CN113061830A - Preparation method of high-entropy alloy coating on surface of nuclear structural material and nuclear radiation-resistant structural material - Google Patents
Preparation method of high-entropy alloy coating on surface of nuclear structural material and nuclear radiation-resistant structural material Download PDFInfo
- Publication number
- CN113061830A CN113061830A CN202110307699.6A CN202110307699A CN113061830A CN 113061830 A CN113061830 A CN 113061830A CN 202110307699 A CN202110307699 A CN 202110307699A CN 113061830 A CN113061830 A CN 113061830A
- Authority
- CN
- China
- Prior art keywords
- entropy alloy
- structural material
- nuclear
- alloy coating
- plasma
- 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.)
- Pending
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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention provides a preparation method of a high-entropy alloy coating on the surface of a nuclear structural material and a nuclear radiation-resistant structural material. The preparation method comprises the following steps: obtaining a high-entropy alloy block by using a high-entropy alloy raw material through an arc melting method; crushing and ball-milling the high-entropy alloy block, and then placing the high-entropy alloy block into a plasma spheroidizing device for plasma spheroidizing to obtain high-entropy alloy spherical powder; and spraying the high-entropy alloy spherical powder onto the surface of the nuclear structural material in a plasma spraying manner to form a high-entropy alloy coating on the surface of the nuclear structural material. The invention prepares the high-entropy alloy spherical powder by electric arc melting, high-energy ball milling and plasma spheroidization, and then forms a compact high-entropy alloy coating on the surface of the structural material for the core by a plasma spraying method, thereby improving the irradiation resistance of the structural material for the core.
Description
Technical Field
The invention relates to the technical field of metal surface protection, in particular to a preparation method of a high-entropy alloy coating on the surface of a nuclear structural material and a nuclear radiation-resistant structural material.
Background
Over the past few decades, clean energy nuclear power has become the third largest energy source in the world. Due to the severe working conditions of the nuclear power station, the used structural materials are generally required to have good comprehensive properties such as high temperature resistance, radiation resistance, corrosion resistance and the like. High entropy alloys, which are widely regarded for their unique structure and excellent properties, are generally defined as being composed of at least five atoms of main elements in a content of between 5 and 35%, which elements form simple solid solutions of crystal structure, rather than complex intermetallic compounds, as compared to conventional alloys. Under the influence of the high-entropy effect, the high-entropy alloy shows excellent performances such as high-temperature thermal stability, corrosion resistance, irradiation resistance and the like different from those of the traditional alloy. However, since the high-entropy alloy has low workability and is expensive to manufacture, it is difficult to use in a structural material for a nuclear reactor. The high-entropy alloy coating can show the advantages similar to those of high-entropy alloy, but the compactness and the irradiation resistance of the high-entropy alloy coating prepared by the conventional method need to be further improved.
Disclosure of Invention
The invention solves the problems that the high-entropy alloy coating prepared by the existing method has poor compactness and low irradiation resistance.
In order to solve the problems, the invention provides a preparation method of a high-entropy alloy coating on the surface of a nuclear structural material, which comprises the following steps:
obtaining a high-entropy alloy block by using a high-entropy alloy raw material through an arc melting method;
crushing and ball-milling the high-entropy alloy block, and then placing the high-entropy alloy block into a plasma spheroidizing device for plasma spheroidizing to obtain high-entropy alloy spherical powder;
and spraying the high-entropy alloy spherical powder onto the surface of the nuclear structural material in a plasma spraying manner to form a high-entropy alloy coating on the surface of the nuclear structural material.
Preferably, the high-entropy alloy raw material comprises at least three of Zr, W, Ta, Hf, V, Ti, Cr and Ce, wherein the molar ratio of each element is Zr: w: ta: hf: v: ti: cr: ce is 0-25:0-25: 0-25:0-25: 0-25:0-25: 0-25: 0-5.
Preferably, the output power of the plasma spheroidizing device is 40kW, the powder feeding speed is 50-180g/min, the central gas and the carrier gas are argon, and the sheath flow gas is argon-hydrogen mixed gas, wherein the flow rate of the central gas is 15-30L/min, the flow rate of the carrier gas is 2-4L/min, and the flow rate of the sheath flow gas is 50-70L/min.
