CN115044870A - 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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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 110
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- 238000002360 preparation method Methods 0.000 title abstract description 15
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- 238000004544 sputter deposition Methods 0.000 claims abstract description 16
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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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
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- 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 percent of Zr is 23.2-41.3 at.%, and the rest is Ta, W, Mo and Cr with nearly equal atomic ratio. A TaWMoCrZr refractory high-entropy alloy coating is prepared on a polished steel substrate and a single crystal silicon substrate by adopting a magnetron sputtering co-sputtering method, wherein 2 direct current power supplies are adopted for a TaWMoCr alloy target, 1 radio frequency power supply is adopted for a Zr target, and the Zr content is adjusted by regulating and controlling the power of the radio frequency target. The prepared TaWMoCrZr refractory high-entropy alloy coating has a completely amorphous structure, uniform components, compact structure, smooth surface, excellent mechanical property and good structure stability, and the application range of the amorphous coating is expanded.
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 hotspot in recent years. The high-entropy alloy coating derived on the basis of the high-entropy alloy also has the performance superior to that of the traditional alloy coating, such as mechanical property, 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 obtained structure is more uniform compared to the 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, is more uniform in structure due to the absence of crystal boundary, dislocation, lattice distortion and other defects of a crystal material, is not easy to corrode due to nonuniformity, and has better corrosion resistance. However, the amorphous alloy is in a metastable state in thermodynamics, and crystallization occurs when the amorphous alloy is heated, so that the original structure and performance of the amorphous alloy disappear due to the crystallization, and the engineering application of the amorphous alloy is influenced. Therefore, the research and development of the amorphous refractory high-entropy alloy coating which has high performance and high thermal stability and has the comprehensive characteristics of the high-entropy alloy and the traditional amorphous alloy and the preparation method thereof have important application value.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an amorphous refractory high-entropy alloy coating and a preparation method thereof.
The invention is realized by the following technical scheme:
the amorphous refractory high-entropy alloy coating comprises the chemical component TaWMoCrZr and the structure of the alloy coating is completely disordered amorphous.
Preferably, the atomic percent ratio of the four elements of Ta, W, Mo and Cr in the TaWMoCrZr amorphous refractory high-entropy alloy coating is 1:1:1:1, and the atomic percent of the Zr element is 23.2-41.3 at.%.
Preferably, the thickness of the coating 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:
co-sputtering by adopting 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 2, cooling the substrate to room temperature to obtain the TaWMoCrZr amorphous refractory high-entropy alloy coating.
The TaWMoCr atomic percent of the amorphous refractory high-entropy alloy coating is Ta: W: Mo: Cr: 29:23:19 at.%.
In the step 1 of the amorphous refractory high-entropy alloy coating, two TaWMoCr alloy targets and one Zr target are adopted for co-sputtering.
When the TaWMoCrZr amorphous refractory high-entropy alloy coating is prepared in the step 1 of the amorphous refractory high-entropy alloy coating, the deposition pressure is 0.3Pa, the rotating speed of the substrate is 15r/min, and the deposition time is 18800 seconds.
And (3) cleaning and vacuum etching the substrate by the amorphous refractory high-entropy alloy coating before step 1.
The substrate of the amorphous refractory high-entropy alloy coating is a steel substrate or a single crystal 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, and the element composition is TaWMoCrZr, wherein the atomic percent of Zr is 23.2-41.3 at.%, and the rest is Ta, W, Mo and Cr with nearly equal atomic ratio. All elements are uniformly distributed in the coating, the structure is compact, the mechanical property and the corrosion and oxidation resistance of the coating are excellent, and a certain structural stability can be kept at a high temperature.
The invention provides a preparation method of an amorphous refractory high-entropy alloy coating, which is characterized in that a TaWMoCrZr refractory high-entropy alloy coating is prepared on a polishing substrate by adopting a magnetron sputtering co-sputtering method, wherein 2 direct current power supplies are adopted for a TaWMoCr alloy target, 1 radio frequency power supply is adopted for a Zr target, the Zr content is adjusted by regulating and controlling the power of the radio frequency target, the deposition rate is high, and the deposited coating is uniform and compact, has few defects, high purity and strong adhesive force. The prepared TaWMoCrZr refractory high-entropy alloy coating has a completely amorphous structure, uniform components, compact structure, smooth surface, excellent mechanical property and good structure stability, and the application range of the amorphous coating is expanded.
