CN114686741A - Refractory high-entropy alloy with coating and preparation method thereof - Google Patents
Refractory high-entropy alloy with coating and preparation method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—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
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- 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
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- 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
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- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
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Abstract
The invention discloses a refractory high-entropy alloy with a coating and a preparation method thereof, wherein the refractory high-entropy alloy comprises an alloy matrix and the coating arranged on the surface of the alloy matrix; the alloy matrix comprises the following components: according to the atomic ratio of 1: 1: 1: 1: 0.5-0.7 of Nb, Mo, Ti, V and Si, wherein the coating is a Cr coating or a Cr-Si coating. The design of the inventionThe prepared high-entropy alloy with the coating has excellent high-temperature oxidation resistance, is oxidized at 1100 ℃ for 24 hours, and has the oxidation weight gain of 140mg/cm2Far lower than the oxidation weight gain (168 mg/cm) of the alloy without Cr protection2)。
Description
Technical Field
The invention relates to the field of high-temperature oxidation resistant materials, in particular to a refractory high-entropy alloy with a coating and a preparation method thereof.
Background
At present, the performance requirements of the fields of aerospace, nuclear power, energy conversion and the like on high-temperature structural materials are continuously improved, the service temperature of the single crystal nickel-based high-temperature alloy reaches 1150 ℃, the melting point of the single crystal nickel-based high-temperature alloy is approached, the performance development reaches the limit of the materials, and the novel high-temperature alloy is urgently needed to be designed.
The traditional metal materials usually take one or two metal elements as main elements, and a small amount of alloying elements are introduced to improve the comprehensive mechanical properties of the metal materials. In 2004, the multi-principal element high-entropy alloy concept is provided, the traditional material design idea is overturned, and the component design space of the alloy is greatly expanded. The high-entropy alloy has the potential of stable service at high temperature due to the high entropy effect, the lattice distortion effect, the slow diffusion effect and the cocktail effect.
The refractory high-entropy alloy designed by taking refractory elements such as Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and the like as main components has high-temperature strength far exceeding that of the traditional high-temperature alloy. Wherein the compression strength of the NbMoTiVSi refractory high-entropy alloy can still reach 900MPa at the temperature of 1100 ℃. Although the NbMoTiVSi refractory high-entropy alloy has excellent high-temperature mechanical properties, the high-temperature oxidation property is poor, and the engineering application of the NbMoTiVSi refractory high-entropy alloy is influenced. Alloying is one of the methods for improving the high-temperature oxidation performance of the alloy, but alloying can reduce the mechanical property of the alloy, and the preparation of the coating on the surface of the alloy is an effective method which can ensure the excellent mechanical property and improve the high-temperature oxidation resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the refractory high-entropy alloy with the coating and the preparation method thereof.
The invention is realized by the following technical scheme.
The refractory high-entropy alloy with the coating is characterized by comprising an alloy substrate and the coating arranged on the surface of the alloy substrate; the alloy matrix comprises the following components: according to the atomic ratio of 1: 1: 1: 1: 0.5-0.7 of Nb, Mo, Ti, V and Si, wherein the coating is a Cr coating or a Cr-Si coating.
Further, the thickness of the Cr coating is 0.5-5 μm.
The preparation method of the alloy is characterized by comprising the following steps:
(1) preparing raw materials required by the alloy matrix according to the atomic ratio;
(2) placing the raw materials in a copper crucible of a vacuum arc furnace, vacuumizing and filling high-purity argon;
(3) alloy smelting is carried out, and alloy cast ingots are obtained through cooling;
(4) turning over the alloy ingot, and repeating the step (3) to obtain an alloy matrix;
(5) cutting an alloy matrix into a substrate with a required size and placing the substrate in a magnetron sputtering clamp;
(6) preparing a high-purity Cr metal ingot by arc melting, cutting the high-purity Cr metal ingot into a target material, placing the target material in a magnetron sputtering direct current target, and then performing magnetron sputtering operation to obtain the refractory high-entropy alloy with the Cr coating.
