CN115305442B - Surface modified tritium breeder and preparation method thereof - Google Patents

Surface modified tritium breeder and preparation method thereof Download PDF

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CN115305442B
CN115305442B CN202211030349.0A CN202211030349A CN115305442B CN 115305442 B CN115305442 B CN 115305442B CN 202211030349 A CN202211030349 A CN 202211030349A CN 115305442 B CN115305442 B CN 115305442B
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tritium
tritium breeder
coating layer
breeder
modified
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CN115305442A (en
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王龙
洪志浩
严觉民
巩保平
张龙
王晓宇
冯勇进
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Southwestern Institute of Physics
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Southwestern Institute of Physics
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/223—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating specially adapted for coating particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18—Non-metallic particles coated with metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0635—Carbides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21B—FUSION REACTORS
    • G21B1/00—Thermonuclear fusion reactors
    • G21B1/11—Details
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/10—Nuclear fusion reactors

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Abstract

The application discloses a surface modified tritium breeder and a preparation method thereof, wherein a magnetron sputtering coating method is adopted to deposit a metal coating layer on the surface of tritium breeder particles, or a metal coating layer and a nonmetal coating layer are sequentially deposited; the number of the metal coating layers is one or more than two; the metal species is a combination of one or more metals; the number of the nonmetallic coating layers is one or more than two, and the nonmetallic species is one or a combination of nonmetallic species. The improved tritium breeder prepared by the method has excellent corrosion compatibility and good tritium release performance, is high in efficiency, good in economy and environment-friendly, can be used for preparing various coating materials, and is beneficial to establishing a surface improved tritium breeder candidate material library of a system.

Description

Surface modified tritium breeder and preparation method thereof
Technical Field
The application relates to the technical field of fusion reactor fuels, in particular to a surface modified tritium breeder and a preparation method thereof.
Background
Controllable nuclear fusion energy is one of the most promising radical outlets for thoroughly solving the energy problem. Hydrogen and its isotopes (deuterium, tritium) are important fuels for magnetically confined nuclear fusion reactors. For the 2GW DEMO exemplary stack, the daily tritium consumption is 313g, the daily tritium yield of ITER is only 0.4g, the CANDU tritium price is 30000 dollars/g, and the tritium released into the environment under normal working conditions is not higher than 1g for one year. In view of economic and safety considerations, efficient utilization of fuel tritium is a major key to commercialization of fusion stacks. Tritium proliferation cladding is a core component for realizing tritium self-sustaining and energy extraction by fusion reactor, and can be realized by Li 6 Is reacted with neutrons 1 n+ 6 Li→ 4 He+3t+4.78mev) on-line tritium production, so developing advanced tritium breeder materials to improve tritium breeder tritium production efficiency has become a focus of research in the field of fusion.
Lithium orthosilicate, lithium titanate ceramics are established as the primary solid tritium breeder candidate materials for tritium breeder cladding and are adopted by ite test cladding designs. Solid tritium breeder materials have been found to be corrosive, such as: low-activation ferrite-martensite steel EUROFER97 steel in solid state tritium breeder Li 4 SiO 4 Corrosion of the surface to form LiFe 8 O 5 、LiFeO 2 、LiCrO 2 And corrosion products. These corrosion products will also remain on the surface of the tritium breeder material, affecting the release of tritium; at the same time, the element component in the structural material diffuses to the contact interface to cause the matrix to be inPartial component segregation causes potential safety hazards. Therefore, there is an urgent need to develop tritium breeder materials that have excellent corrosion compatibility and good tritium release properties.
The surface of the tritium breeder material is modified, a coating layer is prepared on the surface of the tritium breeder material, so that the corrosion compatibility of the tritium breeder material, structural materials, neutron multiplication materials and other materials can be improved, and the tritium release performance of the tritium breeder material can be simultaneously improved through the component optimization and the structural design of the coating layer. However, since the existing powder surface modification method has strong process directivity, a large amount of tritium breeder surface modification research cannot be carried out in a short time, and a system surface modified tritium breeder candidate material library is not established at present, a device and a preparation method which have high development efficiency and can simultaneously realize preparation of various coating materials are urgently needed.
