CN115305442A - Surface modified tritium proliferation agent and preparation method thereof - Google Patents

Surface modified tritium proliferation agent and preparation method thereof Download PDF

Info

Publication number
CN115305442A
CN115305442A CN202211030349.0A CN202211030349A CN115305442A CN 115305442 A CN115305442 A CN 115305442A CN 202211030349 A CN202211030349 A CN 202211030349A CN 115305442 A CN115305442 A CN 115305442A
Authority
CN
China
Prior art keywords
tritium
coating layer
breeder
modified
tritium breeder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202211030349.0A
Other languages
Chinese (zh)
Other versions
CN115305442B (en
Inventor
王龙
洪志浩
严觉民
巩保平
张龙
王晓宇
冯勇进
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southwestern Institute of Physics
Original Assignee
Southwestern Institute of Physics
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southwestern Institute of Physics filed Critical Southwestern Institute of Physics
Priority to CN202211030349.0A priority Critical patent/CN115305442B/en
Publication of CN115305442A publication Critical patent/CN115305442A/en
Application granted granted Critical
Publication of CN115305442B publication Critical patent/CN115305442B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Plasma & Fusion (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a surface modification type 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 a tritium breeder particle, or deposit a metal coating layer and a nonmetal coating layer in sequence; 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 non-metal coating layers is one or more than two, and the non-metal type is the combination of one or more non-metals. The improved tritium breeder prepared by the method has excellent corrosion compatibility and good tritium releasing performance, the preparation method is high in efficiency, good in economy and environment-friendly, the preparation of various coating materials can be realized, and the establishment of a systematic surface improved tritium breeder candidate material library is facilitated.

Description

Surface modified tritium breeder and preparation method thereof
Technical Field
The invention relates to the technical field of fusion reactor fuels, in particular to a surface modification type tritium breeder and a preparation method thereof.
Background
Controllable nuclear fusion energy is one of the fundamental exits that hopefully solve the energy problem completely. Hydrogen and its isotopes (deuterium, tritium) are important fuels for magnetically confined nuclear fusion reactors. For the 2GW DEMO exemplary stack, the daily consumption of tritium is 313g, while the daily tritium production of ITER is only 0.4g, the price of CANDU tritium is 30000 dollar/g, and the amount of tritium released to the environment under normal working conditions is not higher than 1g in one year. In view of economic and safety considerations, efficient utilization of fuel tritium is a key to commercialization of fusion reactors. The tritium breeding blanket is a core component for realizing tritium self-sustaining and energy extraction of the fusion reactor and can pass Li 6 Reacts with neutrons: ( 1 n+ 6 Li→ 4 He +3T + 4.78MeV) on-line tritium production, so that development of advanced tritium breeder materials and improvement of tritium production efficiency of the tritium breeder become research focuses in the fusion field.
Lithium orthosilicate and lithium titanate ceramics are established as candidate materials of main solid tritium breeder of the tritium breeder cladding, and are adopted by the design of an ITER test cladding. Solid tritium breeder materials have been found to be corrosive, such as: low-activation ferrite-martensite steel EUROFER97 steel in solid tritium breeder Li 4 SiO 4 Form LiFe on the surface after corrosion 8 O 5 、LiFeO 2 、LiCrO 2 And the like corrosion products. These corrosion products will also remain on the surface of the tritium breeder material, affecting the release of tritium; meanwhile, the elemental components in the structural material diffuse to the contact interface to cause the segregation of the internal components of the matrix, thereby causing potential safety hazards. Therefore, there is an urgent need to develop a tritium breeder material having excellent corrosion compatibility and tritium release performance.