Preferably, the particle size of the high-entropy alloy spherical powder is 15-70 μm.
Preferably, the crushing and ball milling of the high-entropy alloy block comprises:
crushing the high-entropy alloy block into particles with the size smaller than 2mm to obtain high-entropy alloy particles, placing the high-entropy alloy particles in a stainless steel ball-milling tank for high-energy ball milling, wherein the ball-material ratio is controlled to be 12-15:1 during ball milling, the ball-milling time is 20-36h, and the rotating speed is 250-350rpm during ball milling.
Preferably, the process parameters of the plasma spraying include: the current intensity is 55-650A, the argon flow is 30-40L/min, the hydrogen flow is 8-13L/min, the powder feeding speed is 50-60g/min, the spraying distance is 80-150mm, and the moving speed of the spray gun is 8-1.5 m/s.
Preferably, the thickness of the high-entropy alloy coating is 100-1000 μm.
Preferably, the arc melting process is carried out in an electric arc furnace, the melting atmosphere of the electric arc furnace is argon, and the raw materials are overturned and melted in the electric arc furnace for 5-8 times.
Preferably, the structural material for core is a structural material for core which is subjected to surface treatment, and the surface treatment process includes: cleaning the surface of the nuclear structural material with alcohol, drying, blasting sand on the surface of the nuclear structural material cleaned and dried with the alcohol by using brown corundum with the granularity of 200 meshes, and after the blasting sand is finished, ultrasonically cleaning the blasted nuclear structural material with the alcohol to remove residual particles on the surface to obtain the nuclear structural material.
The invention also provides an irradiation-resistant structural material for the core, which comprises a structural material for the core and the high-entropy alloy coating formed on the surface of the structural material for the core, wherein the high-entropy alloy coating is prepared by adopting the preparation method of the high-entropy alloy coating on the surface of the structural material for the core.
The invention prepares the high-entropy alloy coating which has compact structure, lower porosity and tight combination with the matrix on the surface of the nuclear structural material through the combined action of electric arc melting, plasma spheroidization and plasma spraying. Firstly, compared with a discharge plasma sintering or mechanical alloying method, a powder preparation method combining arc melting and plasma spheroidization can obtain an alloy with more uniform components through the arc melting method, then the alloy is further crushed through high-energy ball milling, and is prepared into spherical powder through the plasma spheroidization method, so that spray powder with higher particle size uniformity is prepared, then plasma electric arc is used as a heat source, the high-entropy alloy spray powder with uniform components is heated to a molten or semi-molten state and is sprayed to the surface of a structural material for the nuclear at high speed, so that a high-entropy alloy coating with firm adhesion is formed on the surface of the structural material for the nuclear, and the irradiation resistance of the structural material for the nuclear is effectively improved.
Drawings
FIG. 1 is a flow chart of a preparation method of a high-entropy alloy coating on the surface of a nuclear structural material in an embodiment of the invention;
FIG. 2 is a SEM image of a coating section of a radiation-resistant structural material for a core prepared in example 1 of the present invention;
FIG. 3 is a comparison graph of the morphology of the coating of the radiation-resistant structural material for nuclei prepared in example 1 of the present invention before and after heavy ion irradiation.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a high-entropy alloy coating on a surface of a structural material for a core, including the following steps:
obtaining a high-entropy alloy block by using a high-entropy alloy raw material through an arc melting method;
crushing and ball-milling the high-entropy alloy block, and then placing the high-entropy alloy block into a plasma spheroidizing device for plasma spheroidizing to obtain high-entropy alloy spherical powder;
and spraying the high-entropy alloy spherical powder onto the surface of the nuclear structural material in a plasma spraying manner to form a high-entropy alloy coating (hereinafter referred to as a coating) on the surface of the nuclear structural material.
The high-entropy alloy raw materials comprise at least three of Zr, W, Ta, Hf, V, Ti, Cr and Ce, wherein Zr is zirconium, W is tungsten, Ta is tantalum, Hf is hafnium, V is vanadium, Ti is titanium, Cr is chromium, Ce is cerium, and the molar ratio of the elements is Zr: w: ta: hf: v: ti: cr: ce is 0-25:0-25: 0-25:0-25: 0-25:0-25: 0-25: 0-5.