Disclosure of Invention
The technical problems to be solved by the application are as follows: the application provides a surface modified tritium breeder and a preparation method thereof, which are capable of solving the problems, and the prepared improved tritium breeder has excellent corrosion compatibility and good tritium release performance, and the preparation method is high in efficiency, good in economy and environment-friendly, can realize preparation of various coating materials, and is beneficial to establishment of a surface modified tritium breeder candidate material library of a system.
The application is realized by the following technical scheme:
a preparation method of a surface modified tritium breeder adopts a magnetron sputtering coating method to deposit a metal coating layer on the surface of tritium breeder particles, or sequentially deposit a metal coating layer and a nonmetal coating layer; the number of the metal coating layers is one or more than two; the metal species is a combination of one or more metals; the number of the nonmetallic coating layers is one or more than two, and the nonmetallic species is one or a combination of nonmetallic species.
The term "plural" as used herein means two or more; the above includes the present number, for example, two or more layers, including two or more layers.
In summary, the coating layer deposited on the surface of the tritium breeder particle by the magnetron sputtering coating method is formed in two cases, namely, a metal layer is deposited on the surface of the tritium breeder particle, and a metal layer and a nonmetal layer are sequentially deposited on the surface of the tritium breeder particle. "the number of layers of the metal coating layer is one or more than two; the metal species is a combination of one or more metals; the number of layers of the nonmetallic coating is one or more than two, and the nonmetallic species is one or a combination of nonmetallic, which is applicable to any one of the other cases.
Each metal coating layer can be formed by sputtering deposition of one metal element or by co-sputtering deposition of more than two metal elements.
Each nonmetallic coating layer can be formed by sputtering deposition of one nonmetallic element or by sputtering deposition of more than two nonmetallic elements. The non-metallic coating may also be an oxide coating, with multiple oxides being co-sputter deposited.
The metal type of the metal layer is selected to be used as a coating layer, so that the lithium in the tritium breeder material is prevented from diffusing and migrating to improve the corrosion compatibility of the tritium breeder material, and the modified tritium breeder can be ensured to have excellent tritium release performance. The nonmetallic coating has more excellent corrosion resistance, and a nonmetallic coating layer can be added on the basis of the metallic coating layer, so that the corrosion compatibility of the tritium breeder material can be enhanced.
The coating layer is deposited on the surface of the tritium breeder particles so as to prevent the lithium element in the tritium breeder material from migrating outwards and prevent the elements in other materials from diffusing into the tritium breeder material.
The preparation method has high efficiency, good economy and environmental friendliness, can simultaneously realize the preparation of various coating materials, develops a large number of tritium proliferation agent surface modification researches in a short time, and rapidly establishes a surface modified tritium proliferation agent candidate material library of the system.
Further alternatively, the tritium breeder particles have a particle size of 0.01mm to 10mm. Preferably, the particle size of the tritium breeder particles is from 0.1mm to 5mm, more preferably the particle size of the tritium breeder particles is from 0.8mm to 2mm.
The shape of the proliferation agent particles is a small sphere or a small sphere-like shape.
Further alternatively, the total thickness of the coating is less than 5 μm.
Further alternatively, the total thickness of the cladding layer is 5nm to 1000nm; more preferably, the total thickness of the coating layer is 5nm to 50nm. For each pair.
In the case of simultaneous deposition of a metallic cladding layer and a non-metallic cladding layer on the surface of tritium breeder particles, it is preferred that the thickness of the metallic cladding layer and the non-metallic cladding layer range from 5nm to 50nm.
Further optionally, the metal species comprises one or more combinations of V, pd, ti, ni, fe, nb, zr; and/or the nonmetallic species comprises SiC, tiO 2 、ZrO 2 、Al 2 O 3 One or more of TiN.
