CN114959584A - TaNbTi-based refractory intermediate-entropy amorphous alloy coating and preparation method thereof - Google Patents
TaNbTi-based refractory intermediate-entropy amorphous alloy coating and preparation method thereof Download PDFInfo
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses a TaNbTi-based refractory mid-entropy amorphous alloy coating and a preparation method thereof. The TaNbTi-based refractory intermediate entropy alloy coating is prepared on a single-side polished monocrystalline silicon substrate by adopting a magnetron sputtering co-sputtering method, the target materials are two TaNbTi alloy targets with the purity of 99.9 wt%, one Cr target with the purity of 99.95 wt% or one Al target with the purity of 99.99 wt%, the TaNbTi-based refractory intermediate entropy alloy coating prepared by the magnetron sputtering co-sputtering technology has a compact and uniform amorphous structure in microstructure, few internal defects, uniform element distribution, extremely small roughness and dimple-shaped pattern appearance of a fracture of a cross section, and has excellent mechanical property, oxidation resistance and corrosion resistance.
Description
Technical Field
The invention belongs to the field of metal surface modification, and particularly relates to a TaNbTi-based refractory intermediate-entropy amorphous alloy coating and a preparation method thereof.
Background
The safety service and the service life of the nuclear reactor cladding material are important factors for restricting the development and the application of the nuclear reactor cladding material. The nuclear fuel cladding material needs to endure the actions of high temperature, abrasion, oxidation, corrosion, irradiation and the like for a long time, the service conditions are very harsh, and particularly, the failure of the cladding material is accelerated by the high-temperature oxidation and corrosion, so that serious disasters and losses such as nuclear leakage are caused.
The cladding material used internationally at present is mainly an iron-based material, and is preferably iron-clad steel. However, the iron-based material is seriously corroded in the lead-bismuth liquid metal, Fe, Cr and Ni elements in steel have high solubility in the lead-bismuth liquid metal, and when the oxygen content is slightly high, the corrosion is mainly oxidized, so that the cladding is damaged, and the hidden danger that the oxide layer partially falls off to block the pipeline can be caused. Therefore, surface modification of materials is currently the most effective means to extend the safe service life of cladding materials. The existing ceramic coatings such as SiC, TiN and the like have the problems of large brittleness, small ductility, poor film-substrate bonding and the like; traditional alloy coatings such as Al-Ti-Fe are easy to form brittle intermetallic compounds and accelerate corrosion.
The medium-entropy alloy effectively reduces the deterioration of the properties such as alloy strength, modulus, ductility and the like caused by atomic mismatch due to the reduction of elements forming a stable phase, shows unique mechanical properties, corrosion oxidation resistance and irradiation resistance, and has wide application prospects in the fields of high-temperature alloys, thermoelectric materials, high-performance alloy coatings, superconducting materials, nuclear cladding structure material coatings and the like. The corrosion oxidation of the fuel cladding generally occurs most easily along local defects such as grain boundaries, micropores and the like, so that an amorphous alloy needs to be designed to solve the problems of the existing fuel cladding material.
And the corrosion and oxidation resistance of the material can be effectively improved due to less defects of the amorphous alloy. Therefore, the medium-entropy amorphous alloy has great potential in corrosion prevention of the nuclear cladding material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a TaNbTi refractory intermediate entropy alloy coating and a preparation method thereof.
The invention is realized by the following technical scheme:
a TaNbTi-based refractory entropy alloy coating is TaNbTiCr or TaNbTiAl, and the microstructure of the TaNbTi-based refractory entropy alloy coating is a disordered amorphous structure.
Preferably, the atomic percentage ratio of elements of TaNbTiCr to TaNbTiAl is 1:1:1: 1.
Preferably, the cross-section fracture of the refractory intermediate entropy alloy coating is in a dimple-like pattern appearance.
Preferably, the thickness of the refractory intermediate entropy alloy coating is 2.3-3.3 μm.
Preferably, the nano indentation hardness of the TaNbTiCr refractory intermediate entropy alloy coating is 8.4-9.0 GPa, and the modulus is 120.0-130.0 GPa;
the TaNbTiAl refractory intermediate entropy alloy coating has the nano indentation hardness of 8.0-8.5 GPa and the modulus of 110.0-120.0 GPa.
