CN116516286B - High-entropy ceramic nitride protective coating for shielding high-energy electrons and preparation method thereof - Google Patents
High-entropy ceramic nitride protective coating for shielding high-energy electrons and preparation method thereof Download PDFInfo
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- 150000004767 nitrides Chemical class 0.000 title claims abstract description 35
- 239000011253 protective coating Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 64
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 31
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 229910052786 argon Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011651 chromium Substances 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 239000012495 reaction gas Substances 0.000 claims abstract description 7
- 239000010937 tungsten Substances 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 238000004544 sputter deposition Methods 0.000 claims description 44
- 239000011248 coating agent Substances 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 42
- 238000000498 ball milling Methods 0.000 claims description 33
- 238000005245 sintering Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 229910000838 Al alloy Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000013077 target material Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- WTKKCYNZRWIVKL-UHFFFAOYSA-N tantalum Chemical compound [Ta+5] WTKKCYNZRWIVKL-UHFFFAOYSA-N 0.000 claims description 2
- HHIQWSQEUZDONT-UHFFFAOYSA-N tungsten Chemical compound [W].[W].[W] HHIQWSQEUZDONT-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000843 powder Substances 0.000 abstract description 25
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- 230000001681 protective effect Effects 0.000 description 4
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- 238000002490 spark plasma sintering Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- SYHGEUNFJIGTRX-UHFFFAOYSA-N methylenedioxypyrovalerone Chemical compound C=1C=C2OCOC2=CC=1C(=O)C(CCC)N1CCCC1 SYHGEUNFJIGTRX-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
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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
- C23C14/06—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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- 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
Abstract
The invention discloses a high-entropy ceramic nitride protective coating for shielding high-energy electrons and a preparation method thereof, and belongs to the technical field of radiation protection. The method utilizes the high-entropy ceramic nitrides of different elements to form solid solutions, realizes the uniform distribution of the elements in the material, fully considers the synergistic effect of the elements in the shielding process, keeps the stability of the material in the shielding process, and avoids the generation of bremsstrahlung as much as possible while realizing the effective shielding of high-energy electrons. The invention is formed by using 5 of aluminum, zirconium, tantalum, titanium, chromium, copper, tungsten and iron powders as raw materials to prepare a high-entropy alloy target, and then using argon as working gas and nitrogen as reaction gas to sputter the high-entropy alloy target on a metal substrate by using a magnetron sputtering technology. The invention is suitable for the actual task environment of the spacecraft and can be used in the fields of deep space exploration and the like.
Description
Technical Field
The invention belongs to the technical field of radiation protection, and particularly relates to a high-entropy ceramic nitride protective coating for shielding high-energy electrons and a preparation method thereof. Can be applied to the fields of spacecrafts, nuclear protection, nuclear reactors and the like, and has very wide application prospect.
Background
The electronic device is used as a supporting product of modern technology, is widely applied to the fields of communication, energy, medical treatment and the like, and is particularly more critical in the national defense fields of aerospace, military industry and the like. There are a large number of electronic systems in the spacecraft, the reliability of the electronic devices directly affects the success or failure of the aerospace mission, but the electronic devices in the spacecraft are susceptible to high-energy electrons in the service environment to fail. Therefore, development of high-efficiency high-energy electron radiation shielding materials for implementing radiation-resistant reinforcement on electronic devices is a necessary measure for promoting development of aerospace industry in China.