But are not limited to the listed materials and other nonmetallic/metallic layer cladding are equally applicable. In the case of metallic and nonmetallic coatings, for example, zrO 2 @Pd@Li 4 SiO 4 。
Further alternatively, the magnetron sputtering coating method comprises the following steps:
pretreatment of raw materials, removal of impurities on the surface of tritium breeder particles and activation of the surface. The pretreatment can be carried out by adopting a plasma cleaning machine to clean the tritium breeder particle raw material, remove impurities and nano oxide layers on the surface of the tritium breeder particle raw material, activate the surface of the tritium breeder raw material and strengthen the binding force between the coating layer and the raw material. The plasma cleaning time is designed to be 10 s-300 s, and the cleaning gas is Ar or Ar+O 2 . Before pretreatment, proper preservation can be performed to isolate substances that are susceptible to reaction therewith.
And (5) sample loading and vacuumizing, and obtaining a vacuum environment. The sample loading is to put tritium breeder raw materials into a sample tray of a powder magnetron sputtering coating system, two or more sputtering cathodes can be arranged in the powder magnetron sputtering coating system, the coating efficiency is high, the controllability is good, and the uniform preparation can be realizedA coating layer with a single-layer or multi-layer structure and good uniformity. The vacuumizing is a high-vacuum system of the powder magnetron sputtering coating system, so that the quality and the impurity components of the prepared coating layer are ensured to be less. The background vacuum of the powder magnetron sputtering coating system can reach 10 -3 ～10 -4 Of the order of Pa.
Sputtering deposition, namely depositing a metal coating layer on the surface of the tritium breeder, or sequentially depositing a metal coating layer and a nonmetal coating layer. After the system reaches high vacuum, a power supply of a sputtering cathode is turned on, sputtering gas is introduced to a set pressure, and starting and pre-sputtering are carried out; and adjusting the vibration frequency and the heating temperature of the sample disk, opening a baffle plate of a sputtering cathode, and performing sputtering coating on tritium breeder powder. And (3) continuing to open the revolution of the cathode target, aligning the other sputtering cathode with the sample, and performing sputtering coating to prepare the coating layer with the multilayer structure.
The magnetron sputtering coating method comprises the following steps:
(1) Preserving and preprocessing raw materials:
the tritium breeder particle raw material is stored in a glove box, and after a sample to be tested is taken out, the tritium breeder raw material is cleaned by a plasma cleaner to remove impurities and a nano oxide layer on the surface of the tritium breeder raw material.
The tritium breeder raw material is stored in a glove box, so that the tritium breeder raw material is prevented from reacting with carbon dioxide and water in the air, and the tritium breeder material is prevented from deteriorating.
The pretreatment is to clean the tritium breeder raw material by a plasma cleaner to remove impurities and nano oxide layers adsorbed on the surface of the tritium breeder raw material, and also to activate the surface of the tritium breeder raw material to enhance the binding force between the coating layer and the raw material
(2) Sample loading and vacuumizing:
putting tritium breeder particle raw materials into a sample tray of a powder magnetron sputtering coating system, and closing a system air vent after loading a cathode target to be sputtered; and (3) pre-vacuumizing the powder magnetron sputtering coating system by using a mechanical pump, and vacuumizing the system by using a molecular pump. Molecular pump vacuuming to 10 -3 Pa and below.
(3) Sputter deposition
The sputtering deposition is to turn on a power supply of a sputtering cathode after the powder magnetron sputtering coating system reaches high vacuum, and to introduce sputtering gas to a certain pressure so as to meet the conditions of magnetron sputtering glow discharge, and atoms in the sputtering cathode begin to deposit after glow discharge, so that the quality of a prepared coating layer is ensured, the sputtering cathode is pre-sputtered, and impurities on the surface of a cathode target are removed; after the glow is stable, a baffle plate of a sputtering cathode is opened, atoms in a cathode target material can be deposited on the surfaces of tritium proliferation agent particle raw materials, and in order to ensure uniformity, the vibration frequency of the tritium proliferation agent particle raw materials in a sample tray is regulated, so that the sputtered atoms are deposited on all surfaces of a tritium proliferation agent particle raw material sample and are uniformly deposited. In order to obtain a non-metal/metal double-layer or multi-layer structure coating layer, after sputtering of one cathode target is finished, the other cathode target is powered on and sputtered, so that the improved tritium breeder material with more excellent corrosion inclusion can be obtained.