The tritium breeder material is modified on the surface, and the coating layer is prepared on the surface, so that the corrosion compatibility of the tritium breeder material and materials such as structural materials and neutron multiplication materials can be improved, and the tritium release performance of the tritium breeder material can be improved simultaneously through the component optimization and the structural design of the coating layer. However, because the existing powder surface modification method has strong process directivity, and can not develop a large amount of tritium breeder surface modification research in a short time, a systematic surface modified tritium breeder candidate material library is not established yet, so that 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 problem to be solved by the invention is as follows: the invention provides a surface modified tritium breeder and a preparation method thereof for solving the problems, wherein the prepared improved tritium breeder has excellent corrosion compatibility and good tritium releasing performance, and the preparation method has high efficiency, good economy and environmental friendliness, can realize the preparation of various coating materials, and is beneficial to establishing a systematic surface modified tritium breeder candidate material library.
The invention is realized by the following technical scheme:
a preparation method of a surface modification type tritium breeding agent adopts a magnetron sputtering coating method to deposit a metal coating layer on the surface of tritium breeding agent 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 non-metal coating layers is one or more than two, and the non-metal type is the combination of one or more non-metals.
The above "plural" means two or more; the above-mentioned "more than" includes the same number, for example, two or more layers, including two layers.
In conclusion, the coating layer deposited on the surface of the tritium breeder particle by the magnetron sputtering coating method has two conditions, wherein one condition is that a metal layer is deposited on the surface of the tritium breeder particle, and the other condition is that the metal layer and a nonmetal layer are sequentially deposited on the surface of the tritium breeder particle. 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 layers of the non-metal coating layer is one or more than two, and the non-metal species is a combination of one or more non-metals.
Each metal coating layer can be formed by sputtering deposition of one metal element or formed by co-sputtering deposition of more than two metal elements.
Each non-metal coating layer can be formed by sputtering deposition of one non-metal element or formed by co-sputtering deposition of more than two non-metal elements. The non-metallic coating may also be an oxide coating, a coating deposited by co-sputtering of multiple oxides.
The metal type of the metal layer selects the metal layer with higher hydrogen permeability as a coating layer, so that the modified tritium breeder can be ensured to have excellent tritium releasing performance while lithium in the tritium breeder material is prevented from diffusing and migrating to improve the corrosion compatibility. The non-metal coating layer has more excellent corrosion resistance, and a layer of non-metal coating layer can be added on the basis of the metal coating layer, so that the corrosion compatibility of the tritium breeder material can be enhanced.
Through depositing a coating layer on the surface of the tritium breeder particle, the lithium element in the tritium breeder material is prevented from moving outwards, and elements in other materials are prevented from diffusing to 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 the surface modification research of a large amount of tritium breeders in a short time, and quickly establishes a systematic surface-modified tritium breeder candidate material library.
Further optionally, the tritium proliferator particles have a particle size of 0.01mm to 10mm. Preferably, the tritium proliferator particles have a particle size of 0.1 to 5mm, and more preferably 0.8 to 2mm.
The shape of the proliferation agent particles is small spherical or small spheroidal.
Further optionally, the total thickness of the cladding layers is less than 5 μm.
Further optionally, the total thickness of the coating layer is 5nm to 1000nm; more preferably, the total thickness of the clad layers is 5nm to 50nm. And (4) pairing.
In the case where the metal coating layer and the nonmetal coating layer are simultaneously deposited on the surface of the tritium proliferator particle, the thickness of the metal coating layer and the thickness of the nonmetal coating layer are preferably in the range of 5nm to 50nm.
Further optionally, the metal species comprises one or more combinations of V, pd, ti, ni, fe, nb, zr; and/or said non-metallic species comprises SiC, tiO 2 、ZrO 2 、Al 2 O 3 And TiN, or a combination thereof.
But is not limited to the listed materials and other non-metallic/metallic layer coatings are equally suitable. In the case of a metal coating layer and a non-metal coating layer, for example, zrO 2 @Pd@Li 4 SiO 4 。
Further optionally, the magnetron sputtering coating method comprises the following steps:
pretreating raw materials, removing impurities on the surface of tritium breeder particles, and activating the surface. And (3) pretreatment, namely cleaning the tritium breeder particle raw material by adopting a plasma cleaning machine to remove impurities and a nano oxide layer on the surface of the tritium breeder particle raw material, and activating the surface of the tritium breeder raw material to enhance 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 the pretreatment, the material may be preserved appropriately to isolate the material which is liable to react with it.