Further, the method further comprises: and placing the prepared refractory high-entropy alloy with the Cr coating in a vacuum heat treatment furnace for heat treatment to obtain the refractory high-entropy alloy with the Cr-Si coating.
Further, in the step (1), the raw materials comprise Nb, Mo, Ti, V and Si with the purity of more than 99.5%; before weighing, the oxide skin on the surface of the raw material is polished by sand paper, and the raw material is placed into industrial grade ethanol for ultrasonic cleaning for 20-25 min.
Further, in the step (2), vacuum is applied to a degree of vacuum of 3X 10-3～5×10-3After Pa, high-purity argon is filled to keep the pressure in the furnace at 5X 10-3～1×10-2MPa。
Further, an alloy smelting process is carried out in the step (3): the arc starting current is 200A, the smelting current is 300A-450A, and after the raw materials in the copper crucible are completely melted into a liquid state, arc smelting is kept for 2-5 min.
Further, in the step (4), the step (3) is repeated six to eight times.
Further, in the step (5), the substrate is placed in front of a magnetron sputtering fixture, the surface of the substrate is polished to a mirror surface after being polished by sand paper, and the substrate is placed in industrial-grade ethanol for ultrasonic cleaning for 20-25 min to remove surface stains.
Further, in the step (5), the alloy matrix is cut into a substrate with the size of 50 × 50 × 5mm, and in the step (6), the size of the target material is Φ 101 × 5 mm.
Further, in the step (6), parameters of the magnetron sputtering technology are as follows: the temperature of the substrate is 300-400 ℃, the power is 150-250 watts, and the sputtering time is 150-200 min; and after the sputtering is finished, cooling for 5 hours and then taking out.
Further, the vacuum heat treatment furnace is used for carrying out a heat treatment process: the heat treatment temperature is 700-900 ℃, the time is 2-5h, and the furnace cooling is carried out.
The invention has the beneficial technical effects that:
1. the refractory high-entropy alloy with the Cr coating is designed and prepared by the invention, and can generate Cr at high temperature2O3And the oxide film prevents oxygen atoms from diffusing into the matrix at high temperature, and can improve the high-temperature oxidation resistance of the high-entropy refractory NbMoTiVSi0.5-0.7 alloy.
2. According to the invention, the Cr coating and the matrix are mutually diffused through a vacuum heat treatment process to form metallurgical bonding, so that the refractory high-entropy alloy with the Cr-Si coating is obtained, and the bonding force between the coating and the matrix is improved. Can prevent the coating from falling off and losing the protective effect on the matrix in a high-temperature oxidation environment.
3. The refractory high-entropy alloy with the coating designed by the invention can generate Cr in a high-temperature environment2O3And SiO2The mixed oxide film of (1). Due to Cr2O3And SiO2The alloy is an antioxidant film, and the high-temperature oxidation resistance of the alloy can be greatly improved by the design.
4. The high-entropy alloy with the Cr-Si coating designed and prepared by the invention has excellent high-temperature oxidation resistance, is oxidized for 24 hours at 1100 ℃, and has the oxidation weight gain of 140mg/cm2Far below the oxidation weight gain (168 mg/cm) of the alloy without Cr protection2)。
Drawings
FIG. 1 is the surface topography of the coating of example 1;
FIG. 2 is a cross-sectional profile of the refractory high entropy alloy with the coating of example 1;
FIG. 3 is the surface topography of the coating of example 2;
FIG. 4 is a cross-sectional profile of the refractory high entropy alloy of example 2 with a coating;
FIG. 5 is the surface topography of the coating of example 3;
FIG. 6 is a cross-sectional profile of the refractory high entropy alloy of example 3 with a coating;
FIG. 7 is the cross-sectional morphology of the refractory high entropy alloy with Cr-Si coating of example 4;
FIG. 8 is a schematic representation of the Cr-unplated samples of example 4 after oxidation;
FIG. 9 is a schematic view of the Cr-plated non-heat treated sample of example 4 after oxidation;
FIG. 10 is a schematic representation of the Cr-plated samples of example 4 after oxidation with a Cr-Si coating formed by heat treatment;
FIG. 11 shows the 1100 ℃ oxidation time of the sample of example 4 for 24h weight gain.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
A coated NbMoTiVSix (x is 0.5) refractory high-entropy alloy, wherein the matrix component of the refractory high-entropy alloy comprises Nb, Mo, Ti, V and Si, and the atomic ratio of Nb to Mo to Ti to V to Si is 1: 1: 1: 1: 0.5, the surface of the alloy substrate is provided with a Cr coating with the thickness of about 5 mu m.