(4) Shut down and sample
And sequentially closing a sputtering cathode power supply and a sputtering gas inlet switch, closing a molecular pump and a mechanical pump, opening a system air release valve after the device is cooled to the temperature, opening a vacuum chamber, taking out a sample, and storing the sample in a glove box.
The closing is to close the cathode power supply and the sputtering gas inlet switch, and after no sputtering gas and no sputtering gas voltage exist, the system cannot perform glow discharge, and the sputtering deposition process is finished. And after the system vacuum system is closed and the sample is fully cooled and cooled to room temperature, the vacuum chamber is opened to take out the sample, so that the bonding force of the cladding layer is prevented from being reduced due to the stress at the interface between the cladding layer and the tritium breeder raw material. To prevent the tritium breeder material from reacting with carbon dioxide and water in the air, the prepared sample is stored in a glove box.
Further alternatively, depositing a multi-layer coating on the surface of tritium breeder particles is accomplished by providing a plurality of sputter cathodes in a magnetron sputter coating system.
Further optionally, in the vacuumizing process, the design parameters include: the vacuum degree of the system is 0.3 Pa-1 Pa;
and/or during sputter deposition, the design parameters include: the power of the cathode power supply is 10W-200W; and/or the cathode pre-sputtering time is 3-5 min; and/or the rotating speed of the sample tray motor is 800 rmp-2000 rmp; and/or the deposition time is 10 s-600 s; and/or the temperature of the sample tray is between room temperature and 300 ℃.
The surface modified tritium breeder is characterized by comprising tritium breeder particles and a metal coating layer from inside to outside in sequence, or comprising tritium breeder particles, a metal coating layer and a nonmetal coating layer, and is prepared by adopting the preparation method of the surface modified tritium breeder.
Further alternatively, the tritium breeder material comprises Li 4 SiO 4 Or Li (lithium) 2 TiO 3 。
The application has the following advantages and beneficial effects:
1. the preparation method of the surface modified tritium breeder provided by the application has the advantages of high efficiency, good economy and environmental friendliness, can simultaneously realize the preparation of various coating materials, develops a large number of surface modification researches on the tritium breeder in a short time, and rapidly establishes a system surface modified tritium breeder candidate material library.
2. The surface modified tritium breeder and the preparation method thereof provided by the application realize the surface modification of tritium breeder particles, and the coating prepared by the method has uniform components and good adhesive force, and the thickness of the surface coating of the tritium breeder can be controlled in nanometer scale.
3. According to the surface modified tritium breeder and the preparation method thereof, one or two or more layers of coating layers are prepared on the surface of the tritium breeder pellet raw material, so that the outward migration of lithium elements in the tritium breeder material is prevented, the diffusion of elements in other materials into the tritium breeder material is prevented, and the corrosion compatibility and the tritium release performance of the tritium breeder material are improved.
4. The prior patent document CN112174156A provides a TiN/C coated lithium orthosilicate tritium breeder, a preparation method and a preparation device system thereof, and also provides a preparation method of the tritium breeder with a coating layer structure, wherein the method is only aimed at a specific tritium breeder material system, equipment is special, the used raw materials are mainly organic reagents, tail gas emission exists, and the device cannot prepare the tritium breeder material with a special multilayer structure; in contrast, the method of the application utilizes a physical sputtering deposition method, no organic waste liquid is generated, the type of the coating layer material can be selected according to the requirement, the equipment universality is good, and the advanced tritium breeder material with special structure and multiple element doping can be prepared.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings:
FIG. 1 is a surface modified tritium breeder of monolayer coating structure. The reference numerals and corresponding part names in fig. 1: 1-tritium breeder particles; 2-metallic or nonmetallic cladding.