In order to obtain a high-entropy alloy coating with a compact structure on the surface of a structural material for a core, in this embodiment, first, high-entropy alloy spherical powder with uniform structure components is prepared by adopting a method of arc melting, high-energy ball milling and plasma spheroidization, then, the high-entropy alloy spherical powder is sprayed on the surface of the structural material for the core by adopting a plasma spraying method, and the compact high-entropy alloy coating is sprayed on the surface of the structural material for the core, so that the binding force between the structural material for the core and the coating is increased.
In the prior art, a mechanical alloying method is generally adopted to prepare a high-entropy alloy powder material, wherein the mechanical alloying is a process of enabling powder to undergo repeated deformation, cold welding and crushing through high-energy ball milling so as to achieve the purpose of alloying elements at an atomic level, namely, various metal or alloy powder is mixed together through ball milling. Compared with the alloy material formed after metal or alloy smelting, mechanical alloying only enables the components to reach or approach the atomic-scale distance on the contacted points, lines and surfaces within limited ball milling time, and finally the obtained mixture is only the uniform distribution of the components, and the full interatomic combination among the components is difficult to achieve to further form uniform solid solution.
In the embodiment, the spherical metal powder with fine and controllable granularity can be prepared by adopting a plasma spheroidization method for preparing powder. The principle of plasma spheroidizing powder preparation is as follows: the powder is sent into the high-temperature plasma by using the high-temperature environment of the thermal plasma and the carrier gas, the powder particles are quickly heated and then surface (or whole) melted, and are condensed into spherical liquid drops under the action of surface tension, and the spherical liquid drops are condensed and solidified after entering a cooling chamber, so that the spherical powder is obtained.
In this embodiment, at least five simple substances of zirconium, tungsten, tantalum, hafnium, vanadium, titanium, chromium, and cerium with a purity of more than 99.99% are alloyed by an arc melting method to prepare a high-entropy alloy block with uniformly distributed components of each metal element. And performing a series of subsequent processing treatments on the alloyed particles, including crushing, ball milling and the like, to obtain small-size alloy particles, namely in the embodiment, crushing the high-entropy alloy blocks into low-granularity high-entropy alloy powder by ball milling, and then melting the high-entropy alloy powder by plasma, and preparing the high-entropy alloy spherical powder by matching with airflow and the like.
Because the simple substances of zirconium, tungsten, tantalum, hafnium, vanadium, titanium, chromium and cerium have high melting points and belong to refractory high-entropy alloys, the embodiment adopts the methods of arc melting, ball milling and plasma spheroidization to prepare the high-entropy alloy powder material with uniformly distributed components, and is beneficial to obtaining a compact coating through subsequent plasma spraying.
Preferably, the molar ratio of each element in the high-entropy alloy raw material is Zr: w: ta: hf: v: ti: cr: ce is 0-10:10-25: 0-10: 0-10: 0-10: 2-25: 0-1. The purity of each metal simple substance is over 99.99 percent. The electric arc melting process is carried out in an electric arc furnace, the melting atmosphere of the electric arc furnace is argon, and the raw materials are turned over and melted for 5-8 times under the protection of high-purity argon in the electric arc melting process so as to ensure the uniformity of element distribution.
In some embodiments, crushing and ball milling the high-entropy alloy block to obtain the high-entropy alloy powder comprises: crushing the high-entropy alloy blocks into particles with the size smaller than 2mm to obtain high-entropy alloy particles, placing the high-entropy alloy particles in a stainless steel ball milling tank for high-energy ball milling, wherein 5mm WC balls are adopted during ball milling, the ball-material ratio is controlled to be 12-15:1, the ball milling time is 20-36h, and the rotating speed during ball milling is 250-350 rpm.
In some embodiments, plasma spheroidizing the high entropy alloy powder comprises: plasma spheroidization is carried out in a plasma spheroidization device, the plasma spheroidization device generally comprises a plasma reaction device, a powder feeding device, a control device and the like, wherein the output power of the plasma spheroidization device is 40kW, the powder feeding speed is 50-180g/min, argon is used as a central gas and a carrier gas, the central gas is a working gas introduced into the plasma reaction device, the working gas is discharged through an external electric field or a high-frequency induction electric field and the like to generate plasma, the carrier gas is a gas for carrying a powder raw material, the flow rate of the central gas is 15-30L/min, the flow rate of the carrier gas is 2-4L/min, a sheath flow gas is an argon-hydrogen mixed gas, a sheath flow gas is a protective gas in the plasma reaction device, and the flow rate of the sheath flow is 50-70L/min.