Loading and vacuumizing to obtain vacuum environment. The sample loading is to put the tritium breeding agent raw material into a sample plate 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 a single-layer or multi-layer structure coating layer with good uniformity can be prepared. The vacuumizing is a high vacuum system of the powder magnetron sputtering coating system, and the quality of the prepared coating layer and the impurity content 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.
And (4) sputtering deposition, namely depositing a metal coating layer on the surface of the tritium breeding agent, or sequentially depositing the metal coating layer and the nonmetal coating layer. After the system reaches high vacuum, turning on a power supply of a sputtering cathode, introducing sputtering gas to set pressure, starting and pre-sputtering; and adjusting the vibration frequency and the heating temperature of the sample plate, opening a baffle of the sputtering cathode, and performing sputtering coating on the tritium breeder powder. And continuing to open the cathode target material for revolution, aligning the other sputtering cathode to the sample, and performing sputtering coating to prepare the multilayer structure coating layer.
The magnetron sputtering coating method comprises the following steps:
(1) Raw material preservation and pretreatment:
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 cleaning machine to remove impurities and a nano oxide layer on the surface of the tritium breeder particle raw material.
The tritium breeder raw material is stored in the 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 utilize a plasma cleaning machine to clean the tritium breeding agent raw material to remove impurities and a nano oxide layer adsorbed on the surface of the tritium breeding agent raw material, and also can activate the surface of the tritium breeding agent raw material to enhance the binding force between the coating layer and the raw material
(2) Sample loading and vacuumizing:
putting a tritium breeder particle raw material into a sample disc of a powder magnetron sputtering coating system, and closing a system gas release port after a cathode target to be sputtered is loaded; magnetic application of mechanical pump to powderAnd pre-vacuumizing the sputtering control coating system, and vacuumizing the system by using a molecular pump. Molecular pump is pumped down to 10 -3 Pa and below.
(3) Sputter deposition
The sputtering deposition is that after the powder magnetron sputtering coating system reaches high vacuum, the power supply of the sputtering cathode is opened, sputtering gas is introduced to certain pressure to meet the condition of magnetron sputtering glow discharge, atoms in the sputtering cathode start to deposit after the glow discharge, and in order to ensure the quality of the prepared coating, the sputtering cathode is pre-sputtered to remove impurities on the surface of the cathode target; after glow is stable, a baffle plate of the sputtering cathode is opened, atoms in the cathode target can be deposited on the surface of the tritium breeder particle raw material, and in order to ensure uniformity, the vibration frequency of the tritium breeder particle raw material in the sample tray is adjusted, so that the sputtered atoms are deposited on all surfaces of the tritium breeder 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 one cathode target material is sputtered, the other cathode target material power supply is started for sputtering, and an improved tritium breeder material with more excellent corrosion inclusion can be obtained.
(4) Shut down and sample
And (3) closing the sputtering cathode power supply and the sputtering gas inlet switch in sequence, closing the molecular pump and the mechanical pump, opening a system air release valve after the device is cooled to the temperature, opening the vacuum chamber, taking out the sample, and storing the sample in the glove box.
And the step of closing is to close the cathode power supply and the sputtering gas inlet switch, and after no sputtering gas and voltage exist, the system cannot perform glow discharge, so that the sputtering deposition process is finished. Because the temperature in the system rises in the deposition process of the coating layer, after the vacuum system of the system is closed, the vacuum chamber is opened to take out the sample after the sample is fully cooled and cooled to the room temperature, so as to prevent the binding force of the coating layer from being reduced due to the stress at the interface of the coating layer and the tritium breeder raw material. In order 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 for preservation.
Further optionally, depositing multiple coating layers on the surface of the tritium breeder particle is realized by arranging a plurality of sputtering cathodes in one magnetron sputtering coating system.