FIG. 2 is a surface modified tritium breeder of a multi-layer cladding structure. The reference numerals and corresponding part names in fig. 2: 1-tritium breeder particles; 2-metal coating, 3-non-metal coating.
FIG. 3 is a schematic diagram of a powder magnetron sputtering coating system. The labels in fig. 3 and the corresponding part names: 1-sample tray; 2-cathode; 3-baffle plates; 4-a system cavity; 5-a vacuum system; 6-sample injection door; 7-sputtering gas inlet; 8-a sputtering gas discharge port; 9-tritium breeder raw material of pellet structure.
FIG. 4 is a scanning electron microscope image of a Zr-coated modified tritium breeder material.
FIG. 5 is a plot of elemental profile of a Zr-coated modified tritium breeder material; wherein the graph (a) shows an electron microscope graph and the graph (b) shows an EDS energy spectrum.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present application, the present application will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present application and the descriptions thereof are for illustrating the present application only and are not to be construed as limiting the present application.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. However, it will be apparent to one of ordinary skill in the art that: no such specific details are necessary to practice the application. In other instances, well-known structures, materials, or methods have not been described in detail in order to avoid obscuring the present application.
Example 1
The embodiment provides a surface-modified tritium breeder, the structural schematic diagram of which is shown in figure 1, wherein the outer layer is a Zr coating layer, and the inner part is Li with a small sphere structure 4 SiO 4 The thickness of the coating layer of the raw material is 100nm, and the diameter of the pellet structure is 0.2mm. The scanning electron microscope of the surface modified tritium breeder material after sputtering and depositing the Zr coating layer is shown in figure 4, and the prepared Zr coating layer is compact and smooth. As can be seen from the elemental composition distribution diagram of FIG. 5, the Zr coating was uniformly applied to the surface of the tritium breeder raw material.
Zr coating Li 4 SiO 4 The preparation steps of the surface modified tritium breeder are as follows:
step 1, raw materials and pretreatment:
will L i4 SiO 4 The raw materials are placed in a glove box, and 50mg of Li is taken from the glove box before the experiment 4 SiO 4 Raw materials. Subsequently Li is taken up 4 SiO 4 The raw materials are flatly paved on a glass sheet, the glass sheet is put into a plasma cleaner for cleaning, ar sputtering gas is introduced into the plasma cleaner, the cleaning time is 300s, and the glass sheet is ready for use after cleaning.
And (3) processing in a powder magnetron sputtering coating system sequentially through a step 2, a step 3 and a step 4, wherein the powder magnetron sputtering coating system is shown in fig. 3, and the names and the reference numerals of the parts recorded in the step 2, the step 3 and the step 4 are shown in fig. 3.
Step 2, sample loading and vacuumizing:
li after plasma cleaning in the step 1 4 SiO 4 The raw materials are placed in a sample tray 1 of a powder magnetron sputtering coating system, which is shown in fig. 3. Incorporating a cathode target Zr (cathode shown as reference number 2 in FIG. 3), the target diameter being 2 inches, thicknessIs 5mm. Closing the sputtering gas discharge port 3; the system cavity 4 is evacuated by means of a vacuum system 5.
Step 3, sputtering deposition:
when the vacuum of the system reaches 2 multiplied by 10 -4 After Pa, turning on a radio frequency power supply of the sputtering cathode, adjusting the power to 100W, introducing sputtering gas Ar through a sputtering gas inlet 7, closing a baffle plate 3 of the cathode 2 after the vacuum degree reaches 0.6Pa, starting glow and pre-sputtering for 10min; the rotation speed of the motor of the sample disk 1 was adjusted to 1800rmp, and the shutter 3 of the sputtering cathode 2 was opened to Li 4 SiO 4 The raw material (namely tritium breeder raw material 9 with a pellet structure) is subjected to sputtering Zr plating, sputtering is carried out for 300 seconds, and the temperature of a sample is 25 ℃.