The invention relates to a refractory high-entropy alloy with a coating, which is prepared by the following specific steps:
(1) selecting Nb, Mo, Ti, V and Si with the purity higher than 99.5% as metallurgical raw materials, polishing oxide skins on the surfaces of the metallurgical raw materials by using sand paper, putting the metallurgical raw materials into industrial grade ethanol for ultrasonic cleaning for 20min, drying, and then, preparing a mixture of Nb, Mo, Ti, V and Si according to the atomic ratio of 1: 1: 1: 1: 0.5 weight Nb, Mo, Ti, V, Si;
(2) smelting alloy in a vacuum non-consumable arc furnace, placing weighed Nb, Mo, Ti, V and Si in a copper crucible, vacuumizing the air pressure in the furnace cavity until the vacuum degree reaches 5 multiplied by 10-3After Pa, high-purity argon is filled to keep the pressure in the furnace at 5X 10-3And (3) MPa, the arcing current is 200A, the smelting current is 300A, after the metal is completely molten into a liquid state, the arc smelting is kept for 3min, and then the current is closed. After the alloy is solidified, turning over the alloy ingot, and repeating the process for 6 times to obtain the NbMoTiVSi0.5 refractory high-entropy alloy;
(3) cutting the refractory high-entropy alloy into substrates with the sizes of 50 multiplied by 5mm, polishing the substrates to a mirror surface after sanding, placing the substrates in industrial grade ethanol for ultrasonic cleaning for 20min, removing surface stains, and placing the substrates in a magnetron sputtering clamp;
(4) preparing a high-purity Cr metal ingot by adopting electric arc melting, cutting the high-purity Cr metal ingot into a target material with the diameter of phi 101 multiplied by 5mm, placing the target material into a magnetron sputtering direct current target, then carrying out magnetron sputtering operation, wherein the magnetron sputtering power is 150W, the time is 3h, the temperature of a substrate is 300 ℃, cooling for 5h and then taking out after sputtering is finished. FIG. 1 shows the surface topography of the film, and FIG. 2 shows the cross-sectional topography of the film.
Example 2
A coated NbMoTiVSix (x is 0.7) refractory high-entropy alloy, wherein the matrix component of the refractory high-entropy alloy comprises Nb, Mo, Ti, V and Si, and the atomic ratio of Nb to Mo to Ti to V to Si is 1: 1: 1: 1: 0.7, the surface of the alloy substrate is provided with a Cr coating with the thickness of about 1.5 mu m.