And screening after plasma spheroidization to obtain high-entropy alloy spherical powder with the particle size of 15-70 mu m, and drying and screening the high-entropy alloy spherical powder to prepare the high-entropy alloy coating on the surface of the nuclear structural material. In the embodiment, a plasma spraying process is adopted, plasma electric arc is used as a heat source for plasma spraying, the powder material is heated to a molten or semi-molten state and is sprayed to the surface of the nuclear structural material at a high speed, and the powder material is spherical powder prepared by adopting the method, namely, arc melting and plasma spheroidizing, and the components are uniformly distributed, so that a compact coating can be obtained during plasma spraying, and the bonding strength between the coating and the surface of the nuclear structural material is high. In addition, before spraying, the surface treatment is carried out on the structural material for the core, which specifically comprises the following steps: cleaning the surface of the nuclear structural material with alcohol, drying, blasting sand on the surface of the nuclear structural material cleaned with alcohol and dried by brown corundum with the granularity of 200 meshes, and after the blasting sand is finished, ultrasonically cleaning the nuclear structural material subjected to blasting sand by using alcohol, and removing residual particles on the surface to obtain the nuclear structural material.
Installing the nuclear structural material subjected to surface treatment on a fixed clamp, and spraying by adopting set spraying process parameters, wherein the current intensity is 55-650A, the argon flow is 30-40L/min, the hydrogen flow is 8-13L/min, the powder feeding speed is 3-5r/min, the spraying distance is 300-380mm, the moving speed of a spray gun is 0.3-0.8m/s, and after multiple times of circulating spraying, the high-entropy alloy coating with the thickness of 100-1000 mu m is prepared.
The present invention will be described in detail with reference to specific examples.
Example 1
The WTaCrVTiZr high-entropy alloy block is prepared by using W, Ta, Cr, V, Ti and Zr with the purity of over 99.99% as raw materials and utilizing an arc melting method, wherein the mole percentage of each element atom in the raw materials is W25%, Ta 25%, Cr 25%, V10%, Ti 8% and Zr 7%.
The prepared high-entropy alloy block is subjected to mechanical crushing, ball milling and plasma spheroidization to obtain high-entropy alloy spherical powder, and the high-entropy alloy spherical powder is sieved to obtain spherical powder with the particle size of 30 microns, wherein the ball-material ratio during ball milling is 15:1, the ball milling time is 24 hours, and the rotating speed is 300 rpm; the output power of the plasma spheroidizing device is 40kW, the powder feeding speed is 150g/min, the central gas and the carrier gas are argon, the flow rate of the central gas is 20L/min, the flow rate of the carrier gas is 3L/min, the sheath flow gas is argon-hydrogen mixed gas, and the flow rate of the sheath flow is 60L/min.
Spraying spherical powder onto the nuclear structural material by adopting a plasma spraying method, preparing a high-entropy alloy coating on the surface of the nuclear structural material, and obtaining the nuclear radiation-resistant structural material, wherein the plasma spraying process parameters are as follows: the current intensity is 500A, the argon flow is 30L/min, the hydrogen flow is 10L/min, the powder feeding speed is 4r/min, the spraying distance is 350mm, and the moving speed of the spray gun is 0.5 m/s.
The cross section of the coating of the radiation-resistant structural material for the core prepared in the embodiment is detected by a scanning electron microscope, and the result is shown in fig. 2, and as can be seen from fig. 2, the coating has a compact structure and is well combined with a matrix.
The coating prepared in the embodiment has the thickness of 800 microns, and the hardness of the coating is detected by using a Vickers hardness tester and is up to 1380 HV.
The change of the coating structure morphology before and after heavy ion irradiation of the radiation-resistant structural material for the core prepared in the embodiment is shown in FIG. 3, and as can be seen from FIG. 3, the coating layer has a thickness of 10MeV and a thickness of 7 × 1016Au+/cm2Swelling phenomenon is not found after heavy ion irradiation, which shows that the irradiation-resistant structural material for the nucleus prepared by the embodiment has excellent irradiation swelling resistance.