Preferably, the TaNbTiCr refractory intermediate entropy alloy coating has the surface roughness of R a ：0.75nm；
The surface roughness of the TaNbTiAl refractory intermediate entropy alloy coating is R a ：0.20nm。
A preparation method of TaNbTi-based refractory intermediate-entropy amorphous alloy coating comprises the following steps:
depositing and preparing a TaNbTi-based refractory intermediate entropy alloy coating on a substrate by adopting a magnetron sputtering co-sputtering method, and then cooling to room temperature to obtain the TaNbTi-based refractory intermediate entropy alloy coating;
the magnetron sputtering co-sputtering method comprises the following steps:
carrying out co-sputtering by adopting a TaNbTi alloy target and a Cr target or an Al target, wherein the deposition pressure is 0.3-0.5 Pa, the deposition temperature is room temperature, and the rotating speed of a basal disc is generally 15 r/min;
the direct current power of the TaNbTi alloy target is 90-120W, the radio frequency power supply power of the Cr target is 40-60W, the purity of the Al target is 99.99 wt%, and the radio frequency power supply power is 110-130W.
Preferably, the substrate is cleaned and vacuum etched prior to magnetron sputtering co-sputtering.
Preferably, the atomic ratio of the TaNbTi alloy target is: ta Nb Ti 30.8:32.5:36.7 at.%.
Preferably, two TaNbTi alloy targets are adopted for co-sputtering to prepare the TaNbTi-based refractory medium-entropy alloy coating.
Compared with the prior art, the invention has the following beneficial technical effects:
the TaNbTi-based refractory mid-entropy alloy coating provided by the invention is of an amorphous structure, has a dimple-like pattern appearance of a fracture section, is uniform and compact in microstructure, is good in film-substrate combination, and has better mechanical properties, oxidation resistance and corrosion resistance. Ta and Nb elements in the TaNbTi-based refractory intermediate entropy alloy coating are high-melting-point elements, can keep stable structure under the condition of 1600 ℃ and show excellent high-temperature strength and oxidation resistance. Ti is a metal element with low density, can effectively improve plasticity and is generated 2 O 3 、TiO 2 The passive film can effectively improve the oxidation resistance and corrosion resistance of the material. Cr is a hard metal material, is favorable for improving the hardness and the strength, and is 2 O 3 Is an oxide film with good protection effect. CrTaO formed by interaction between different atoms under oxygen atmosphere 4 And TiTaO 4 Has better antioxidant effect than Cr 2 O 3 The protective film of (1). Also, the atomic radius of Cr is relatively small, which may cause a certain lattice distortion and may even form an amorphous phase. The Al element has better intersolubility with other high-melting point elements, can inhibit the precipitation of Laves phase, avoid the damage to plasticity, and can form a layer of compact Al on the surface of the alloy 2 O 3 Protective layer for significantly improving the alloy temperature between 700 ℃ and 1000 DEG CThe antioxidant property of the composition. Therefore, Cr and Al are added into TaNbTi, so that a compact, uniform and few-defect tissue, high hardness and strength and strong oxidation resistance are expected to be obtained.
The TaNbTi-based refractory intermediate entropy alloy coating provided by the invention is prepared by simultaneously depositing a TaNbTi alloy target and a Cr target or an Al target by a magnetron sputtering co-sputtering method, wherein the direct current power of the two TaNbTi alloy targets is 100W, the radio frequency power of the Cr target is 45W, the radio frequency power of the Al target is 125W, the time is 16800s, the thickness of the deposited TaNbTiCr coating is about 2.65 mu m, and the thickness of the TaNbTiAl coating is about 3.00 mu m. The preparation method adopting magnetron sputtering co-sputtering has the advantages of high deposition rate, small substrate temperature rise, uniform element distribution, low atomic diffusion rate, high disorder degree and difficult grain nucleation, so that a long-range disordered amorphous structure is very easy to obtain. The amorphous coating has no crystal boundary, few defects such as holes, dislocation and the like, uniform and compact structure, and incomparable mechanical property and corrosion resistance compared with the crystalline coating.