The invention relates to a refractory high-entropy alloy with a coating, which is prepared by the following specific steps:
(1) selecting Nb, Mo, Ti, V and Si with the purity higher than 99.5% as metallurgical raw materials, polishing oxide skins on the surfaces of the metallurgical raw materials by using sand paper, putting the metallurgical raw materials into industrial grade ethanol for ultrasonic cleaning for 25min, drying, and then, preparing a mixture of Nb, Mo, Ti, V and Si according to the atomic ratio of 1: 1: 1: 1: 0.7 weight Nb, Mo, Ti, V, Si;
(2) smelting alloy in a vacuum non-consumable arc furnace, placing weighed Nb, Mo, Ti, V and Si in a copper crucible, vacuumizing the air pressure in the furnace cavity until the vacuum degree reaches 5 multiplied by 10-3After Pa, high-purity argon is filled to keep the pressure in the furnace at 5X 10-3And (3) MPa, the arcing current is 200A, the smelting current is 450A, after the metal is completely melted into a liquid state, the arc smelting is kept for 3min, and then the current is closed. To be alloyedAfter solidification, the alloy ingot is turned over, and the process is repeated for 8 times to obtain the NbMoTiVSi0.7 refractory high-entropy alloy;
(3) cutting the refractory high-entropy alloy into substrates with the size of 50 multiplied by 5mm, polishing the substrates to a mirror surface after sanding, placing the substrates in industrial grade ethanol for ultrasonic cleaning for 25min, removing surface stains, and placing the substrates in a magnetron sputtering clamp;
(4) preparing a high-purity Cr metal ingot by adopting electric arc melting, cutting the high-purity Cr metal ingot into a phi 101 multiplied by 5mm target material, placing the target material in a magnetron sputtering direct current target, and then performing magnetron sputtering operation, wherein the magnetron sputtering power is 150W, the magnetron sputtering time is 150min, and the substrate temperature is 350 ℃. FIG. 3 shows the surface topography of the film, and FIG. 4 shows the cross-sectional topography of the film.
Example 3
A coated NbMoTiVSix (x is 0.7) refractory high-entropy alloy, wherein the matrix component of the refractory high-entropy alloy comprises Nb, Mo, Ti, V and Si, and the atomic ratio of Nb to Mo to Ti to V to Si is 1: 1: 1: 1: 0.7, the surface of the alloy substrate is provided with a Cr coating with the thickness of about 0.8 mu m.
The invention relates to a refractory high-entropy alloy with a coating, which is prepared by the following specific steps:
(1) selecting Nb, Mo, Ti, V and Si with the purity higher than 99.5% as metallurgical raw materials, polishing oxide skins on the surfaces of the metallurgical raw materials by using sand paper, putting the metallurgical raw materials into industrial grade ethanol for ultrasonic cleaning for 20min, drying, and then, preparing a mixture of Nb, Mo, Ti, V and Si according to the atomic ratio of 1: 1: 1: 1: 0.7 weight Nb, Mo, Ti, V, Si;
(2) smelting alloy in a vacuum non-consumable arc furnace, placing weighed Nb, Mo, Ti, V and Si in a copper crucible, vacuumizing the air pressure in the furnace cavity until the vacuum degree reaches 3 multiplied by 10-3After Pa, high-purity argon is filled to maintain the pressure in the furnace at 9X 10-3And (3) MPa, the arcing current is 200A, the smelting current is 400A, after the metal is completely molten into a liquid state, the arc smelting is kept for 5min, and then the current is closed. After the alloy is solidified, turning over the alloy ingot, repeating the process for 7 times to obtain the NbMoTiVSi0.7 refractory high-entropy alloy;
(3) cutting the refractory high-entropy alloy into substrates with the size of 50 multiplied by 5mm, polishing the substrates to a mirror surface after sanding, placing the substrates in industrial grade ethanol for ultrasonic cleaning for 25min, removing surface stains, and placing the substrates in a magnetron sputtering clamp;
(4) preparing a high-purity Cr metal ingot by adopting electric arc melting, cutting the high-purity Cr metal ingot into a phi 101 multiplied by 5mm target material, placing the target material in a magnetron sputtering direct current target, and then performing magnetron sputtering operation, wherein the magnetron sputtering power is 250W, the magnetron sputtering time is 180min, and the substrate temperature is 400 ℃. FIG. 5 is a film surface topography and FIG. 6 is a film cross-sectional topography.
Example 4
The invention discloses a coated NbMoTiVSix (x is 0.7) refractory high-entropy alloy, which comprises Nb, Mo, Ti, V and Si as matrix components, wherein the atomic ratio of Nb to Mo to Ti to V to Si is 1: 1: 1: 1: 0.7, the surface of the alloy substrate is provided with a Cr-Si coating with the thickness of about 2 mu m.