Example 2
The method comprises the steps of taking Zr, W, Ta, Hf, V, Ti, Cr and Ce elementary metals with purity of over 99.99% as raw materials, and preparing a ZrWTaHfVTiCrCe high-entropy alloy block by an arc melting method, wherein the atomic mole percentage content of each element in the raw materials is Zr 20%, W15%, Ta 15%, Hf 10%, V10%, Ti 10%, Cr 18% and Ce 2.
The prepared high-entropy alloy block is subjected to mechanical crushing, ball milling and plasma spheroidization to obtain high-entropy alloy spherical powder, and the high-entropy alloy spherical powder is sieved to obtain spherical powder with the particle size of 15 microns, wherein the ball-material ratio during ball milling is 12:1, the ball milling time is 36h, and the rotating speed is 350 rpm; the output power of the plasma spheroidizing device is 40kW, the powder feeding speed is 50g/min, the central gas and the carrier gas are argon, the flow rate of the central gas is 15L/min, the flow rate of the carrier gas is 2L/min, the sheath flow gas is argon-hydrogen mixed gas, and the flow rate of the sheath flow is 50L/min.
Spraying spherical powder onto the nuclear structural material by adopting a plasma spraying method, preparing a high-entropy alloy coating on the surface of the nuclear structural material, and obtaining the nuclear radiation-resistant structural material, wherein the plasma spraying process parameters are as follows: the current intensity is 650A, the argon flow is 40L/min, the hydrogen flow is 13L/min, the powder feeding speed is 3r/min, the spraying distance is 300mm, and the moving speed of the spray gun is 0.3 m/s.
The coating thickness of the radiation-resistant structural material for the core prepared in the embodiment is 500 microns, and the coating hardness is 1270 HV.
Example 3
The method comprises the steps of taking Zr, W, Ta, Hf, V, Ti, Cr and Ce elementary metals with purity of over 99.99% as raw materials, and preparing a ZrWTaHfVTiCrCe high-entropy alloy block by utilizing an arc melting method, wherein the atomic mole percentage content of each element in the raw materials is Zr 10%, W10%, Ta 10%, Hf 25%, V25%, Ti 10%, Cr 5% and Ce 5%.
The prepared high-entropy alloy block is subjected to mechanical crushing, ball milling and plasma spheroidization to obtain high-entropy alloy spherical powder, and the high-entropy alloy spherical powder is sieved to obtain spherical powder with the particle size of 70 microns, wherein the ball-material ratio during ball milling is 15:1, the ball milling time is 20 hours, and the rotating speed is 300 rpm; the output power of the plasma spheroidizing device is 40kW, the powder feeding speed is 180g/min, the central gas and the carrier gas are argon, the flow rate of the central gas is 30L/min, the flow rate of the carrier gas is 4L/min, the sheath flow gas is argon-hydrogen mixed gas, and the flow rate of the sheath flow is 70L/min.
Spraying spherical powder onto the nuclear structural material by adopting a plasma spraying method, preparing a high-entropy alloy coating on the surface of the nuclear structural material, and obtaining the nuclear radiation-resistant structural material, wherein the plasma spraying process parameters are as follows: the current intensity is 55A, the argon flow is 35L/min, the hydrogen flow is 8L/min, the powder feeding speed is 5r/min, the spraying distance is 380mm, and the moving speed of the spray gun is 0.8 m/s.
The coating thickness of the radiation-resistant structural material for the core prepared in the embodiment is 100 micrometers, and the coating hardness is 1350 HV.
Example 4
The method comprises the following steps of taking Zr, W, Ta, Hf, V, Ti, Cr and Ce metal simple substances with purity of over 99.99% as raw materials, and preparing a ZrWTaHfVTiCrCe high-entropy alloy block by using an arc melting method, wherein the raw materials comprise the following elements in atomic mole percentage: zr 15%, W15%, Ta 15%, Hf 10%, V17%, Ti 25%, Cr 2%, Ce 1%.