Further optionally, during the vacuum pumping, the design parameters include: the vacuum degree of the system is 0.3 Pa-1 Pa;
and/or during sputter deposition, 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 disc motor is 800 rmp-2000 rmp; and/or the deposition time is 10s to 600s; 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 or comprising the tritium breeder particles, the metal coating layer and a non-metal coating layer from inside to outside in sequence, and is prepared by the preparation method of the surface-modified tritium breeder.
Further alternatively, the tritium breeder starting material comprises Li 4 SiO 4 Or Li 2 TiO 3 。
The invention has the following advantages and beneficial effects:
1. the preparation method of the surface modified tritium breeder and the preparation method thereof provided by the invention have the advantages of high efficiency, good economy and environmental friendliness, can simultaneously realize the preparation of various coating materials, develop the surface modification research of a large amount of tritium breeders in a short time and quickly establish a systematic surface modified tritium breeder candidate material library.
2. The surface modification type tritium breeder and the preparation method thereof provided by the invention realize surface modification of tritium breeder particles, 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 a nanometer scale.
3. The improved tritium breeder material is characterized in that one or two or more layers of coating layers are prepared on the surface of a tritium breeder pellet raw material, so that lithium in the tritium breeder material is prevented from migrating outwards, elements in other materials are prevented from diffusing to the tritium breeder material, and the corrosion compatibility and tritium release performance of the tritium breeder material are improved.
4. The existing 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 a tritium breeder with a coating structure, the method is only specific to a specific tritium breeder material system, the device is special, most of the used raw materials are organic reagents, tail gas emission exists, and the device cannot prepare tritium breeder materials with a special multilayer structure; in contrast, the method of physical sputtering deposition is utilized, 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 a special structure and doped with various elements can be prepared.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 shows a surface-modified tritium breeding agent having a single-layer coating structure. Reference numbers and corresponding part names in fig. 1: 1-tritium proliferator particles; 2-metallic or non-metallic coating.
FIG. 2 is a surface modified tritium breeder for a multi-layer coating structure. Reference numbers and corresponding part names in fig. 2: 1-tritium proliferator particles; 2-metal coating layer and 3-nonmetal coating layer.
FIG. 3 is a schematic diagram of a powder magnetron sputtering coating system. Reference numbers and corresponding part names in fig. 3: 1-sample tray; 2-a cathode; 3-a baffle plate; 4-system cavity; 5-a vacuum system; 6-a sample introduction door; 7-inlet of sputtering gas; 8-sputtering gas relief; 9-tritium breeder raw material with a small sphere structure.
FIG. 4 is a scanning electron microscope image of a Zr-coated modified tritium breeder material.
FIG. 5 is a distribution diagram of elements of a Zr-coated modified tritium breeder material; wherein (a) shows an electron micrograph and (b) shows an EDS energy spectrum.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and the accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limiting the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that: it is not necessary to employ these specific details to practice the present invention. In other instances, well-known structures, materials, or methods have not been described in detail in order to avoid obscuring the present invention.
Example 1
This example provides a surface-modified tritium breeder, which is a material having a structure schematically shown in FIG. 1, and has an outer Zr coating layer and an inner Li pellet structure 4 SiO 4 The thickness of the raw material and the coating layer is 100nm, and the diameter of the pellet structure is 0.2mm. The scanning electron microscope of the surface modified tritium breeder material after the Zr coating is sputtered and deposited is shown in figure 4, and the prepared Zr coating is compact and smooth. As is clear from the elemental composition distribution chart in FIG. 5, the Zr coating layer completely and uniformly covered the surface of the tritium growth agent raw material.
Zr coated Li 4 SiO 4 The preparation steps of the surface-modified tritium proliferator of (1) are as follows:
step 1, raw material and pretreatment:
will L i4 SiO 4 The raw materials were stored in a glove box, from which 50mg Li was taken before the experiment 4 SiO 4 Raw materials. Subsequently adding Li 4 SiO 4 The raw materials are flatly laid on a glass sheet and are placed into a plasma cleaning machine for cleaning, ar sputtering gas is introduced into the plasma cleaning machine, the cleaning time is 300s, and the raw materials are used for standby after cleaning.