And 4, closing and sampling:
after sputtering for 300s, a sputtering cathode power supply and a sputtering gas inlet switch are sequentially turned off, a vacuum system is turned off, a sputtering gas air discharge port 8 of the system is opened after the device is cooled to the temperature, a sample inlet door 6 of the system is opened, and Li coated by Zr is taken out 4 SiO 4 The material was stored in a glove box.
Example 2
The embodiment provides a surface-modified tritium breeder, the structural schematic diagram of which is shown in figure 2, wherein the outer layer is a SiC coating layer, the middle layer is a Pd coating layer, and the inner part is Li with a small sphere structure 2 TiO 3 The thickness of the outer layer coating layer of the raw material is 50nm, the thickness of the middle layer coating layer is 10nm, and the particle size of the internal pellet structure is 0.2mm.
SiC-Pd coated Li 2 TiO 3 The preparation steps of the surface modified tritium breeder material are as follows:
step 1, raw materials and pretreatment:
li is mixed with 2 TiO 3 The raw materials are placed in a glove box, 60mgLi is taken out of the glove box before the experiment 2 TiO 3 Raw materials. Subsequently Li is taken up 2 TiO 3 Spreading the raw materials on a glass sheet, putting the glass sheet into a plasma cleaning machine for cleaning, and introducing Ar+H into the plasma cleaning machine 2 As sputtering gas, the cleaning time is 10s, and the cleaning is finished and is to be finishedIs used.
And (3) processing in a powder magnetron sputtering coating system sequentially through a step 2, a step 3 and a step 4, wherein the powder magnetron sputtering coating system is shown in fig. 3, and the names and the reference numerals of the parts recorded in the step 2, the step 3 and the step 4 are shown in fig. 3.
Step 2, sample loading and vacuumizing:
li after plasma cleaning in the step 1 2 TiO 3 The raw materials are placed in a sample tray 1 of a powder magnetron sputtering coating system, which is shown in fig. 3. Cathode targets Pd and SiC (cathode shown as reference numeral 2 in fig. 3) were loaded, the target diameter being 2 inches and the thickness being 5mm. Closing the sputtering gas discharge port 8; the system cavity 4 is evacuated by means of a vacuum system 5.
Step 3, sputter deposition
The system vacuum reaches 1X 10 -3 After Pa, turning on a radio frequency power supply of a sputtering cathode Pd, adjusting the power to 50W, introducing sputtering gas Ar through a sputtering gas inlet 7, closing a baffle plate 3 of a cathode 2 after the vacuum degree reaches 0.4Pa, starting glow and pre-sputtering for 5min; the rotation speed of the motor of the sample disk 1 was adjusted to 2000rmp, and the shutter 3 of the sputtering cathode 2 was opened to Li 2 TiO 3 Sputtering Pd on the raw materials for 10s; turning off the direct current power supply of the sputtering cathode Pd, turning on the radio frequency power supply of the sputtering cathode SiC, adjusting the power to 200W, turning off the baffle plate 3 of the cathode 2 to start and pre-sputter for 5min, adjusting the rotating speed of the motor of the sample disk 1 to 2000rmp, and turning on the baffle plate 3 of the sputtering cathode 2 to perform Li 2 TiO 3 The raw materials are subjected to sputtering plating of SiC for 50s, and the temperature of the sample is 100 ℃.
Step 4, closing and sampling
After sputtering, the power supply of the sputtering cathode 2 and the sputtering gas inlet switch are sequentially turned off, the vacuum system is turned off, the sputtering gas air discharge port is opened after the device is cooled to the temperature, the sample inlet door 6 of the system is opened, and Li coated by SiC-Pd is taken out 2 TiO 3 The material was stored in a glove box.