Because of reasonable selection of alloy elements and reasonable optimization of the preparation method, the alloy material can realize preparation of high-entropy amorphous alloy material without low temperature, which is different from the situation that metal melt needs to be quenched to low temperature when amorphous alloy is prepared in the prior art.
Drawings
FIG. 1 is an XRD result diagram of the TaWMoCrZr amorphous refractory high-entropy alloy coating.
FIG. 2 shows (TaWMoCr) Zr prepared in example 1 of the present invention 23.2 And (3) an amorphous refractory high-entropy alloy coating AFM surface topography.
FIG. 3 shows (TaWMoCr) Zr prepared in example 1 of the present invention 23.2 SEM plane and section pictures of the amorphous refractory high-entropy alloy coating.
Wherein, the diagram a is (TaWMoCr) Zr 23.2 SEM plan view of amorphous refractory high-entropy alloy coating;
FIG. b shows (TaWMoCr) Zr 23.2 A cross-sectional photograph of the amorphous refractory high-entropy alloy coating;
FIG. 4 shows (TaWMoCr) Zr prepared in example 2 of the present invention 41.3 And (4) selecting a TEM (transverse electric and magnetic field) area for electron diffraction and high-resolution pictures of the amorphous refractory high-entropy alloy coating.
Wherein, the diagram a is (TaWMoCr) Zr 41.3 TEM selected area electron diffraction picture of amorphous refractory high-entropy alloy coating;
FIG. b shows (TaWMoCr) Zr 41.3 High-resolution photos of the amorphous refractory high-entropy alloy coating;
FIG. 5 (TaWMoCr) Zr prepared in example 2 of the present invention 41.3 EDS element surface scanning pictures of the amorphous refractory high-entropy alloy coating.
Detailed Description
The present invention will now be described in further detail with reference to the attached drawings, which are illustrative, but not limiting, of the present invention.
A TaWMoCrZr amorphous refractory high-entropy alloy coating is prepared by adopting a magnetron sputtering co-sputtering method, the organization structure of the TaWMoCrZr amorphous high-entropy alloy coating is a completely disordered amorphous state, the chemical components of the TaWMoCrZr amorphous high-entropy alloy coating comprise the following components in atomic percentage, the atomic percentage of the four elements including Ta, W, Mo and Cr is approximately 1:1:1, and the atomic percentage of the 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 the TaWMoCrZr amorphous refractory high-entropy alloy coating, which comprises the following steps:
step 1: and cleaning the substrate for improving the binding force of the coating and the substrate.
The substrate is a steel substrate or a single crystal silicon substrate.
The cleaning method of the steel matrix comprises the following steps:
sequentially grinding and polishing a steel matrix by using 600#, 1000#, 1500# and 2000# sandpaper, ultrasonically cleaning the polished steel matrix in acetone and absolute ethyl alcohol for 10 minutes, and drying.
The polishing and cleaning method of the single crystal silicon substrate comprises the following steps:
the single-side polished monocrystalline silicon substrate is sequentially subjected to ultrasonic cleaning in acetone and absolute ethyl alcohol for 10 minutes and dried, so that the surface of the substrate is clean and free of dirt, dust and other foreign particles, the polished substrate is subjected to ultrasonic cleaning, and the bonding force between a coating and the substrate is improved.
Step 2: and (4) carrying out vacuum etching on the substrate cleaned in the step (1).
Specifically, the substrate after ultrasonic cleaning is fixed on a base plate, an automatic machine is accompanied and sent into a magnetron sputtering coating chamber, and the vacuum degree is pumped till the back bottom vacuum degree is 4.0 multiplied by 10 -4 Pa below; the power is 200W, the gas flow is 60sccm, and the etching is carried out for 5 minutes, so that the bonding force between the coating and the substrate is improved.