After the coating deposition is finished, the coating is naturally cooled to room temperature in a vacuum coating chamber, and because a certain temperature rise occurs in the deposition process, the coating is suddenly removed and contacts with air, so that the coating is oxidized, and the coating is debonded and broken from the substrate due to the difference of the thermal expansion coefficients of the coating and the substrate.
Drawings
FIG. 1 is an XRD diffraction result diagram of TaNbTi-based refractory intermediate entropy alloy coating of the invention;
wherein, the figure a is an XRD diffraction result diagram of the TaNbTiCr refractory intermediate entropy alloy coating;
and the figure b is an XRD diffraction result diagram of the TaNbTiAl refractory intermediate entropy alloy coating.
FIG. 2 is a TEM high-resolution image of TaNbTi-based refractory medium-entropy alloy coating of the invention;
wherein, the image a is a TEM high-resolution image of TaNbTiCr refractory medium-entropy alloy coating;
FIG. b is an image of the diffraction ring of FIG. 2 a;
FIG. c is a TEM high resolution image of TaNbTiAl refractory intermediate entropy alloy coating;
fig. d is an image of the diffraction ring of fig. 2 c.
FIG. 3 is an SEM sectional photograph and an EDS energy spectrum analysis chart of a TaNbTi-based refractory medium entropy alloy coating of the invention;
wherein, the picture a is an SEM sectional picture of TaNbTiCr refractory intermediate entropy alloy coating;
FIG. b is an EDS (electron-dispersive spectroscopy) energy spectrum analysis chart of a TaNbTiCr refractory intermediate entropy alloy coating;
FIG. c is an SEM cross-sectional photograph of TaNbTiAl refractory intermediate entropy alloy coating;
and the figure d is an EDS energy spectrum analysis chart of the TaNbTiAl refractory intermediate entropy alloy coating.
FIG. 4 is a diagram showing the nano-indentation hardness results of TaNbTi-based refractory medium-entropy alloy coatings;
wherein, the graph a is a nano indentation hardness curve graph of TaNbTiCr refractory intermediate entropy alloy coating;
and the graph b is a nano indentation hardness curve chart of the TaNbTiAl refractory intermediate entropy alloy coating.
FIG. 5 is an AFM micrograph of a TaNbTi-based refractory mid-entropy alloy coating according to the invention;
wherein, the picture a is an AFM micrograph of TaNbTiCr refractory intermediate entropy alloy coating;
FIG. b is a 3DAFM micrograph of TaNbTiCr refractory intermediate entropy alloy coating;
FIG. c is an AFM micrograph of TaNbTiAl refractory intermediate entropy alloy coating;
FIG. d is a 3DAFM micrograph of TaNbTiAl refractory intermediate 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.
The TaNbTi-based refractory mid-entropy alloy coating is TaNbTiCr or TaNbTiAl, the chemical composition atoms of the alloy coating are in equal atomic ratio, namely the atomic percentage ratio of elements is 1:1:1:1, the structure of the alloy coating is a disordered amorphous structure, and a fracture of the section is in a dimple-shaped pattern shape.
The thickness of the alloy coating is 2.5-3.3 mu m.
The nano indentation hardness of the TaNbTiCr refractory intermediate entropy alloy coating is 8.4-9.0 GPa, and the modulus is 120.0-130.0 GPa; in the TaNbTiCr refractoryThe surface roughness of the entropy alloy coating is R a ：0.75nm；
The TaNbTiAl refractory entropy alloy coating has the nano indentation hardness of 8.0-8.5 GPa and the modulus of 110.0-120.0 GPa, and the surface roughness of the TaNbTiAl refractory entropy alloy coating is Ra: 0.20 nm.
The TaNbTi-based refractory intermediate entropy alloy coating has the advantages of uniform and compact structure, extremely small roughness, few defects, uniform distribution of internal alloy elements, high purity and good film-substrate combination. The TaNbTi-based refractory medium-entropy alloy coating has excellent mechanical property, oxidation resistance and corrosion resistance.