And (3) sequentially carrying out treatment in a powder magnetron sputtering coating system in the steps of 2, 3 and 4, wherein the powder magnetron sputtering coating system is shown in figure 3, and the names and the reference signs of the parts recorded in the steps of 2, 3 and 4 are all shown in figure 3.
Step 2, sample loading and vacuumizing:
cleaning the plasma cleaned Li in the step 1 4 SiO 4 The raw materials were placed in a sample pan 1 of a powder magnetron sputtering coating system as shown in fig. 3. A cathode target Zr (cathode indicated by reference numeral 2 in fig. 3) was charged, the target having a diameter of 2 inches and a thickness of 5mm. The sputtering gas relief port 3 is closed; the system chamber 4 is evacuated by means of a vacuum system 5.
Step 3, sputtering deposition:
when the vacuum of the system reaches 2 x 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, and after the vacuum degree reaches 0.6Pa, closing a baffle 3 of the cathode 2, starting and pre-sputtering for 10min; the motor of the sample plate 1 was set to a rotation speed of 1800rmp and the shutter 3 of the sputtering cathode 2 was opened for Li 4 SiO 4 The raw material (namely the tritium breeder raw material 9 with a small ball structure) is sputtered for Zr plating for 300s, and the sample temperature is 25 ℃.
Step 4, closing and sampling:
after sputtering for 300s, sequentially closing a sputtering cathode power supply and a sputtering gas inlet switch, closing the vacuum system, opening a sputtering gas outlet 8 of the system after the device is cooled to the temperature, opening a sample inlet door 6 of the system, and taking out Zr-coated Li 4 SiO 4 The material was stored in a glove box.
Example 2
The embodiment provides a surface modified tritium breeding agent, the structural schematic diagram of the surface modified tritium breeding agent material is shown in figure 2, the outer layer is a SiC coating layer, the middle layer is a Pd coating layer, and the inside is Li with a pellet structure 2 TiO 3 The raw materials, the thickness of the outer layer coating layer is 50nm, the thickness of the middle layer coating layer is 10nm, and the particle size of the inner small ball 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 material and pretreatment:
mixing Li 2 TiO 3 The raw materials were stored in a glove box, and 60mgLi was taken out from the glove box before the experiment 2 TiO 3 Raw materials. Subsequently adding Li 2 TiO 3 Spreading the raw materials on a glass sheet, cleaning the glass sheet in a plasma cleaning machine, and introducing Ar + H into the plasma cleaning machine 2 And as sputtering gas, the cleaning time is 10s, and the cleaning is finished for standby.
And (4) sequentially carrying out treatment in a powder magnetron sputtering coating system in the steps 2, 3 and 4, wherein the powder magnetron sputtering coating system is shown in figure 3, and the names and the reference signs of the parts recorded in the steps 2, 3 and 4 are shown in figure 3.
Step 2, sample loading and vacuumizing:
cleaning the plasma cleaned Li in the step 1 2 TiO 3 The raw materials were placed in a sample pan 1 of a powder magnetron sputtering coating system as shown in fig. 3. Cathode targets Pd and SiC (cathode indicated by reference numeral 2 in fig. 3) were charged, the target diameter being 2 inches and the thickness being 5mm. The sputtering gas relief port 8 is closed; the system chamber 4 is evacuated by means of a vacuum system 5.