And step 3: and depositing and preparing the TaWMoCrZr refractory high-entropy alloy coating on the substrate by adopting a magnetron sputtering co-sputtering method, wherein the atomic percent of Zr is 23.2-41.3% respectively.
Wherein, two TaWMoCr alloy targets with the purity of 99.9 wt.% (Ta: W: Mo: Cr: 29:23:19 at.%) are adopted, the TaWMoCr alloy targets adopt direct current power supplies with the power of 100W, the Zr target with the purity of 99.9 wt.% adopts 1 radio frequency power supply with the power of 100-200W, the deposition pressure is set to be 0.3Pa, the rotating speed of a base plate is 15r/min, and the vacuum degree is 4.0 x 10 -4 And (3) below Pa, simultaneously starting 2 direct current power supplies and 1 radio frequency power supply to start co-sputtering deposition, wherein 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 deposition, the substrate is fully cooled to room temperature in a high vacuum coating chamber and then taken out, so that debonding and cracking caused by the difference of the thermal expansion coefficients of the substrate and the coating material can be prevented, and oxidation with air due to high temperature can be prevented. Finally depositing TaWMoCrZr amorphous refractory high-entropy alloy coatings with different Zr contents.
Example 1
A preparation method of a TaWMoCrZr amorphous refractory high-entropy alloy coating comprises the following steps:
step 1: and (3) sequentially grinding the steel substrate by 600#, 1000#, 1500# and 2000# abrasive paper until the steel substrate completely covers the scratches of the previous pass, and then polishing until the steel substrate is bright and has no obvious scratches.
Step 2: and ultrasonically cleaning the polished steel substrate and the monocrystalline silicon substrate in acetone and absolute ethyl alcohol respectively for 10min, and drying by using a blower.
And step 3: respectively fixing the steel substrate and the monocrystalline silicon substrate on a base plate, mechanically and automatically conveying into a vacuum coating chamber, and vacuumizing until the vacuum degree of the back bottom is lower than 4.0 multiplied by 10 -4 Pa。
And 4, step 4: and after vacuumizing, etching the steel substrate and the monocrystalline silicon substrate for 5 minutes at the power of 200W and the gas flow of 60 sccm.
And 5: respectively preparing TaWMoCrZr refractory high-entropy alloy coatings on the etched steel substrate and monocrystalline silicon substrate by adopting a magnetron sputtering co-sputtering method.
Wherein, the TaWMoCr alloy target has 99.9 wt% purity (Ta: W: Mo: Cr ═ 29:29:23:19 at.%) and adopts 2 direct current power supplies, the power is 100W, the Zr target has 99.9 wt% purity and adopts 1 radio frequency power supply, the radio frequency power supply has 100W power, the working air pressure is set to 0.3Pa, the rotating speed of the basal disc is 15r/min, and the total deposition time is 18800 s.
Step 6: after deposition, the steel substrate and the monocrystalline silicon substrate are naturally cooled in a high vacuum deposition chamber for 7 hours and then taken out, and TaWMoCrZr amorphous refractory high-entropy alloy coatings are respectively obtained on the steel substrate and the monocrystalline silicon substrate, wherein the thicknesses of the TaWMoCrZr amorphous refractory high-entropy alloy coatings are 3.5 mu m.
Microstructure characterization and mechanical property tests are carried out on the prepared TaWMoCrZr refractory high-entropy alloy coating, Zr element is uniformly distributed and accounts for 23.2 at.%, the structure is completely amorphous, the nano-indentation hardness is 10.93GPa, and the Young modulus is 136 GPa.
FIG. 2 shows an AFM surface topography of the TaWMoCrZr refractory high-entropy alloy coating prepared by the embodiment, the coating surface is smooth, and the roughness is 0.236 nm; FIG. 3 shows SEM images and sectional photographs of the TaWMoCrZr refractory high-entropy alloy coating prepared by the embodiment, which have no crystal grain appearance.
Example 2
A preparation method of a TaWMoCrZr amorphous refractory high-entropy alloy coating comprises the following steps:
step 1: and (3) sequentially grinding the steel substrate by 600#, 1000#, 1500# and 2000# abrasive paper until the steel substrate completely covers the scratches of the previous pass, and then polishing until the steel substrate is bright and has no obvious scratches.