The prepared high-entropy alloy block is subjected to mechanical crushing, ball milling and plasma spheroidization to obtain high-entropy alloy spherical powder, and the high-entropy alloy spherical powder is sieved to obtain spherical powder with the particle size of 50 microns, wherein the ball-material ratio during ball milling is 15:1, the ball milling time is 30 hours, and the rotating speed is 250 rpm; the output power of the plasma spheroidizing device is 40kW, the powder feeding speed is 100g/min, the central gas and the carrier gas are argon, the flow rate of the central gas is 25L/min, the flow rate of the carrier gas is 4L/min, the sheath flow gas is argon-hydrogen mixed gas, and the flow rate of the sheath flow is 70L/min.
Spraying spherical powder onto the nuclear structural material by adopting a plasma spraying method, preparing a high-entropy alloy coating on the surface of the nuclear structural material, and obtaining the nuclear radiation-resistant structural material, wherein the plasma spraying process parameters are as follows: the current intensity is 300A, the argon flow is 40L/min, the hydrogen flow is 12L/min, the powder feeding speed is 4r/min, the spraying distance is 350mm, and the moving speed of the spray gun is 0.6 m/s.
The coating thickness of the radiation-resistant structural material for the core prepared in the embodiment is 1000 microns, and the coating hardness is 1290 HV.
EXAMPLE five
The difference between the embodiment and the embodiment one is that the raw materials for arc melting are simple metal substances of Zr, W, Ta, Cr and Ti with purity of over 99.99%, wherein the atomic mole percentage of each element is as follows: zr 25%, W10%, Ta 25%, Cr 25% and Ti 15%.
The coating thickness of the radiation-resistant structural material for the core prepared in the embodiment is 250 micrometers, and the coating hardness is 1310 HV.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. A preparation method of a high-entropy alloy coating on the surface of a nuclear structural material is characterized by comprising the following steps:
obtaining a high-entropy alloy block by using a high-entropy alloy raw material through an arc melting method;
crushing and ball-milling the high-entropy alloy block, and then placing the high-entropy alloy block into a plasma spheroidizing device for plasma spheroidizing to obtain high-entropy alloy spherical powder;
and spraying the high-entropy alloy spherical powder onto the surface of the nuclear structural material in a plasma spraying manner to form a high-entropy alloy coating on the surface of the nuclear structural material.
2. The method for preparing the high-entropy alloy coating on the surface of the nuclear structural material according to claim 1, wherein the high-entropy alloy raw material comprises at least three of Zr, W, Ta, Hf, V, Ti, Cr and Ce, and the molar ratio of each element is Zr: w: ta: hf: v: ti: cr: ce is 0-25:0-25: 0-25:0-25: 0-25:0-25: 0-25: 0-5.
3. The method for preparing the high-entropy alloy coating on the surface of the nuclear structural material, according to claim 1, wherein the output power of the plasma spheroidizing device is 40kW, the powder feeding speed is 50-180g/min, the central gas and the carrier gas are argon, the sheath flow gas is argon-hydrogen mixed gas, the flow rate of the central gas is 15-30L/min, the flow rate of the carrier gas is 2-4L/min, and the flow rate of the sheath flow gas is 50-70L/min.
4. The method for preparing the surface high-entropy alloy coating layer of the structural material for the core according to claim 1, wherein the particle size of the high-entropy alloy spherical powder is 15-70 μm.
5. The method for preparing the high-entropy alloy coating on the surface of the nuclear structural material according to claim 1, wherein the step of crushing and ball-milling the high-entropy alloy block comprises the following steps:
crushing the high-entropy alloy block into particles with the size smaller than 2mm to obtain high-entropy alloy particles, placing the high-entropy alloy particles in a stainless steel ball-milling tank for high-energy ball milling, wherein the ball-material ratio is controlled to be 12-15:1 during ball milling, the ball-milling time is 20-36h, and the rotating speed is 250-350rpm during ball milling.
6. The method for preparing the high-entropy alloy coating on the surface of the nuclear structural material according to claim 1, wherein the plasma spraying process parameters comprise: the current intensity is 55-650A, the argon flow is 30-40L/min, the hydrogen flow is 8-13L/min, the powder feeding speed is 50-60g/min, the spraying distance is 80-150mm, and the moving speed of the spray gun is 8-1.5 m/s.