The tissue structure of the TaNbTi-based refractory intermediate-entropy alloy coating is an amorphous structure, the amorphous alloy has the composition characteristics of multi-principal-element alloy and the structural characteristics of short-range order and long-range disorder, and the tissue has no defects of crystal boundary, dislocation and the like, and has the properties of high strength, high elastic limit, high fracture toughness, wear resistance, corrosion resistance and the like. Therefore, the characteristics of the structural properties of the medium-entropy alloy and the amorphous alloy are combined, and the prepared medium-entropy amorphous alloy coating has excellent mechanical properties and has no defect structures such as crystal boundaries and the like on the structure, so that the coating shows excellent corrosion and oxidation resistance, and is the most direct and effective method for improving the service performance of a fuel cladding material in a short period. The TaNbTi alloy contains the component elements with good thermal stability and excellent high-temperature strength, and Cr and Al are typical antioxidant elements and can form a compact protective oxide film at high temperature to prevent further oxidation.
A preparation method of the TaNbTi-based refractory medium-entropy alloy coating comprises the following steps:
step 1: the substrate is cleaned, and the binding force between the coating and the substrate is improved.
Specifically, the substrate is a single crystal silicon substrate or a T91 iron-horse steel substrate, the substrate is sequentially subjected to ultrasonic cleaning in acetone and ethanol for 10 minutes and dried, the surface of the substrate is clean and free of dirt and dust adhesion, the surface roughness of the single crystal silicon substrate after ultrasonic cleaning is less than 0.8nm, the polished single crystal silicon substrate is subjected to ultrasonic cleaning, the bonding force between a coating and the substrate is favorably improved, and the film forming quality is improved.
Step 2: and carrying out vacuum etching on the cleaned substrate.
Fixing the ultrasonically cleaned monocrystalline silicon substrate on a base plate, conveying into a magnetron sputtering coating chamber by an automatic machine, vacuumizing until the vacuum degree of the back bottom is below 4.0 multiplied by 10 < -4 > Pa, and etching for 5min at the etching power of 200W.
And 3, step 3: and depositing and preparing the TaNbTi-based refractory mid-entropy alloy coating on the monocrystalline silicon substrate by adopting a magnetron sputtering co-sputtering method.
Specifically, two TaNbTi alloy targets, and one Cr target or one Al target are used. The TaNbTi alloy targets have the purity of 99.9 wt.% (Ta: Nb: Ti: 30.8:32.5:36.7 at.%), the two TaNbTi alloy targets are direct current targets, the power supply is 90-120W, the deposition pressure is 0.3-0.5 Pa, the deposition temperature is room temperature, and the rotating speed of a basal disc is generally 15 r/min.
The purity of the Cr target is 99.95 wt.%, the power of a radio frequency power supply is 40-60W, and the thickness of the obtained TaNbTiCr refractory entropy alloy coating is about 2.65 mu m.
The purity of the Al target is 99.99 wt.%, the power of a radio frequency power supply is 110-130W, and the thickness of the obtained TaNbTiAl refractory intermediate entropy alloy coating is about 2.5-3.0 μm.
And 4, because the base material has certain temperature rise in the deposition process, naturally cooling the base material to room temperature in a vacuum coating chamber after the deposition of the coating in order to prevent the oxidation of the coating and the deterioration of the film-base combination.
A TaNbTi-based refractory intermediate entropy alloy coating is deposited on the surface of a silicon substrate by adopting a magnetron sputtering co-sputtering method, and the principle is as follows: ar gas collides with electrons to be ionized under the action of an electric field, the ionized Ar + carries high energy to accelerate to bombard a cathode target under the action of the electric field, after the Ar gas elastically collides with target atoms, partial kinetic energy is transferred to the target atoms, when the partial kinetic energy is greater than the binding energy of the target surface atoms, the atoms are separated from the target and sputtered out, and the sputtered target atoms are deposited on a substrate to form a film. When multi-target co-sputtering is carried out, different target material atoms are bombarded and sputtered on the substrate at the same time, the atoms are uniformly distributed, and because the sputtering rates of the different atoms are different, the content of the different target material atoms in the coating can be controlled by regulating and controlling the sputtering power.
In the deposition process, because of the continuous bombardment of particles, certain temperature rise is generated, the coating is suddenly removed and contacts with air, the coating is oxidized, and the coating is debonded and broken from the base body due to the difference of the thermal expansion coefficients of the coating and the base body, so that the coating is naturally cooled to room temperature in a vacuum coating chamber after the deposition is finished, and then the coating is taken out of the plate for sampling.