Step 2: and ultrasonically cleaning the polished steel substrate and the monocrystalline silicon substrate in acetone and absolute ethyl alcohol respectively for 10min, and drying by using a blower.
And step 3: fixing the steel substrate on a base plate, mechanically and automatically conveying the steel substrate into a vacuum coating chamber in a companion manner, and pumpingVacuum to a degree of vacuum below 4.0X 10 -4 Pa。
And 4, step 4: and after vacuumizing, etching the steel substrate for 5 minutes at the power of 200W and the gas flow of 60 sccm.
And 5: and preparing the TaWMoCrZr refractory high-entropy alloy coating on the etched steel substrate by adopting a magnetron sputtering co-sputtering method.
Wherein, the TaWMoCr alloy target has 99.9 wt% purity (Ta: W: Mo: Cr ═ 29:29:23:19 at.%) and uses 2 DC power supplies, the power is 100W, the Zr target has 99.9 wt% purity and uses 1 RF power supply, the power is 150W, the working pressure is set to 0.3Pa, the rotating speed of the basal disc is 15r/min, and the total deposition time is 18800 s.
And 6: and after deposition, naturally cooling the steel substrate in a high vacuum deposition chamber for 7 hours, and taking out to obtain the TaWMoCrZr amorphous refractory high-entropy alloy coating with the thickness of 4.2 μm.
Microstructure characterization and mechanical property tests are carried out on the prepared TaWMoCrZr refractory high-entropy alloy coating, Zr elements are uniformly distributed, the percentage of Zr elements is 33.5 at.%, the structure is completely amorphous, the nano-indentation hardness is 10.79GPa, and the Young modulus is 125.37 GPa.
Example 3
A preparation method of a TaWMoCrZr amorphous refractory high-entropy alloy coating comprises the following steps:
step 1: and (3) sequentially grinding the steel substrate by 600#, 1000#, 1500# and 2000# abrasive paper until the steel substrate completely covers the scratches of the previous pass, and then polishing until the steel substrate is bright and has no obvious scratches.
Step 2: and ultrasonically cleaning the polished steel substrate and the monocrystalline silicon substrate in acetone and absolute ethyl alcohol respectively for 10min, and drying by using a blower.
And step 3: respectively fixing the steel substrate and the monocrystalline silicon substrate on a base plate, mechanically and automatically conveying into a vacuum coating chamber, and vacuumizing until the vacuum degree of the back bottom is lower than 4.0 multiplied by 10 -4 Pa。
And 4, step 4: and after vacuumizing, etching the steel substrate and the monocrystalline silicon substrate for 5 minutes at the power of 200W and the gas flow of 60 sccm.
And 5: respectively preparing TaWMoCrZr refractory high-entropy alloy coatings on the etched steel substrate and monocrystalline silicon substrate by adopting a magnetron sputtering co-sputtering method.
Wherein, the TaWMoCr alloy target has 99.9 wt% purity (Ta: W: Mo: Cr ═ 29:29:23:19 at.%) and uses 2 DC power supplies with power of 100W, the Zr target has 99.9 wt% purity and uses 1 RF power supply with power of 200W, the working pressure is set to 0.3Pa, the rotating speed of the base plate is 15r/min, and the total deposition time is 18800 s.
Step 6: after deposition, the steel substrate and the monocrystalline silicon substrate are naturally cooled in a high vacuum deposition chamber for 7 hours and then taken out, and TaWMoCrZr amorphous refractory high-entropy alloy coatings are respectively obtained on the steel substrate and the monocrystalline silicon substrate, and the thicknesses of the TaWMoCrZr amorphous refractory high-entropy alloy coatings are 5.0 mu m.
Microstructure characterization and mechanical property tests are carried out on the prepared TaWMoCrZr refractory high-entropy alloy coating, Zr elements are uniformly distributed, the percentage of Zr elements is 41.3 at.%, the structure is completely amorphous, the nano-indentation hardness is 10.01GPa, and the Young modulus is 118 GPa.