7. The method for preparing the high-entropy alloy coating on the surface of the nuclear structural material as claimed in claim 1, wherein the thickness of the high-entropy alloy coating is 100-1000 μm.
8. The method for preparing the surface high-entropy alloy coating of the structural material for the nuclear, according to claim 1, is characterized in that an electric arc melting process is carried out in an electric arc furnace, the melting atmosphere of the electric arc furnace is argon, and the raw material is overturned and melted in the electric arc furnace for 5-8 times.
9. The method for preparing the high-entropy alloy coating layer on the surface of the structural material for the core as claimed in claim 1, wherein the structural material for the core is a structural material for the core which is subjected to surface treatment, and the surface treatment process comprises the following steps: cleaning the surface of the nuclear structural material with alcohol, drying, blasting sand on the surface of the nuclear structural material cleaned and dried with the alcohol by using brown corundum with the granularity of 200 meshes, and after the blasting sand is finished, ultrasonically cleaning the blasted nuclear structural material with the alcohol to remove residual particles on the surface to obtain the nuclear structural material.
10. An irradiation-resistant structural material for a core, which comprises a structural material for a core and a high-entropy alloy coating formed on the surface of the structural material for a core, wherein the high-entropy alloy coating is prepared by the preparation method of the high-entropy alloy coating on the surface of the structural material for a core according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110307699.6A CN113061830A (en) | 2021-03-23 | 2021-03-23 | Preparation method of high-entropy alloy coating on surface of nuclear structural material and nuclear radiation-resistant structural material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110307699.6A CN113061830A (en) | 2021-03-23 | 2021-03-23 | Preparation method of high-entropy alloy coating on surface of nuclear structural material and nuclear radiation-resistant structural material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113061830A true CN113061830A (en) | 2021-07-02 |
Family
ID=76563044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110307699.6A Pending CN113061830A (en) | 2021-03-23 | 2021-03-23 | Preparation method of high-entropy alloy coating on surface of nuclear structural material and nuclear radiation-resistant structural material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113061830A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114807715A (en) * | 2022-04-14 | 2022-07-29 | 中国原子能科学研究院 | Alloy and nuclear reactor component with alloy coating on surface |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104561878A (en) * | 2013-10-29 | 2015-04-29 | 比亚迪股份有限公司 | High-entropy alloy powder for spray coating and preparation method thereof, as well as composite material and preparation method thereof |
| US20180025794A1 (en) * | 2016-07-22 | 2018-01-25 | Westinghouse Electric Company Llc | Spray methods for coating nuclear fuel rods to add corrosion resistant barrier |
| CN108145170A (en) * | 2017-12-11 | 2018-06-12 | 中南大学 | A kind of preparation method of infusibility high-entropy alloy spherical powder |
| CN109666911A (en) * | 2019-01-29 | 2019-04-23 | 成都理工大学 | The high entropy alloy coating and preparation method thereof of nuclear-used zirconium alloy involucrum surface refractory corrosion |
| KR20190070173A (en) * | 2017-12-12 | 2019-06-20 | 한국생산기술연구원 | High entropy alloy powder and method for manufacturing the same |
| CN110129716A (en) * | 2019-05-23 | 2019-08-16 | 天津大学 | A kind of preparation method of high entropy alloy coating |
| CN111118378A (en) * | 2019-12-31 | 2020-05-08 | 西安西工大超晶科技发展有限责任公司 | High-entropy alloy for nuclear and preparation method thereof |
| CN111926232A (en) * | 2020-07-07 | 2020-11-13 | 燕山大学 | High-entropy alloy material and preparation method thereof |
| CN112317752A (en) * | 2020-11-11 | 2021-02-05 | 北京科技大学 | TiZrNbTa high-entropy alloy for 3D printing and preparation method and application thereof |
-
2021
- 2021-03-23 CN CN202110307699.6A patent/CN113061830A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104561878A (en) * | 2013-10-29 | 2015-04-29 | 比亚迪股份有限公司 | High-entropy alloy powder for spray coating and preparation method thereof, as well as composite material and preparation method thereof |