Conventional electron shielding materials often use a single metal material such as aluminum, lead, tantalum, tungsten, etc., and research on the shielding materials is now being conducted more and more. Upon incidence of electrons on the shielding material, the electrons lose energy primarily by inelastic collisions with the out-of-core electrons of the shielding material, a manner known as ionization loss, which is proportional to the atomic number of the medium, meaning that the radiant energy loss in high atomic number materials is much greater than in low atomic number materials. Meanwhile, the electron incidence can cause the generation of the bremsstrahlung radiation due to inelastic collision with atomic nuclei of the shielding material, the energy loss mode is called radiation energy loss, the energy loss mode is particularly obvious when high-energy electrons are incident into the high-atomic-number material, the electromagnetic radiation emitted by the bremsstrahlung radiation has high penetrating capacity, the shielding material can be greatly damaged, and the low-atomic-number material has high absorption capacity on the bremsstrahlung radiation. In recent years, there has been a growing enthusiasm for the study of electronic shielding materials, and a great deal of research and development has been conducted on electronic shielding materials. However, the developed materials still have the defects that the actual needs are difficult to meet, and the main appearance is that: the developed material only considers the shielding performance of low-energy electrons and ignores the shielding effect of high-energy electrons; only the loss of electron energy by the shielding material is considered and the energy generated by bremsstrahlung is ignored. Therefore, development of a radiation shielding material capable of realizing effective shielding of high-energy electrons is required while considering the manufacturing process and cost thereof.
The prior art and materials are rarely provided with high-entropy ceramics as radiation shielding materials, the material design is single, and the development and utilization of novel materials are less researched.
The traditional material shielding only considers ionization damage of high-energy electrons, and the influence of bremsstrahlung radiation is ignored, so that the shielding material is invalid, and compared with the design singleness of the traditional shielding material.
In addition, some researchers have studied combinations of different element materials, but such combined structures often have uneven element distribution, dense defects and other conditions, and cannot maintain the stability of the material performance, so that the application is limited.
Disclosure of Invention
The invention aims to provide a high-entropy ceramic nitride protective coating for shielding high-energy electrons and a preparation method thereof.
According to the invention, solid solutions can be formed in the high-entropy ceramic nitrides of different elements, so that the elements are uniformly distributed in the material, the synergistic effect of the elements in the shielding process is fully considered, the stability of the material in the shielding process is maintained, and the shielding performance of the material is greatly improved.
According to the invention, the element types of the high-entropy ceramic nitride are selectively matched, so that the same material contains element components (Ta and W) with high ionization loss and element components (Al and Ti) with low radiation energy loss, and the multi-element coordination is utilized, so that the effective shielding of high-energy electrons is realized.
In order to solve the technical problems, the invention provides a high-entropy ceramic nitride protective coating for shielding high-energy electrons, which is formed by preparing a high-entropy alloy target material by taking 5 of aluminum, zirconium, tantalum, titanium, chromium, copper, tungsten and iron powder as raw materials, and then sputtering the high-entropy alloy target material on a metal substrate by using a magnetron sputtering technology by taking argon as working gas and nitrogen as reaction gas; specifically, the method comprises the following steps:
step 1, weighing raw materials, ball milling, separating and drying the ball materials, and sintering the ball materials by discharge plasma under the protection of argon to obtain a high-entropy alloy target;
and step 2, sputtering a high-entropy alloy target on the metal substrate by utilizing magnetron sputtering, wherein argon accounts for 10% -40% of the total volume of nitrogen and argon.
Further defined, the metal substrate is one of an aluminum alloy and a titanium alloy.
Further defined, the high entropy ceramic nitride protective coating material is (AlCrTaTiZr) N x 、(AlCrCuFeZr)N x 、(AlCrTiWZr)N x 、(AlCrTiCuZr)N x 。
Further defined is that the molar content of aluminum is 5% -35%, the molar content of zirconium is 5% -35%, the molar content of tantalum is 5% -35%, the molar content of titanium is 5% -35%, the molar content of chromium is 5% -35%, the molar content of copper is 5% -35%, the molar content of tungsten is 5% -35%, and the molar content of iron is 5% -35%.
Further defined, the purity of argon is 99.99% by volume and the purity of nitrogen is 99.99% by volume.
Further defined, in step 1, the ball to material ratio is (1-5): 1, e.g., 1:1, 2:1, 3:1, 4:1, 5:1, etc.
Further defined, in step 1, the ball milling speed is 100rpm to 500rpm, such as 100rpm, 200rpm, 300rpm, 400rpm, 500rpm, etc.
Further defined, in step 1, the ball milling time is 50h-100h, such as 50h, 60h, 70h, 80h, 90, 100h, etc.
Further defined, in step 1, drying is performed at 80 ℃ for at least 5 hours.