The preparation method comprises the following steps:
(1) selecting Nb, Mo, Ti, V and Si with the purity higher than 99.5% as metallurgical raw materials, polishing oxide skins on the surfaces of the metallurgical raw materials by using sand paper, putting the metallurgical raw materials into industrial grade ethanol for ultrasonic cleaning for 23min, drying, and then, preparing a mixture of Nb, Mo, Ti, V and Si according to the atomic ratio of 1: 1: 1: 1: 0.7 weight Nb, Mo, Ti, V, Si;
(2) smelting alloy in a vacuum non-consumable arc furnace, placing weighed Nb, Mo, Ti, V and Si in a copper crucible, vacuumizing the pressure in the furnace cavity until the vacuum degree reaches 4 × 10-3After Pa, high-purity argon is filled to maintain the pressure in the furnace at 7X 10-3And (3) MPa, the arcing current is 200A, the smelting current is 450A, after the metal is completely molten into a liquid state, the arc smelting is kept for 5min, and then the current is closed. After the alloy is solidified, turning over the alloy ingot, and repeating the process for 6 times to obtain the NbMoTiVSi0.7 refractory high-entropy alloy;
(3) cutting the refractory high-entropy alloy into substrates with the size of 50 multiplied by 5mm, polishing the substrates to a mirror surface after sanding, placing the substrates in industrial grade ethanol for ultrasonic cleaning for 25min, removing surface stains, and placing the substrates in a magnetron sputtering clamp;
(4) preparing a high-purity Cr metal ingot by adopting electric arc melting, cutting the high-purity Cr metal ingot into a phi 101 multiplied by 5mm target material, placing the target material in a magnetron sputtering direct current target, and then performing magnetron sputtering operation, wherein the magnetron sputtering power is 230W, the magnetron sputtering time is 170min, and the substrate temperature is 380 ℃;
(5) performing tube sealing treatment on the film to ensure that the film is not oxidized when being subjected to heat treatment;
(6) and (3) placing the sealed sample in a vacuum heat treatment furnace for high-temperature heat treatment at 800 ℃ for 4 hours, wherein the purpose of the heat treatment is to ensure that Cr and Si elements are mutually diffused to form a Cr-Si coating, so that the high-temperature oxidation resistance of the film is improved.
And (3) placing the sample in an oxidation furnace for a high-temperature oxidation test, wherein the oxidation temperature is 1100 ℃ and the time is 24 hours. For comparison, the test subjects the samples plated with Cr to oxidation treatment under the same conditions. FIG. 8 is a schematic diagram after oxidation of a Cr-unplated sample, FIG. 9 is a schematic diagram after oxidation of a Cr-plated non-heat treated sample, and FIG. 10 is a schematic diagram after oxidation of a Cr-plated heat treated sample. As can be seen from the schematic diagram, the sample without plating Cr is oxidized seriously, the oxide layer is thickest, and the oxidation product of the oxide layer is Nb2O5+TiO2+V2O5+SiO2(ii) a The oxidation degree of the sample is reduced after the Cr plating, the thickness of the oxide film is thinned, and the oxide outside the oxide layer is Cr2O3The internal oxidation product is Nb2O5+TiO2+V2O5+SiO2(ii) a The high-temperature oxidation resistance of the sample after heat treatment is obviously improved, the oxide layer is thinnest, and the oxide outside the oxide layer is Cr2O3+SiO2The internal oxidation product being Nb2O5+TiO2+V2O5. The samples which were not heat-treated formed protective Cr even in a high-temperature environment2O3But the oxide film has poor bonding force and is peeled off, and the oxidation performance is lower than that of a sample subjected to heat treatment.