Step 3, sputter deposition
The vacuum of the system reaches 1 x 10 -3 After Pa, turning on a radio frequency power supply of the sputtering cathode Pd, adjusting the power to 50W, introducing sputtering gas Ar through a sputtering gas inlet 7, closing a baffle 3 of the cathode 2 after the vacuum degree reaches 0.4Pa, and performing glow starting and pre-sputtering for 5min; the motor of the sample plate 1 was set to rotate at 2000rmp and the shutter 3 of the sputtering cathode 2 was opened for Li 2 TiO 3 Carrying out sputtering Pd plating on the raw materials for 10s; turning off the DC power supply of the sputtering cathode Pd, turning on the SiC radio frequency power supply of the sputtering cathode, adjusting the power to 200W, turning off the baffle 3 of the cathode 2 for starting and pre-sputtering for 5min, adjusting the rotating speed of the motor of the sample disc 1 to 2000rmp, turning on the baffle 3 of the sputtering cathode 2, and subjecting Li to ion exchange 2 TiO 3 The raw materials are sputtered to be plated with SiC for 50s, and the temperature of a sample is 100 ℃.
Step 4, closing and sampling
After sputtering is finished, the power supply of the sputtering cathode 2 and the sputtering gas inlet switch are sequentially closed, the vacuum system is closed, the sputtering gas vent is opened after the device is cooled to the temperature, the sample inlet door 6 of the system is opened, and the SiC-Pd bag is taken outCoated Li 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 (3) carrying out a contact corrosion test on the low-activation ferritic martensitic steel CLF-1 at the test temperature of 550 ℃ for 120h. With uncoated Li 2 TiO 3 In contrast, coated Li 2 TiO 3 Migration and diffusion of lithium elements do not occur, 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 CLF-1 steel diffuses to the surface of the CLF-1 steel, the diffusion depth is about 100nm, and 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-charged thermal desorption test 2 TiO 3 Tritium release performance was evaluated. Deuterium filling temperature is 300 ℃, pressure is 100kPa, and hydrogen filling time is 3h; after the hydrogen charging is finished, the thermal desorption test is carried out on the sample, and the temperature rise rate is 10 ℃/min. And (3) testing results: coated Li 2 TiO 3 Deuterium release temperature of 350 ℃, uncoated Li 2 TiO 3 The deuterium releasing temperature of (1) was 410 ℃. SiC-Pd coated Li 2 TiO 3 Has better deuterium releasing performance.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A method for preparing a surface-modified tritium breeder is characterized in that,
depositing a metal coating layer on the surface of the tritium breeder particle by adopting a magnetron sputtering coating method, or sequentially depositing the 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 non-metal coating layers is one or more than two, and the non-metal type is the combination of one or more non-metals.
2. The method for preparing the surface modified tritium breeder as claimed in claim 1, wherein the particle size of the tritium breeder particle is 0.01 mm-10 mm.
3. A method for producing a surface-modified tritium proliferator as claimed in claim 1, wherein the total thickness of the coating layer is less than 5 μm.
4. The method for producing a surface-modified tritium proliferator as claimed in claim 3, wherein the total thickness of the coating layer is 5nm to 1000nm.
5. A method for preparing a surface-modified tritium proliferator as claimed in claim 1, wherein the metal species comprises one or more combinations of V, pd, ti, ni, fe, nb, zr; and/or said non-metallic species comprises SiC, tiO 2 、ZrO 2 、Al 2 O 3 And TiN or a combination of two or more thereof.
6. The method for preparing a surface-modified tritium breeder as claimed in any one of claims 1 to 5, wherein the magnetron sputtering coating method comprises the steps of:
pretreating raw materials, removing impurities on the surface of tritium breeder particles, and activating the surface;
loading a sample and vacuumizing to obtain a vacuum environment;
and (4) sputtering deposition, namely depositing a metal coating layer on the surface of the tritium breeding agent, or sequentially depositing the metal coating layer and the nonmetal coating layer.
7. The method for preparing a surface-modified tritium breeder as claimed in claim 6, wherein deposition of multiple coatings on the surface of tritium breeder particles is achieved by arranging multiple sputtering cathodes in a magnetron sputtering coating system.
8. A method for producing a surface-modified tritium proliferator according to claim 6,
in the process of vacuumizing, the design parameters comprise: the vacuum degree of the system is 0.3 Pa-1 Pa;
and/or during sputter deposition, design parameters include: the power of the cathode power supply is 10W-200W; and/or the cathode pre-sputtering time is 3min to 5min; and/or the rotating speed of the sample disc motor is 800 rmp-2000 rmp; and/or the deposition time is 10s to 600s; and/or the temperature of the sample tray is between room temperature and 300 ℃.