Corrosion resistance: siC-Pd coated Li prepared in example 2 was prepared by a static embedding method 2 TiO 3 And carrying out a contact corrosion test with the low-activation ferrite martensitic steel CLF-1, wherein the test temperature is 550 ℃, and the test time is 120h. With uncoated Li 2 TiO 3 In contrast, coated Li 2 TiO 3 No migration and diffusion of lithium element occurs, and no Li element signal is detected on the surface of the CLF-1 steel; uncoated Li 2 TiO 3 The lithium element in the alloy is diffused to the surface of the CLF-1 steel, and the diffusion depth is about 100nm, so that the CLF-1 steel is corroded. SiC-Pd coated Li 2 TiO 3 Has better corrosion compatibility.
Tritium release properties: siC-Pd coated and uncoated Li prepared in example 2 was subjected to a deuterium-filled thermal desorption test 2 TiO 3 Tritium release performance was evaluated. Deuterium filling temperature is 300 ℃, pressure is 100kPa, and hydrogen filling time is 3 hours; and (3) carrying out thermal desorption test on the sample after the hydrogen filling is finished, wherein the heating rate is 10 ℃/min. Test results: coated Li 2 TiO 3 Deuterium release temperature of 350 ℃, uncoated Li 2 TiO 3 The deuterium release temperature of (2) is 410 ℃. SiC-Pd coated Li 2 TiO 3 Has better deuterium release performance.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the application, and is not meant to limit the scope of the application, but to limit the application to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the application are intended to be included within the scope of the application.

Claims (9)

1. A preparation method of a surface modified tritium breeder is characterized in that,
depositing a metal coating layer on the surface of tritium breeder particles by adopting a magnetron sputtering coating method, or sequentially depositing a metal coating layer and a nonmetal coating layer;
the number of the metal coating layers is one or more than two; the metal species includes one or more combinations of V, pd, ti, ni, fe, nb, zr;
the non-metal coating layer has one or two layersAbove the layer, the nonmetallic species include SiC, tiO 2 、ZrO 2 、Al 2 O 3 One or more of TiN.
2. The method for preparing a surface-modified tritium breeder according to claim 1, wherein the particle size of the tritium breeder particles is 0.01 mm-10 mm.
3. The method of preparing a surface modified tritium breeder of claim 1, wherein the total thickness of the coating is less than 5 μm.
4. The method for preparing a surface-modified tritium breeder according to claim 3, wherein the total thickness of the coating layer is 5 nm-1000 nm.
5. The method for preparing a surface-modified tritium breeder according to any one of claims 1 to 4, wherein the magnetron sputtering coating method comprises the following steps:
pretreating raw materials, removing impurities on the surfaces of tritium breeder particles and activating the surfaces;
sample loading and vacuumizing, and obtaining a vacuum environment;
sputtering deposition, namely depositing a metal coating layer on the surface of the tritium breeder, or sequentially depositing a metal coating layer and a nonmetal coating layer.
6. The method for preparing a surface-modified tritium breeder according to claim 5, wherein the deposition of the multi-layer coating on the surface of the tritium breeder particles is achieved by providing a plurality of sputtering cathodes in a magnetron sputtering coating system.
7. The method for preparing a surface-modified tritium breeder as claimed in claim 5, wherein,
in the vacuumizing process, design parameters include: the vacuum degree of the system is 0.3 Pa-1 Pa;
and/or during sputter deposition, the design parameters include: the power of the cathode power supply is 10W-200W; and/or the cathode pre-sputtering time is 3 min-5 min; and/or the rotating speed of the sample tray motor is 800 rmp-2000 rmp; and/or the deposition time is 10 s-600 s; and/or the temperature of the sample tray is room temperature to 300 ℃.
8. A surface-modified tritium breeder, characterized in that the surface-modified tritium breeder comprises tritium breeder particles and a metal coating layer sequentially from inside to outside, or comprises tritium breeder particles, a metal coating layer and a nonmetal coating layer, and is prepared by the preparation method of the surface-modified tritium breeder according to any one of claims 1 to 7.
9. The surface modified tritium breeder of claim 8, wherein the tritium breeder material comprises Li 4 SiO 4 Or Li (lithium) 2 TiO 3 。
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