Further defined, in step 1, the sintering process: the pressure is controlled between 35MPa and 70MPa, the pulse current breaking ratio is 36ms to 6ms, the temperature is firstly increased to 800 ℃ to 1000 ℃ at the speed of 40 ℃/min to 50 ℃/min, the temperature is increased to 1200 ℃ to 1800 ℃ at the speed of 25 ℃/min to 30 ℃/min, the temperature is kept for at least 20min, and the temperature is reduced to 900 ℃ at the speed of 40 ℃/min to 50 ℃/min
Naturally cooling along with the furnace at the temperature of 1200 ℃.
In the step 1, the sintering pressure is selected from 35MPa, 40MPa, 45MPa, 50MPa, 55MPa, 60MPa, 65MPa, 70MPa and the like.
Further defined, in step 2, the magnetron sputtering step is as follows: polishing metal matrix, sequentially ultrasonic cleaning with acetone and absolute ethanol, drying, placing into sputtering chamber, and vacuum-pumping the sputtering chamber to 2.6X10% 3 Pa, introducing argon and nitrogen, wherein the total gas flow is 20mL/min, the sputtering current is 1A, the sputtering power is 160W-200W, the coating time is 5min-10min, and the coating air pressure is 1.1X10% -1 Pa, the sputtering temperature is 150-350 ℃, the substrate temperature is 50-450 ℃, and the magnetron sputtering is completed and then the substrate is cooled in a normal temperature environment.
In step 2, the substrate temperature is 50 ℃, 150 ℃, 250 ℃, 350 ℃, 450 ℃ and the like;
in step 2, sputtering power such as 160W, 170W, 180W, 190W, 200W, etc.;
in step 2, the flow ratio of nitrogen to argon (nitrogen accounts for 10%, 20%, 30%, 40% of the total volume of nitrogen and argon) is as follows.
The invention firstly uses the high-entropy ceramic nitride coating as a shielding material of high-energy electrons, and improves the shielding performance of the traditional metal material for shielding the high-energy electrons by utilizing the special element modulation flexibility of the high-entropy ceramic.
When high-energy electrons enter the high-entropy ceramic nitride, a part of energy can be consumed by collision with the extra-atomic electrons of the elements with low atomic numbers, the proportion of bremsstrahlung generated when the electrons after energy reduction and the extra-atomic electrons of the elements with high atomic numbers continue to collide is far smaller than that of the materials with high-energy electrons entering the elements with high atomic numbers, the rays of the bremsstrahlung easily penetrate through shielding materials, the high-energy electrons can be effectively prevented from being generated by shielding the high-energy electrons with high-low atomic numbers, and the shielding effect of the materials is greatly enhanced.
The high-entropy ceramic nitride has obvious effect of high-entropy materials, so that the high-entropy ceramic nitride has excellent thermodynamic stability, can keep stability in mechanical, thermal and other aspects under extreme conditions (pressure, temperature and irradiation), has practical use value, and has profound significance for development of radiation protection materials for aerospace tasks.
The invention uses the high-entropy ceramic nitride coating as a shielding material of high-energy electrons, and can effectively control the compactness of the coating material and the combination of the coating material and the substrate material by adjusting the types of elements, the proportion of metal elements, the selection of the substrate and the adjustment of relevant parameters of the magnetron sputtering technology.
The high-entropy ceramic nitride can be formed by selecting any metal element in a certain range, and the composition of the elements is designed according to different shielding requirements, and when the high-entropy ceramic nitride contains metal elements (Ta and W) with high atomic numbers and metal elements (Al and Ti) with low atomic numbers, a plurality of metal elements are mutually cooperated, and meanwhile, the probability of interaction with high-energy electrons is increased due to the close packing of the elements, so that the high-entropy ceramic nitride coating has an excellent shielding effect on the high-energy electrons.
The invention has more obvious lattice distortion when nitrogen atoms and metal elements form solid solution, larger lattice stacking density and larger probability of action with microscopic particles in the high-entropy nitride ceramics when high-energy electrons are incident into the shielding material with the same area in the original atomic distance calibration, and can effectively play a role in shielding the high-energy electrons.