9. A surface-modified tritium breeder, which is characterized by comprising tritium breeder particles and a metal coating layer from inside to outside in sequence, or comprising the tritium breeder particles, the metal coating layer and a non-metal coating layer, and is prepared by the preparation method of the surface-modified tritium breeder according to any one of claims 1 to 8.
10. A surface modified tritium breeder as claimed in claim 9 wherein the tritium breeder raw material comprises Li 4 SiO 4 Or Li 2 TiO 3 。
CN202211030349.0A 2022-08-26 2022-08-26 Surface modified tritium breeder and preparation method thereof Active CN115305442B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211030349.0A CN115305442B (en) 2022-08-26 2022-08-26 Surface modified tritium breeder and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211030349.0A CN115305442B (en) 2022-08-26 2022-08-26 Surface modified tritium breeder and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115305442A true CN115305442A (en) 2022-11-08
CN115305442B CN115305442B (en) 2023-09-19

Family

ID=83865594

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211030349.0A Active CN115305442B (en) 2022-08-26 2022-08-26 Surface modified tritium breeder and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115305442B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5923300A (en) * 1982-07-29 1984-02-06 三菱原子力工業株式会社 Tritium target
JPH05288874A (en) * 1992-04-09 1993-11-05 Hitachi Ltd Blanket of nuclear fusion device
JPH06263550A (en) * 1993-03-10 1994-09-20 Ngk Insulators Ltd Li-containing ceramics coated with metal
JPH11211868A (en) * 1998-01-29 1999-08-06 Japan Atom Energy Res Inst Coated lithium compound grain
CN111155052A (en) * 2019-12-06 2020-05-15 中国工程物理研究院核物理与化学研究所 Er2O3Preparation method and application of coating
CN112174155A (en) * 2020-09-28 2021-01-05 中科院过程工程研究所南京绿色制造产业创新研究院 Carbon-coated lithium orthosilicate tritium breeder and preparation method and preparation device system thereof
CN112174196A (en) * 2020-09-28 2021-01-05 中科院过程工程研究所南京绿色制造产业创新研究院 TiN/C coated lithium titanate tritium proliferation agent and preparation method and preparation device system thereof
CN112174195A (en) * 2020-09-28 2021-01-05 中科院过程工程研究所南京绿色制造产业创新研究院 Carbon-coated lithium titanate tritium proliferation agent and preparation method and preparation device system thereof
CN114414462A (en) * 2021-12-20 2022-04-29 核工业西南物理研究院 Hydrogen and isotope permeation testing device and method under corrosion coordination
WO2022106609A1 (en) * 2020-11-19 2022-05-27 Tokamak Energy Ltd Breeder blanket

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5923300A (en) * 1982-07-29 1984-02-06 三菱原子力工業株式会社 Tritium target
JPH05288874A (en) * 1992-04-09 1993-11-05 Hitachi Ltd Blanket of nuclear fusion device
JPH06263550A (en) * 1993-03-10 1994-09-20 Ngk Insulators Ltd Li-containing ceramics coated with metal
JPH11211868A (en) * 1998-01-29 1999-08-06 Japan Atom Energy Res Inst Coated lithium compound grain
CN111155052A (en) * 2019-12-06 2020-05-15 中国工程物理研究院核物理与化学研究所 Er2O3Preparation method and application of coating
CN112174155A (en) * 2020-09-28 2021-01-05 中科院过程工程研究所南京绿色制造产业创新研究院 Carbon-coated lithium orthosilicate tritium breeder and preparation method and preparation device system thereof
CN112174196A (en) * 2020-09-28 2021-01-05 中科院过程工程研究所南京绿色制造产业创新研究院 TiN/C coated lithium titanate tritium proliferation agent and preparation method and preparation device system thereof
CN112174195A (en) * 2020-09-28 2021-01-05 中科院过程工程研究所南京绿色制造产业创新研究院 Carbon-coated lithium titanate tritium proliferation agent and preparation method and preparation device system thereof