The oxidation samples were taken at regular intervals and the oxidation weight gain was measured and the results are shown in FIG. 11. High temperature oxidation weight gain (160.7 mg/cm) of Cr-plated samples2) Is far lower than that of an uncoated Cr sample (168 mg/cm)2) The Cr element is proved to have good high-temperature protection effect; the sample with the Cr-Si coating after heat treatment has the oxidation weight gain of 140mg/cm2Proved that the Cr-Si coating formed after heat treatment can be obviously improvedThe alloy has high temperature oxidation resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (12)
1. The refractory high-entropy alloy with the coating is characterized by comprising an alloy substrate and the coating arranged on the surface of the alloy substrate; the alloy matrix comprises the following components: according to the atomic ratio of 1: 1: 1: 1: 0.5-0.7 of Nb, Mo, Ti, V and Si, wherein the coating is a Cr coating or a Cr-Si coating.
2. A refractory high entropy alloy with a coating according to claim 1, wherein the Cr coating thickness is 0.5-5 μm.
3. A method of producing a refractory high entropy alloy with a coating according to claim 1, characterized in that the method steps comprise:
(1) preparing raw materials required by the alloy matrix according to the atomic ratio;
(2) placing the raw materials in a copper crucible of a vacuum arc furnace, vacuumizing and filling high-purity argon;
(3) alloy smelting is carried out, and alloy cast ingots are obtained through cooling;
(4) turning over the alloy ingot, and repeating the step (3) to obtain an alloy matrix;
(5) cutting an alloy matrix into a substrate with a required size and placing the substrate in a magnetron sputtering clamp;
(6) preparing a high-purity Cr metal ingot by arc melting, cutting the high-purity Cr metal ingot into a target material, placing the target material in a magnetron sputtering direct current target, and then performing magnetron sputtering operation to obtain the refractory high-entropy alloy with the Cr coating.
4. The method of manufacturing according to claim 3, further comprising: and placing the prepared refractory high-entropy alloy with the Cr coating in a vacuum heat treatment furnace for heat treatment to obtain the refractory high-entropy alloy with the Cr-Si coating.
5. The method according to claim 3 or 4, wherein in the step (1), the raw material comprises Nb, Mo, Ti, V, Si; before weighing, the oxide skin on the surface of the raw material is polished by sand paper, and the raw material is placed into industrial grade ethanol for ultrasonic cleaning for 20-25 min.
6. The production method according to claim 3 or 4, wherein in the step (2), the vacuum is applied to a degree of vacuum of 3X 10-3～5×10-3After Pa, high-purity argon is filled to keep the pressure in the furnace at 5X 10-3～1×10-2MPa。
7. The production method according to claim 3 or 4, wherein an alloy melting process is performed in the step (3): the arc starting current is 200A, the smelting current is 300A-450A, and after the raw materials in the copper crucible are completely melted into a liquid state, arc smelting is kept for 2-5 min.
8. The production method according to claim 3 or 4, wherein in the step (4), the step (3) is repeated six to eight times.
9. The preparation method according to claim 3 or 4, wherein in the step (5), the substrate is placed in a magnetron sputtering fixture, the surface of the substrate is polished to a mirror surface after being sanded, and the substrate is placed in industrial grade ethanol for ultrasonic cleaning for 20-25 min to remove surface stains.
10. The production method according to claim 3 or 4, wherein in the step (5), the alloy matrix is cut into a substrate having a size of 50 x 5mm, and in the step (6), the target has a size of Φ 101 x 5 mm.
11. The preparation method according to claim 3 or 4, wherein in the step (6), parameters of the magnetron sputtering technology are as follows: the temperature of the substrate is 300-400 ℃, the power is 150-250 watts, and the sputtering time is 150-200 min; and after the sputtering is finished, cooling for 5 hours and then taking out.
12. The manufacturing method according to claim 4, wherein the heat treatment process is performed in the vacuum heat treatment furnace by: the heat treatment temperature is 700-900 ℃, the time is 2-5h, and the furnace cooling is carried out.
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