The nitride has the characteristics of high density, high effective atomic number, stable structural performance and excellent mechanical performance under extreme conditions (pressure, temperature and irradiation), is suitable for the actual task environment of a spacecraft, and can be used in the fields of deep space exploration and the like.
For a further understanding of the nature and the technical aspects of the present invention, reference should be made to the following detailed description of the invention and the accompanying drawings, which are provided for reference and illustration only and are not intended to limit the invention.
Drawings
FIG. 1 shows (AlCrTaTiZr) N prepared in example 1 of the present invention x XRD pattern of the high entropy ceramic nitride coating;
FIG. 2 shows (AlCrTaTiZr) N prepared in example 1 of the present invention x SEM test results of the high entropy ceramic nitride powder;
FIG. 3 shows (AlCrTaTiZr) N prepared in example 1 of the present invention x High entropy ceramic nitride coating has a high electron energy (fluence of 1×10) 16 e/cm, energy 1 MeV) shielding dose simulation test results;
FIG. 4 shows the hardness and modulus test results of the high-entropy ceramic nitrides prepared in examples 1, 2, 3 and 4 according to the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1:
the embodiment provides a high-entropy ceramic nitride (AlCrTaTiZr) N for effectively shielding high-energy electrons x The preparation method of the coating is that the coating is obtained by plating a high-entropy alloy target on a metal substrate through magnetron sputtering under nitrogen atmosphere.
1. The preparation of the preset high-entropy alloy powder is as follows:
metal powder of aluminum (20%), chromium (20%), tantalum (20%), titanium (20%) and zirconium (20%) is used as a ball milling material, the metal powder is added into a ball milling tank according to the equimolar ratio of elements, and the ball material ratio is determined to be 5:1 according to the size of a ball milling device; the ball milling tank is filled into a ball mill, corresponding parameters are set, the ball milling rotating speed is 400rpm, and the ball milling time is 60 hours. And setting the parameters, and separating the ball materials after ball milling is finished. After separation, the powder was dried in a vacuum oven for 5 hours at 60 ℃.
2. Sintering the high-entropy alloy powder into a high-entropy alloy target by using spark plasma sintering:
the temperature rising rate is 50 ℃/min in the temperature range from room temperature to 1000 ℃, the temperature rising rate is 30 ℃/min after 1000 ℃, the sintering temperature is 1300 ℃, and the heat preservation time is 20min. In the cooling process, the cooling rate is 50 ℃/min within the range from the sintering temperature to 1000 ℃, and the cooling is carried out naturally along with the furnace below 1000 ℃. In the sintering process, the pulse current on-off ratio is set to 36ms to 6ms, flowing argon is used as a protective atmosphere to prevent powder oxidation, and the air pressure is 50MPa.
3. Plating a high-entropy alloy target on a metal substrate by magnetron sputtering under nitrogen atmosphere:
the metal substrate is made of aluminum alloy, the polished aluminum alloy substrate is cleaned by acetone and absolute ethyl alcohol in an ultrasonic mode, and the polished aluminum alloy substrate is placed into a sputtering chamber after being dried. Vacuum degree of sputtering chamber is pumped to 2.6X10 before sputtering film 3 Pa, introducing working gas argon (pure)99.99% and a reaction gas nitrogen (purity 99.99%), wherein the flow ratio of nitrogen and argon is 10%, the total gas flow is 20mL/min, the sputtering current is 1A, the sputtering power is 160W, the coating time is 5min, and the coating air pressure is 1.1X10% -1 Pa, the sputtering temperature was 250 ℃.
And performing magnetron sputtering according to the setting, and cooling the magnetron sputtering at room temperature after the magnetron sputtering is completed. The surface of the coating was polished to a mirror surface using a polisher and sand paper.
Example 2:
the embodiment provides a high-entropy ceramic nitride (AlCrCuFeZr) N for effectively shielding high-energy electrons x The preparation method of the coating is that the coating is obtained by plating a high-entropy alloy target on a metal substrate through magnetron sputtering under nitrogen atmosphere.
1. The preparation of the pre-set oxide powder is as follows:
metal powder of aluminum (20%), chromium (20%), copper (20%), iron (20%), zirconium (20%) is used as a ball milling material, the metal powder is added into a ball milling tank according to the equimolar ratio of elements, and the ball material ratio is determined to be 5:1 according to the size of a ball milling device; the ball milling tank is filled into a ball mill, corresponding parameters are set, the ball milling rotating speed is 400rpm, and the ball milling time is 60 hours. And setting the parameters, and separating the ball materials after ball milling is finished. After separation, the powder was dried in a vacuum oven for 5 hours at 60 ℃.
2. Sintering the high-entropy alloy powder into a high-entropy alloy target by using spark plasma sintering:
the temperature rising rate is 40 ℃/min in the temperature range from room temperature to 900 ℃, the temperature rising rate is 25 ℃/min after 1000 ℃, the sintering temperature is 1200 ℃, and the heat preservation time is 20min. In the cooling process, the cooling rate is 40 ℃/min within the range from the sintering temperature to 900 ℃, and the cooling is carried out naturally along with the furnace below 900 ℃. In the sintering process, the pulse current on-off ratio is set to 36ms to 6ms, flowing argon is used as a protective atmosphere to prevent powder oxidation, and the air pressure is 35MPa.
3. Plating a high-entropy alloy target on a metal substrate by magnetron sputtering under nitrogen atmosphere:
metal substrate selectionSelecting aluminum alloy, ultrasonically cleaning the polished aluminum alloy matrix with acetone and absolute ethyl alcohol, drying and then placing into a sputtering chamber. Vacuum degree of sputtering chamber is pumped to 2.6X10 before sputtering film 3 Pa, introducing working gas argon (purity is 99.99%) and reaction gas nitrogen (purity is 99.99%), wherein the flow ratio of nitrogen to argon is 20%, the total gas flow is 20mL/min, the sputtering current is 1A, the sputtering power is 160W, the coating time is 5min, and the coating air pressure is 1.1X10% -1 Pa, the sputtering temperature was 350 ℃.
And performing magnetron sputtering according to the setting, and cooling the magnetron sputtering at room temperature after the magnetron sputtering is completed. The surface of the coating was polished to a mirror surface using a polisher and sand paper.
Example 3:
the embodiment provides a high-entropy ceramic nitride (AlCrTiWZr) N for effectively shielding high-energy electrons x The preparation method of the coating is that the coating is obtained by plating a high-entropy alloy target on a metal substrate through magnetron sputtering under nitrogen atmosphere.
1. The preparation of the pre-set oxide powder is as follows:
metal powder of aluminum (20%), chromium (20%), titanium (20%), tungsten (20%) and zirconium (20%) is used as a ball milling material, the metal powder is added into a ball milling tank according to the equimolar ratio of elements, and the ball material ratio is determined to be 5:1 according to the size of a ball milling device; the ball milling tank is filled into a ball mill, corresponding parameters are set, the ball milling rotating speed is 200rpm, and the ball milling time is 100h. And setting the parameters, and separating the ball materials after ball milling is finished. After separation, the powder was dried in a vacuum oven for 5 hours at 60 ℃.
2. Sintering the high-entropy alloy powder into a high-entropy alloy target by using spark plasma sintering:
the temperature rising rate is 40 ℃/min in the temperature range from room temperature to 1200 ℃, the temperature rising rate is 25 ℃/min after 1000 ℃, the sintering temperature is 1400 ℃, and the heat preservation time is 20min. In the cooling process, the cooling rate is 40 ℃/min within the range of sintering temperature to 1200 ℃, and the cooling is carried out naturally along with the furnace below 900 ℃. In the sintering process, the pulse current on-off ratio is set to 36ms to 6ms, flowing argon is used as a protective atmosphere to prevent powder oxidation, and the air pressure is 50MPa.