WO2022106609A1 (en) * 2020-11-19 2022-05-27 Tokamak Energy Ltd Breeder blanket
CN114414462A (en) * 2021-12-20 2022-04-29 核工业西南物理研究院 Hydrogen and isotope permeation testing device and method under corrosion coordination

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SHOICHI NASU;SHINJI NAGATA;KIICHIRO YOSHII: "Compatibility of Lithium Oxide Single Crystals with Tungsten Sputtered Films", POWDER METALLURGICAL HIGH PERFORMANCE MATERIALS VOL.1: HIGH PERFORMANCE P/M METALS, vol. 52, no. 6, pages 427 - 429 *
SHOICHI NASU;SHINJI NAGATA;KIICHIRO YOSHII: "Compatibility of Lithium Oxide Single Crystals with Tungsten Sputtered Films", vol. 52, no. 6 *
T. HERNÁNDEZ ET AL.: "Effect of irradiation on the stability of the corrosion layer produced in EUROFER by contact with lithium ceramics", JOURNAL OF NUCLEAR MATERIALS, vol. 545, pages 152614 *

Also Published As

Publication number Publication date
CN115305442B (en) 2023-09-19

Similar Documents

Publication Publication Date Title
CN108914039B (en) Nuclear zirconium alloy protective coating material and preparation method thereof
CN110055496B (en) Preparation process for preparing Cr coating on surface of nuclear zirconium alloy substrate
Huang et al. Preparation and properties of FeAl/Al2O3 composite tritium permeation barrier coating on surface of 316L stainless steel
CN109972098A (en) A kind of preparation method of cladding materials surface C rN thick coating
CN108796454A (en) A kind of used by nuclear reactor zirconium cladding surface metal coating PVD preparation processes
CN109943811B (en) Preparation method of coating for zirconium alloy cladding
CN100393909C (en) Method for depositing thermal barrier coating of porous dentrite ceramic layer by electron beam physical vapor deposition process
Huang et al. Microstructural evolution of Cr-coated Zr-4 alloy prepared by multi-arc ion plating during high temperature oxidation
CN109546076B (en) Preparation method of sandwich structure type lithium-sulfur battery positive plate
CN104561891A (en) Double-component gradient hydrogen permeation barrier coating and preparation method thereof
CN110499494A (en) It is a kind of using Zr as Cr/Al monofilm of substrate and preparation method thereof
CN115305442A (en) Surface modified tritium proliferation agent and preparation method thereof
CN109811316A (en) Long-lived phase zircaloy coating of a kind of high burnup and preparation method thereof
Yan et al. Properties of oxide coating on the surface of ZrH 1.8 prepared by microarc oxidation with different positive voltages
Zhao et al. Initial oxidation behavior of ferritic stainless steel interconnect with sputtered NiFe2 alloy coating
CN111155052A (en) Er2O3Preparation method and application of coating
CN114134456B (en) Magnetron sputtering preparation method of Cr coating of zirconium alloy cladding
CN115142018A (en) High-entropy alloy coating resistant to high-temperature liquid lead/lead bismuth alloy corrosion and preparation method thereof
CN106637116B (en) A kind of simple preparation method of secondary film
Van den Berghe et al. SELENIUM fuel: surface engineering of U (Mo) particles to optimise fuel performance
CN214422533U (en) Zirconium hydride composite hydrogen-resistant coating structure
CN115044868A (en) Oxide ceramic and two-dimensional material composite hydrogen-resistant coating and preparation method thereof
CN110184604A (en) A kind of used by nuclear reactor high rigidity clad and preparation method thereof
CN105132982B (en) A kind of preparation method of uranium and its alloy surface ceramic coating
CN117253968A (en) Preparation method of layered oxide of sodium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant