CN115044870B - Amorphous refractory high-entropy alloy coating and preparation method thereof - Google Patents
Amorphous refractory high-entropy alloy coating and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 106
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 103
- 238000000576 coating method Methods 0.000 title claims abstract description 95
- 239000011248 coating agent Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 36
- 239000010959 steel Substances 0.000 claims abstract description 36
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 21
- 238000004544 sputter deposition Methods 0.000 claims abstract description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 238000001771 vacuum deposition Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000007373 indentation Methods 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
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- 230000006399 behavior Effects 0.000 description 1
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- 235000013339 cereals Nutrition 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major 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
- 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
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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Abstract
The invention discloses an amorphous refractory high-entropy alloy coating and a preparation method thereof, wherein the element composition is TaWMoCrZr, the atomic percentage of Zr is 23.2-41.3 at%, and the rest is Ta, W, mo, cr with near-equal atomic ratio. And preparing TaWMoCrZr refractory high-entropy alloy coating on the polished steel substrate and the monocrystalline silicon substrate by adopting a magnetron sputtering co-sputtering method, wherein the TaWMoCr alloy target adopts 2 direct current power supplies, the Zr target adopts 1 radio frequency power supply, and the Zr content is regulated by regulating and controlling the power of the radio frequency target. The TaWMoCrZr refractory high-entropy alloy coating prepared is of a completely amorphous structure, has the advantages of uniform components, compact structure, smooth surface, excellent mechanical property and good tissue stability, and expands the application range of the amorphous coating.
Description
Technical Field
The invention belongs to the field of high-entropy alloy coating materials, and particularly relates to an amorphous refractory high-entropy alloy coating and a preparation method thereof.
Background
The high-entropy alloy has wide application prospect due to the unique tissue structure and excellent comprehensive performance, and becomes a research hot spot in recent years. The high-entropy alloy coating which is derived on the basis of the high-entropy alloy has performances which are superior to those of the traditional alloy coating, such as mechanical properties, corrosion resistance, wear resistance, oxidation resistance, irradiation resistance and the like.
In addition to the "high entropy effect" during the preparation of the high entropy alloy coating, the extremely fast cooling rate also makes the coating prone to form a single FCC, BCC, HCP solid solution structure, even an amorphous phase, and the resulting structure is more uniform than a bulk high entropy alloy.
The amorphous alloy has higher yield strength, hardness and elastic limit and lower elastic modulus due to the long-range disordered and short-range ordered atomic stacking structure, and has more uniform structure, less corrosion caused by non-uniformity and better corrosion resistance due to the fact that the amorphous alloy has no defects of crystal grain boundaries, dislocation, lattice distortion and the like of a crystal material. However, amorphous alloy is in a metastable state in thermodynamics, crystallization occurs when heated, and the crystallization causes the original structure and performance of the amorphous alloy to disappear, thereby influencing the engineering application of the amorphous alloy. Therefore, the amorphous refractory high-entropy alloy coating with high performance, high thermal stability and comprehensive characteristics of the high-entropy alloy and the traditional amorphous alloy and the preparation method thereof are developed, and the amorphous refractory high-entropy alloy coating has important application value.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide an amorphous refractory high-entropy alloy coating and a preparation method thereof, and the prepared amorphous refractory high-entropy alloy coating has uniform microstructure, good corrosion and oxidation resistance, and excellent high-temperature tissue stability and mechanical property.
The invention is realized by the following technical scheme:
An amorphous refractory high-entropy alloy coating has a chemical composition of TaWMoCrZr and a tissue structure of completely disordered amorphous state.
Preferably, the TaWMoCrZr amorphous refractory high-entropy alloy coating has a Ta, W, mo, cr atomic percent ratio of four elements of 1:1:1:1, and a Zr element atomic percent of 23.2-41.3 at.%.
Preferably, the coating thickness is 3.5-5 μm.
Preferably, the nano indentation hardness of the TaWMoCrZr amorphous high-entropy alloy coating is 10-11 GPa, and the Young modulus is 118-136 GPa.
A preparation method of an amorphous refractory high-entropy alloy coating comprises the following steps:
step 1, preparing TaWMoCrZr amorphous refractory high-entropy alloy coating on a substrate by adopting a magnetron sputtering co-sputtering method, wherein the sputtering method is as follows:
co-sputtering a TaWMoCr alloy target and a Zr target, wherein the direct current power of the TaWMoCr alloy target is 100W, and the radio frequency power of the Zr target is 100-200W;
And step 2, cooling the substrate to room temperature to obtain TaWMoCrZr amorphous refractory high-entropy alloy coating.
The TaWMoCr atomic percent of the amorphous refractory high-entropy alloy coating is Ta:W:Mo:Cr=29:29:23:19 at.%.
The amorphous refractory high-entropy alloy coating step1 uses two TaWMoCr alloy targets to co-sputter with one Zr target.
When TaWMoCrZr amorphous refractory high-entropy alloy coating is prepared in the step 1, the deposition air pressure is 0.3Pa, the rotating speed of a base plate is 15r/min, and the deposition time is 18800 seconds.
The amorphous refractory high-entropy alloy coating is subjected to cleaning and vacuum etching on the substrate before the step 1.
The substrate is a steel substrate or a monocrystalline silicon substrate.
Compared with the prior art, the invention has the following beneficial technical effects:
The TaWMoCrZr alloy coating is an amorphous phase high-entropy alloy material, the element composition is TaWMoCrZr, the atomic percentage of Zr is 23.2-41.3 at%, and the rest is Ta, W, mo, cr with nearly equal atomic ratio. The elements are uniformly distributed in the coating, the structure is compact, the mechanical property and the anti-corrosion and oxidation performance are excellent, and certain structure stability can be maintained at high temperature.
According to the preparation method of the amorphous refractory high-entropy alloy coating, the TaWMoCrZr refractory high-entropy alloy coating is prepared on a polishing substrate by adopting a magnetron sputtering co-sputtering method, wherein a TaWMoCr alloy target adopts 2 direct current power supplies, a Zr target adopts 1 radio frequency power supply, the Zr content is regulated by regulating the power of the radio frequency target, the deposition rate is high, and the deposited coating is uniform and compact, few in defects, high in purity and strong in adhesive force. The TaWMoCrZr refractory high-entropy alloy coating prepared is of a completely amorphous structure, has the advantages of uniform components, compact structure, smooth surface, excellent mechanical property and good tissue stability, and expands the application range of the amorphous coating.
Because of reasonable selection of the alloy elements and reasonable optimization of the preparation method, the alloy material can realize the preparation of the high-entropy amorphous alloy material without low temperature unlike the prior art that the metal melt is required to be quenched to low temperature when the amorphous alloy is prepared.
Drawings
FIG. 1 is a XRD pattern for an amorphous refractory high entropy alloy coating of the invention TaWMoCrZr.
FIG. 2 is an AFM surface topography of the (TaWMoCr) Zr 23.2 amorphous refractory high-entropy alloy coating prepared in example 1 of the present invention.
FIG. 3 is a SEM plan and cross-sectional photograph of a (TaWMoCr) Zr 23.2 amorphous refractory high-entropy alloy coating prepared according to example 1 of the present invention.
Wherein, figure a is a SEM plan view of (TaWMoCr) Zr 23.2 amorphous refractory high-entropy alloy coating;
FIG. b is a photograph of a cross-section of (TaWMoCr) Zr 23.2 amorphous refractory high-entropy alloy coating;
FIG. 4 is a TEM selected area electron diffraction and high resolution photograph of (TaWMoCr) Zr 41.3 amorphous refractory high-entropy alloy coating prepared in example 2 of the present invention.
Wherein, figure a is (TaWMoCr) electron diffraction photograph of TEM selected area of Zr 41.3 amorphous refractory high-entropy alloy coating;
FIG. b is a high resolution photograph of (TaWMoCr) Zr 41.3 amorphous refractory high entropy alloy coating;
FIG. 5 is a facial scan of the EDS element of the (TaWMoCr) Zr 41.3 amorphous refractory high-entropy alloy coating prepared in example 2 of the present invention.
Detailed Description
The invention will now be described in further detail with reference to the accompanying drawings, which illustrate but do not limit the invention.
The TaWMoCrZr amorphous refractory high-entropy alloy coating is prepared by a magnetron sputtering co-sputtering method, the structure of the coating is a completely disordered amorphous state, the atomic percentage of the chemical components is Ta, W, mo, cr, the atomic percentage ratio of four elements is approximately 1:1:1:1, and the atomic percentage of Zr element is 23.2-41.3 at%.
The thickness of the coating is 3.5-5 mu m, the nano indentation hardness of the TaWMoCrZr amorphous high-entropy alloy coating is 10-11 GPa, and the Young modulus is 118-136 GPa.
The invention also provides a preparation method of TaWMoCrZr amorphous refractory high-entropy alloy coating, comprising the following steps:
step 1: and cleaning the substrate to improve the binding force between the coating and the substrate.
The matrix is a steel matrix or a monocrystalline silicon matrix.
The cleaning method of the steel matrix comprises the following steps:
The steel matrix is polished after being sequentially polished by No. 600, no. 1000, no. 1500 and No. 2000 sand paper, and the polished steel matrix is ultrasonically cleaned in acetone and absolute ethyl alcohol for 10 minutes and dried.
The polishing and cleaning method of the monocrystalline silicon substrate comprises the following steps:
And (3) ultrasonically cleaning the single-sided polished monocrystalline silicon substrate in acetone and absolute ethyl alcohol for 10 minutes and drying, so that the surface of the substrate is clean, no foreign particles such as dirt and dust are attached, and the polished substrate is ultrasonically cleaned, thereby being beneficial to improving the bonding force of the coating and the substrate.
Step 2: and (3) carrying out vacuum etching on the substrate cleaned in the step (1).
Specifically, fixing the ultrasonically cleaned substrate on a substrate, conveying the substrate into a magnetron sputtering coating chamber by an automatic machine, and vacuumizing until the back vacuum degree is below 4.0 multiplied by 10 -4 Pa; the power of 200W and the air flow of 60sccm are adopted for etching for 5 minutes, which is beneficial to improving the binding force between the coating and the matrix.
Step 3: and a TaWMoCrZr refractory high-entropy alloy coating is prepared on the substrate by adopting a magnetron sputtering co-sputtering method, wherein the atomic percentages of Zr are 23.2-41.3 percent respectively.
Wherein, two TaWMoCr alloy targets with the purity of 99.9wt.% (Ta: W: mo: cr=29:29:23:19 at.%) are adopted, a TaWMoCr alloy target adopts a direct current power supply, the power is 100W, the Zr target with the purity of 99.9wt.% adopts 1 radio frequency power supply, the power is 100-200W, the deposition air pressure is set to 0.3Pa, the rotating speed of a base plate is 15r/min, the vacuum degree is below 4.0x10 -4 Pa, 2 direct current power supplies and 1 radio frequency power supply are simultaneously started to start co-sputtering deposition, the deposition time is 18800s, and the thickness of the obtained TaWMoCrZr refractory high-entropy alloy coating is 3.5-5 mu m.
Step 6: after the deposition, the substrate is fully cooled to room temperature in the high vacuum coating chamber and then taken out, so that the debonding and cracking caused by the difference of the thermal expansion coefficients of the substrate and the coating material are prevented, and the oxidation of the substrate and air caused by high temperature can be prevented. And finally, taWMoCrZr amorphous refractory high-entropy alloy coatings with different Zr contents are deposited.
Example 1
A preparation method of TaWMoCrZr amorphous refractory high-entropy alloy coating comprises the following steps:
Step 1: the steel substrate is polished by using No. 600, no. 1000, no. 1500 and No. 2000 sand paper in sequence until the steel substrate is completely covered with the scratches of the previous pass, and then polished until the steel substrate is bright and has no obvious scratches.
Step 2: the polished steel substrate and the monocrystalline silicon substrate were ultrasonically cleaned in acetone and absolute ethanol, respectively, for 10min, and dried with a blower.
Step 3: and respectively fixing the steel substrate and the monocrystalline silicon substrate on a base plate, then mechanically and automatically conveying the steel substrate and the monocrystalline silicon substrate into a vacuum coating chamber, and vacuumizing until the back vacuum degree is lower than 4.0 multiplied by 10 -4 Pa.
Step 4: after vacuumizing, etching the steel substrate and the monocrystalline silicon substrate, wherein the power is 200W, the air flow is 60sccm, and etching is performed for 5 minutes.
Step 5: and respectively preparing TaWMoCrZr refractory high-entropy alloy coating on the etched steel substrate and the etched monocrystalline silicon substrate by adopting a magnetron sputtering co-sputtering method.
Wherein, taWMoCr alloy target purity 99.9wt.% (Ta: W: mo: cr=29:29:23:19 at.%) adopts 2 direct current power supplies, power is 100W, zr target purity 99.9wt.% adopts 1 radio frequency power supply, radio frequency power supply power is 100W, working air pressure set value is 0.3Pa, base plate rotating speed is 15r/min, total deposition time is 18800s.
Step 6: and after the deposition is finished, naturally cooling the steel substrate and the monocrystalline silicon substrate in a high vacuum deposition chamber for 7 hours, and taking out to obtain TaWMoCrZr amorphous refractory high-entropy alloy coatings on the steel substrate and the monocrystalline silicon substrate respectively, wherein the thickness of each coating is 3.5 mu m.
And carrying out microstructure characterization and mechanical property test on the prepared TaWMoCrZr refractory high-entropy alloy coating, wherein Zr elements are uniformly distributed and occupy 23.2 at%, the structure is completely amorphous, the nano indentation hardness is 10.93GPa, and the Young modulus is 136GPa.
FIG. 2 shows an AFM surface topography of TaWMoCrZr refractory high-entropy alloy coating prepared in this example, the coating surface was smooth with a roughness of 0.236nm; FIG. 3 is a SEM plan view and a cross-sectional view of TaWMoCrZr refractory high-entropy alloy coating prepared in this example, without grain morphology.
Example 2
A preparation method of TaWMoCrZr amorphous refractory high-entropy alloy coating comprises the following steps:
Step 1: the steel substrate is polished by using No. 600, no. 1000, no. 1500 and No. 2000 sand paper in sequence until the steel substrate is completely covered with the scratches of the previous pass, and then polished until the steel substrate is bright and has no obvious scratches.
Step 2: the polished steel substrate and the monocrystalline silicon substrate were ultrasonically cleaned in acetone and absolute ethanol, respectively, for 10min, and dried with a blower.
Step 3: fixing the steel matrix on the base plate, then mechanically and automatically conveying the steel matrix into a vacuum coating chamber, and vacuumizing until the back vacuum degree is lower than 4.0 multiplied by 10 -4 Pa.
Step 4: after vacuumizing, etching the steel substrate for 5 minutes at a power of 200W and an air flow of 60 sccm.
Step 5: and preparing TaWMoCrZr refractory high-entropy alloy coating on the etched steel substrate by adopting a magnetron sputtering co-sputtering method.
Wherein, taWMoCr alloy target purity 99.9wt.% (Ta: W: mo: cr=29:29:23:19 at.%) adopts 2 direct current power supplies, power is 100W, zr target purity 99.9wt.% adopts 1 radio frequency power supply, power is 150W, working air pressure set value is 0.3Pa, base plate rotational speed is 15r/min, total deposition time is 18800s.
Step 6: and after the deposition is finished, naturally cooling the steel matrix in a high vacuum deposition chamber for 7 hours, and taking out to obtain TaWMoCrZr amorphous refractory high-entropy alloy coating, wherein the thickness of the coating is 4.2 mu m.
And carrying out microstructure characterization and mechanical property test on the prepared TaWMoCrZr refractory high-entropy alloy coating, wherein Zr elements are uniformly distributed and occupy 33.5 at%, the microstructure is completely amorphous, the nano indentation hardness is 10.79GPa, and the Young modulus is 125.37GPa.
Example 3
A preparation method of TaWMoCrZr amorphous refractory high-entropy alloy coating comprises the following steps:
Step 1: the steel substrate is polished by using No. 600, no. 1000, no. 1500 and No. 2000 sand paper in sequence until the steel substrate is completely covered with the scratches of the previous pass, and then polished until the steel substrate is bright and has no obvious scratches.
Step 2: the polished steel substrate and the monocrystalline silicon substrate were ultrasonically cleaned in acetone and absolute ethanol, respectively, for 10min, and dried with a blower.
Step 3: and respectively fixing the steel substrate and the monocrystalline silicon substrate on a base plate, then mechanically and automatically conveying the steel substrate and the monocrystalline silicon substrate into a vacuum coating chamber, and vacuumizing until the back vacuum degree is lower than 4.0 multiplied by 10 -4 Pa.
Step 4: after vacuumizing, etching the steel substrate and the monocrystalline silicon substrate, wherein the power is 200W, the air flow is 60sccm, and etching is performed for 5 minutes.
Step 5: and respectively preparing TaWMoCrZr refractory high-entropy alloy coating on the etched steel substrate and the etched monocrystalline silicon substrate by adopting a magnetron sputtering co-sputtering method.
Wherein, taWMoCr alloy target purity 99.9wt.% (Ta: W: mo: cr=29:29:23:19 at.%) adopts 2 direct current power supplies, power is 100W, zr target purity 99.9wt.% adopts 1 radio frequency power supply, power is 200W, working air pressure set value is 0.3Pa, base plate rotational speed is 15r/min, total deposition time is 18800s.
Step 6: and after the deposition is finished, naturally cooling the steel substrate and the monocrystalline silicon substrate in a high vacuum deposition chamber for 7 hours, and taking out to obtain TaWMoCrZr amorphous refractory high-entropy alloy coatings on the steel substrate and the monocrystalline silicon substrate respectively, wherein the thicknesses of the high-entropy alloy coatings are 5.0 mu m.
And carrying out microstructure characterization and mechanical property test on the prepared TaWMoCrZr refractory high-entropy alloy coating, wherein Zr elements are uniformly distributed and occupy 41.3 at%, the microstructure is completely amorphous, the nano indentation hardness is 10.01GPa, and the Young modulus is 118GPa.
FIG. 1 is an XRD pattern of TaWMoCrZr refractory high-entropy alloy coating, and TaWMoCrZr refractory high-entropy alloy coating of both Zr components of example 1 and example 3 shows distinct amorphous steamed bread peaks.
FIG. 4 is a TEM selected area electron diffraction and high resolution photograph of TaWMoCrZr refractory high-entropy alloy coating prepared by this embodiment; FIG. 5 is a facial scan of EDS elements of a (TaWMoCr) Zr41.3 amorphous refractory high-entropy alloy coating having a Zr content of 41.3at.% prepared in this example, with the elements being uniformly distributed in the structure; the TaWMoCrZr refractory high-entropy alloy coating has excellent mechanical property and high-temperature tissue stability.
For TaWMoCrZr refractory high-entropy alloy coatings, as the enthalpy of mixing of Zr element and Ta, W, mo, cr is smaller (3, -9, -53, -12kJ/mol, respectively), as the Zr content increases, the enthalpy of mixing of the alloy system decreases, which is beneficial to the formation of disordered amorphous structures, so that the TaWMoCrZr amorphous refractory high-entropy alloy coating is formed when the Zr atomic percentage is 23.2-41.3 at.%. The amorphous refractory high-entropy alloy has a disordered structure with long-range disorder and short-range order, and has no microscopic defects such as vacancies, dislocation, grain boundaries and the like in the crystalline refractory high-entropy alloy and anisotropy caused by different orientations, so that the amorphous refractory high-entropy alloy can show mechanical behaviors, corrosion and oxidation resistance and the like which are completely different from those of the crystalline high-entropy alloy. The amorphous high-entropy alloy has high strength and large elastic strain limit, has excellent corrosion and oxidation resistance due to the fact that no perishable tissue such as microscopic defects exists, has strong capturing capability on bubbles/vacancies and the like caused by irradiation, has strong radiation damage resistance, and has poor plastic deformation capability due to a localized shear deformation mechanism, which is one of research hot spots of the existing amorphous high-entropy alloy.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (6)
1. An amorphous refractory high-entropy alloy coating is characterized in that the chemical composition of the alloy coating is TaWMoCrZr, and the tissue structure is completely disordered amorphous;
TaWMoCrZr is an amorphous refractory high-entropy alloy coating, the atomic percentage ratio of Ta, W, mo, cr elements is 1:1:1:1, and the atomic percentage of Zr element is 23.2-41.3 at%;
the preparation method of the amorphous refractory high-entropy alloy coating comprises the following steps:
step 1, preparing TaWMoCrZr amorphous refractory high-entropy alloy coating on a substrate by adopting a magnetron sputtering co-sputtering method, wherein the sputtering method is as follows:
Co-sputtering two TaWMoCr alloy targets and a Zr target, wherein the direct current power of the TaWMoCr alloy target is 100W, and the radio frequency power of the Zr target is 100-200W;
The atomic percentage of the TaWMoCr alloy target is Ta: W: mo: cr=29:29:23:19 at.%;
And step 2, cooling the substrate to room temperature to obtain TaWMoCrZr amorphous refractory high-entropy alloy coating.
2. An amorphous refractory high-entropy alloy coating according to claim 1, wherein the coating thickness is 3.5-5 μm.
3. The amorphous refractory high-entropy alloy coating according to claim 1, wherein the TaWMoCrZr amorphous refractory high-entropy alloy coating has a nanoindentation hardness of 10-11 GPa and a young's modulus of 118-136 GPa.
4. The amorphous refractory high-entropy alloy coating according to claim 1, wherein the deposition pressure is 0.3Pa, the substrate rotation speed is 15r/min, and the deposition time is 18800 seconds when the amorphous refractory high-entropy alloy coating is prepared TaWMoCrZr in step 1.
5. The amorphous refractory high-entropy alloy coating according to claim 1, wherein the substrate is cleaned and vacuum etched prior to step 1.
6. The amorphous refractory high-entropy alloy coating according to claim 1, wherein the substrate is a steel substrate or a monocrystalline silicon substrate.
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