3. Plating a high-entropy alloy target on a metal substrate by magnetron sputtering under nitrogen atmosphere:
the metal substrate is made of aluminum alloy, the polished aluminum alloy substrate is cleaned by acetone and absolute ethyl alcohol in an ultrasonic mode, and the polished aluminum alloy substrate is placed into a sputtering chamber after being dried. Vacuum degree of sputtering chamber is pumped to 2.6X10 before sputtering film 3 Pa, introducing working gas argon (purity is 99.99%) and reaction gas nitrogen (purity is 99.99%), wherein the flow ratio of nitrogen to argon is 30%, the total gas flow is 20mL/min, the sputtering current is 1A, the sputtering power is 200W, the coating time is 5min, and the coating air pressure is 1.1X10% -1 Pa, the sputtering temperature was 50 ℃.
And performing magnetron sputtering according to the setting, and cooling the magnetron sputtering at room temperature after the magnetron sputtering is completed. The surface of the coating was polished to a mirror surface using a polisher and sand paper.
Example 4:
the embodiment provides a high-entropy ceramic nitride (AlCrTiCuZr) N for effectively shielding high-energy electrons x The preparation method of the coating is that the coating is obtained by plating a high-entropy alloy target on a metal substrate through magnetron sputtering under nitrogen atmosphere.
Metal powder of aluminum (20%), chromium (20%), titanium (20%), copper (20%), zirconium (20%) is used as a ball milling material, the metal powder is added into a ball milling tank according to the equimolar ratio of elements, and the ball material ratio is determined to be 5:1 according to the size of a ball milling device; the ball milling tank is filled into a ball mill, corresponding parameters are set, the ball milling rotating speed is 500rpm, and the ball milling time is 50 hours. And setting the parameters, and separating the ball materials after ball milling is finished. After separation, the powder was dried in a vacuum oven for 5 hours at 60 ℃.
2. Sintering the high-entropy alloy powder into a high-entropy alloy target by using spark plasma sintering:
the temperature rising rate is 40 ℃/min in the temperature range from room temperature to 900 ℃, the temperature rising rate is 25 ℃/min after 1000 ℃, the sintering temperature is 1200 ℃, and the heat preservation time is 20min. In the cooling process, the cooling rate is 40 ℃/min within the range from the sintering temperature to 900 ℃, and the cooling is carried out naturally along with the furnace below 900 ℃. In the sintering process, the pulse current on-off ratio is set to 36ms to 6ms, flowing argon is used as a protective atmosphere to prevent powder oxidation, and the air pressure is 35MPa.
3. Plating a high-entropy alloy target on a metal substrate by magnetron sputtering under nitrogen atmosphere:
the metal substrate is made of aluminum alloy, the polished aluminum alloy substrate is cleaned by acetone and absolute ethyl alcohol in an ultrasonic mode, and the polished aluminum alloy substrate is placed into a sputtering chamber after being dried. Vacuum degree of sputtering chamber is pumped to 2.6X10 before sputtering film 3 Pa, introducing working gas argon (purity is 99.99%) and reaction gas nitrogen (purity is 99.99%), wherein the flow ratio of nitrogen to argon is 40%, the total gas flow is 20mL/min, the sputtering current is 1A, the sputtering power is 190W, the coating time is 5min, and the coating air pressure is 1.1X10% -1 Pa, the sputtering temperature was 150 ℃.
And performing magnetron sputtering according to the setting, and cooling the magnetron sputtering at room temperature after the magnetron sputtering is completed. The surface of the coating was polished to a mirror surface using a polisher and sand paper.
The following experiments are adopted to verify the effects of the invention:
radiation protection performance test: (AlCrTaTiZr) N prepared in example 1 was used x High entropy ceramic nitride coating has a high electron energy (fluence of 1×10) 16 e/cm, energy 1 MeV) shielding dose shielding, the results are shown in figure 3, and the simulation result shows that compared with the traditional aluminum material with the same thickness, (AlCrTaTiZr) N x The high-entropy ceramic nitride coating has better shielding performance.
Mechanical property test: the modulus and hardness of each high-entropy ceramic nitride prepared in experimental examples 1, 2, 3 and 4 are analyzed by using a nano indentation tester, and the results are shown in fig. 4, and the test results show that each high-entropy ceramic nitride coating has higher elastic modulus and hardness, and the high-entropy ceramic nitride coating has excellent mechanical properties.