| US20180025794A1 (en) * | 2016-07-22 | 2018-01-25 | Westinghouse Electric Company Llc | Spray methods for coating nuclear fuel rods to add corrosion resistant barrier |
| CN108145170A (en) * | 2017-12-11 | 2018-06-12 | 中南大学 | A kind of preparation method of infusibility high-entropy alloy spherical powder |
| KR20190070173A (en) * | 2017-12-12 | 2019-06-20 | 한국생산기술연구원 | High entropy alloy powder and method for manufacturing the same |
| CN109666911A (en) * | 2019-01-29 | 2019-04-23 | 成都理工大学 | The high entropy alloy coating and preparation method thereof of nuclear-used zirconium alloy involucrum surface refractory corrosion |
| CN110129716A (en) * | 2019-05-23 | 2019-08-16 | 天津大学 | A kind of preparation method of high entropy alloy coating |
| CN111118378A (en) * | 2019-12-31 | 2020-05-08 | 西安西工大超晶科技发展有限责任公司 | High-entropy alloy for nuclear and preparation method thereof |
| CN111926232A (en) * | 2020-07-07 | 2020-11-13 | 燕山大学 | High-entropy alloy material and preparation method thereof |
| CN112317752A (en) * | 2020-11-11 | 2021-02-05 | 北京科技大学 | TiZrNbTa high-entropy alloy for 3D printing and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王雪姣 等: ""高熵合金:面向聚变堆抗辐照损伤的新型候选材料"", 《材料导报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114807715A (en) * | 2022-04-14 | 2022-07-29 | 中国原子能科学研究院 | Alloy and nuclear reactor component with alloy coating on surface |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Influence of Y2O3 addition on the microstructure of TiC reinforced Ti-based composite coating prepared by laser cladding | |
| KR102639133B1 (en) | Process for producing spheroidized powder from feedstock materials | |
| CN103752836B (en) | A kind of method preparing fine grain spherical niobium titanium base alloy powder | |
| CN113061763B (en) | High-entropy alloy and preparation method thereof | |
| CN102717086B (en) | Method for preparing high-niobium titanium-aluminum alloy spherical micro powder in short process | |
| CN112317752B (en) | TiZrNbTa high-entropy alloy for 3D printing and preparation method and application thereof | |
| CN108705096B (en) | Preparation method of fine-particle-size spherical 18Ni300 powder | |
| JP5046890B2 (en) | Ag-based sputtering target | |
| CN109434117B (en) | Preparation method of spherical zirconium-niobium alloy powder for 3D printing | |
| TW202106893A (en) | Spherical tantalum-titanium alloy powder, products containing the same, and methods of making the same | |
| CN107119211B (en) | A kind of preparation method of 3D printing Ni3Al base alloy powder | |
| WO2022174766A1 (en) | Titanium alloy powder for selective laser melting 3d printing, and selective laser melting titanium alloy and preparation thereof | |
| CN110340371A (en) | A kind of preparation method of granule intensified titanium-base compound material increasing material manufacturing powder | |
| JPH05504172A (en) | Plasma spraying of rapidly solidifying aluminum-based alloys | |
| CN111850543A (en) | Laser cladding seven-element high-entropy alloy coating and preparation method thereof | |
| CN106048380A (en) | High-entropy alloy based composite coating and preparation method thereof | |
| CN105562680B (en) | The method that a kind of high-entropy alloy powder and hot pressed sintering prepare high-entropy alloy coating | |
| JP2009287106A (en) | Method for producing titanium spherical powder, and titanium spherical powder | |
| CN113061830A (en) | Preparation method of high-entropy alloy coating on surface of nuclear structural material and nuclear radiation-resistant structural material | |
| CN110340343A (en) | Laser Melting Deposition increasing material manufacturing and heat treatment method using PREP TC4 powder | |
| CN113462911B (en) | Preparation method of tough corrosion-resistant AZ80 magnesium alloy | |
| CN110756807B (en) | Laser melting deposition method of hydrogenated titanium dehydrogenated powder | |
| CN113073320A (en) | Method for preparing high-entropy alloy coating on surface of nuclear structural material and nuclear radiation-resistant structural material | |
| Wang et al. | Effect of laser power on the microstructure and mechanical properties of laser-assisted cold sprayed 7075 aluminum alloy deposits | |
| CN113843415B (en) | Tantalum-niobium alloy powder and preparation method thereof |
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 |