Fig. 1 is an XRD result diagram of the tawmocrrzr refractory high-entropy alloy coating, and both the tawmocrrzr refractory high-entropy alloy coatings of the two Zr components of example 1 and example 3 show a distinct amorphous steamed bread peak.
FIG. 4 shows TEM selected-area electron diffraction and high-resolution photographs of a TaWMoCrZr refractory high-entropy alloy coating prepared by the present embodiment; FIG. 5 is a scanning image of the EDS elements of the amorphous refractory high-entropy alloy coating of (TaWMoCr) Zr41.3 with Zr content of 41.3 at.%, wherein the elements are uniformly distributed in the structure, prepared by the present example; the TaWMoCrZr refractory high-entropy alloy coating has excellent mechanical property and high-temperature structure stability.
For the TaWMoCrZr refractory high-entropy alloy coating, because the mixing enthalpy of the Zr element and Ta, W, Mo and Cr is small (3, -9, -53 and-12 kJ/mol respectively), the mixing enthalpy of an alloy system is reduced along with the increase of Zr content, which is beneficial to the formation of a disordered amorphous structure, and therefore when the Zr atomic percentage is 23.2 to 41.3 at.%, the TaWMoCrZr amorphous refractory high-entropy alloy coating is formed. The amorphous refractory high-entropy alloy has a disordered structure with long-range disorder and short-range order, does not have microscopic defects such as vacancies, dislocations, grain boundaries and the like in the crystalline refractory high-entropy alloy and anisotropy caused by different orientations, and therefore, can show mechanical behavior, 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, shows excellent corrosion and oxidation resistance due to no corrosion-prone structures such as microscopic defects and the like, and has strong capture capacity on bubbles/vacancies introduced by irradiation and strong irradiation damage resistance in addition, but has poor plastic deformation capacity caused by a localized shear deformation mechanism, which is one of the research hotspots of the conventional amorphous high-entropy alloy.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The amorphous refractory high-entropy alloy coating is characterized in that the chemical component of the alloy coating is TaWMoCrZr, and the organization structure of the alloy coating is completely disordered amorphous.
2. The amorphous refractory high-entropy alloy coating of claim 1, wherein the TaWMoCrZr amorphous refractory high-entropy alloy coating has a ratio of atomic percentages of Ta, W, Mo and Cr of 1:1:1:1, and an atomic percentage of Zr of 23.2 to 41.3 at.%.
3. An amorphous refractory high-entropy alloy coating according to claim 1, wherein the coating thickness is 3.5-5 μm.
4. The amorphous refractory high-entropy alloy coating of claim 1, wherein the TaWMoCrZr amorphous high-entropy alloy coating has a nanoindentation hardness of 10-11 GPa and a Young's modulus of 118-136 GPa.
5. A method for preparing the amorphous refractory high-entropy alloy coating layer according to any one of claims 1 to 4, characterized by comprising the following steps:
step 1, preparing a TaWMoCrZr amorphous refractory high-entropy alloy coating on a substrate by adopting a magnetron sputtering co-sputtering method, wherein the sputtering method comprises the following steps:
co-sputtering by adopting 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 2, cooling the substrate to room temperature to obtain the TaWMoCrZr amorphous refractory high-entropy alloy coating.
6. The method for preparing the amorphous refractory high-entropy alloy coating layer according to claim 5, wherein TaWMoCr is Ta: W: Mo: Cr: 29:23:19 at.%.
7. The method for preparing the amorphous refractory high-entropy alloy coating layer according to claim 5, wherein two TaWMoCr alloy targets and one Zr target are adopted for co-sputtering in step 1.
8. The method for preparing the amorphous refractory high-entropy alloy coating layer according to claim 5, wherein in the step 1, when the TaWMoCrZr amorphous refractory high-entropy alloy coating layer is prepared, the deposition pressure is 0.3Pa, the rotating speed of the substrate is 15r/min, and the deposition time is 18800 seconds.
9. The method for preparing the amorphous refractory high-entropy alloy coating layer according to claim 5, wherein the substrate is cleaned and vacuum etched before step 1.
10. The method for preparing an amorphous refractory high-entropy alloy coating layer according to claim 5, wherein the substrate is a steel substrate or a single-crystal silicon substrate.
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