Claims (9)
1. The high-entropy ceramic nitride protective coating for shielding high-energy electrons is characterized in that the coating is formed by preparing a high-entropy alloy target material by taking 5 of aluminum, zirconium, tantalum, titanium, chromium, copper, tungsten and iron powder as raw materials, and then sputtering the high-entropy alloy target material on a metal substrate by using a magnetron sputtering technology by taking argon as working gas and nitrogen as reaction gas;
the high-entropy ceramic nitride protective coating material is (AlCrTaTiZr) N x 、(AlCrCuFeZr)N x 、(AlCrTiWZr)N x 、(AlCrTiCuZr)N x ；
The magnetron sputtering step is as follows:
polishing metal matrix, sequentially ultrasonic cleaning with acetone and absolute ethanol, drying, placing into sputtering chamber, and vacuum-pumping the sputtering chamber to 2.6X10% 3 Pa, introducing argon and nitrogen, wherein the total gas flow is 20mL/min, the sputtering current is 1A, the sputtering power is 160W-200W, the coating time is 5min-10min, and the coating air pressure is 1.1X10% -1 Pa, the sputtering temperature is 150-350 ℃, the substrate temperature is 50-450 ℃, and the magnetron sputtering is completed and then the substrate is cooled in a normal temperature environment.
2. The coating of claim 1, wherein the metal substrate is an aluminum alloy, a titanium alloy.
3. The coating of claim 1, wherein the molar content of aluminum is 5% -35%, the molar content of zirconium is 5% -35%, the molar content of tantalum is 5% -35%, the molar content of titanium is 5% -35%, the molar content of chromium is 5% -35%, the molar content of copper is 5% -35%, the molar content of tungsten is 5% -35%, and the molar content of iron is 5% -35%.
4. The coating of claim 1, wherein the purity of argon is 99.99% by volume and the purity of nitrogen is 99.99% by volume.
5. A method of producing a coating according to any one of claims 1 to 4, wherein the method is carried out by:
step 1, weighing raw materials, ball milling, separating and drying the ball materials, and sintering the ball materials by discharge plasma under the protection of argon to obtain a high-entropy alloy target;
and step 2, sputtering a high-entropy alloy target on the metal substrate by utilizing magnetron sputtering, wherein nitrogen accounts for 10-40% of the total volume of the nitrogen and the argon.
6. The process according to claim 5, wherein in step 1, the ball-to-material ratio is (1-5) 1, the ball milling speed is 100rpm-500rpm, and the time is 50h-100h.
7. The process according to claim 5, wherein in step 1, the drying is carried out at 60℃to 80℃for at least 5 hours.
8. The method according to claim 5, wherein in step 1, the sintering process: the pressure is controlled between 35MPa and 70MPa, the pulse current breaking ratio is 36ms to 6ms, the temperature is firstly increased to 800 ℃ to 1000 ℃ at the speed of 40 ℃/min to 50 ℃/min, the temperature is increased to 1200 ℃ to 1800 ℃ at the speed of 25 ℃/min to 30 ℃/min, the temperature is kept for at least 20min, the temperature is reduced to 900 ℃ to 1200 ℃ at the speed of 40 ℃/min to 50 ℃/min, and the temperature is naturally cooled along with the furnace.
9. The method according to claim 5, wherein in step 2, the magnetron sputtering step is as follows:
polishing metal matrix, sequentially ultrasonic cleaning with acetone and absolute ethanol, drying, placing into sputtering chamber, and vacuum-pumping the sputtering chamber to 2.6X10% 3 Pa, introducing argon and nitrogen, wherein the total gas flow is 20mL/min, the sputtering current is 1A, the sputtering power is 160W-200W, the coating time is 5min-10min, and the coating air pressure is 1.1X10% -1 Pa, the sputtering temperature is 150-350 ℃, the substrate temperature is 50-450 ℃, and the magnetron sputtering is completed and then the substrate is cooled in a normal temperature environment.
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