a tungsten substrate; Based on a pure tungsten target, a pure tungsten layer is prepared on the surface of the helium-rich tungsten layer using magnetron sputtering, thus obtaining the hydrogen-blocking isotope diffusion material on the surface of the tungsten substrate.

3. The preparation method according to claim 2, characterized in that, The conditions for plasma irradiation include: applying a bias voltage below -200V to the tungsten substrate, and the temperature of the tungsten substrate being 100~400℃; the helium plasma flux being not less than 10. 19 ions / m 2 s, irradiation dose is 10 24 ~10 27 ions / m 2 .

4. The preparation method according to claim 2, characterized in that, The magnetron sputtering is performed in an argon atmosphere with a flow rate of 20-100 sccm.

5. The preparation method according to claim 2 or 4, characterized in that, The conditions for magnetron sputtering include: applying a bias voltage of -20 to -50V to the helium-rich tungsten layer, maintaining the helium-rich tungsten layer at a rotation rate of 5 to 10 r / min, and the temperature of the helium-rich tungsten layer not exceeding 60°C.

6. The application of the hydrogen-blocking isotope diffusion material according to claim 1 or the hydrogen-blocking isotope diffusion material prepared by any one of claims 2 to 5 in the first wall material.

7. A first wall material, comprising the hydrogen isotope diffusion barrier material of claim 1 or the hydrogen isotope diffusion barrier material prepared by the preparation method of any one of claims 2 to 5.

8. The application of the first wall material as described in claim 7 in a fusion reactor.

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