Example 1
A preparation method of TaNbTiCr refractory intermediate-entropy alloy coating comprises the following steps:
step 1: and ultrasonically cleaning the single-side polished monocrystalline silicon substrate in acetone and ethanol for 10min respectively, and drying by using a blower.
Step 2: fixing the substrate on a base plate, mechanically and automatically feeding the substrate into a vacuum coating chamber with vacuum degree of the back bottom lower than 4.0 × 10 before deposition -4 Pa, and etching for 5min with the etching power of 200W.
And 3, step 3: and preparing the TaNbTiCr refractory intermediate entropy alloy coating by magnetron sputtering co-sputtering.
Wherein, the purity of TaNbTi alloy target is 99.9 wt.% (Ta: Nb: Ti: 30.8:32.5:36.7 at.%), the power of two direct current targets is 100W, the purity of Cr target is 99.9 wt.%, the power of radio frequency power supply is 45W, the set value of working air pressure is 0.3Pa, the deposition temperature is room temperature, and the rotating speed of the basal disc is 15 r/min.
And 4, step 4: after deposition, the substrate is naturally cooled in a vacuum coating chamber for 5 hours and then taken out to obtain the TaNbTiCr refractory intermediate entropy alloy coating with the thickness of about 2.65 mu m.
Example 2
A preparation method of TaNbTiCr refractory intermediate-entropy alloy coating comprises the following steps:
step 1: the single-side polished T91 iron-horse steel substrate is ultrasonically cleaned in acetone and ethanol for 10min respectively and dried by a blower.
Step 2: fixing the substrate on a base plate, mechanically and automatically feeding the substrate into a vacuum coating chamber with vacuum degree of the back bottom lower than 4.0 × 10 before deposition -4 Pa, and etching for 5min with the etching power of 200W.
And 3, step 3: and preparing the TaNbTiCr refractory intermediate entropy alloy coating by magnetron sputtering co-sputtering.
Wherein, the purity of TaNbTi alloy target is 99.9 wt.% (Ta: Nb: Ti: 30.8:32.5:36.7 at.%), the power of two direct current targets is 100W, the purity of Cr target is 99.9 wt.%, the power of radio frequency power supply is 45W, the set value of working air pressure is 0.3Pa, the deposition temperature is room temperature, and the rotating speed of the basal disc is 15 r/min.
And 4, step 4: after deposition, the substrate is naturally cooled in a vacuum coating chamber for 5 hours and then taken out to obtain the TaNbTiCr refractory intermediate entropy alloy coating with the thickness of about 2.65 mu m.
Microstructure characterization and mechanical property test are carried out on the prepared TaNbTiCr refractory intermediate entropy alloy coating, the TaNbTiCr refractory intermediate entropy alloy coating is of an amorphous structure, the structure is compact and uniform, the section fracture is in a dimple-shaped pattern shape, the nano indentation hardness is 8.48GPa, the modulus is 127.03GPa, the roughness is Ra: 0.75 nm.
Example 3
The difference between the embodiment 3 and the embodiment 2 lies in the step 3, and the rest parts are the same, specifically as follows:
and step 3: and preparing the TaNbTiCr refractory intermediate entropy alloy coating by magnetron sputtering co-sputtering.
Wherein, the purity of TaNbTi alloy target is 99.9 wt.% (Ta: Nb: Ti: 30.8:32.5:36.7 at.%), the power of two direct current targets is 90W, the purity of Cr target is 99.9 wt.%, the power of radio frequency power supply is 40W, the set value of working air pressure is 0.4Pa, the deposition temperature is room temperature, and the rotating speed of the basal disc is 15 r/min.
The thickness of the obtained TaNbTiAl refractory intermediate entropy alloy coating is about 2.3 mu m, the nano indentation hardness of the TaNbTiCr refractory intermediate entropy alloy coating is 8.4GPa, and the modulus is 120 GPa.
Example 4
The difference between the embodiment 4 and the embodiment 2 lies in the step 3, and the rest parts are the same, specifically as follows:
and step 3: and preparing the TaNbTiCr refractory intermediate entropy alloy coating by magnetron sputtering co-sputtering.
Wherein, the purity of TaNbTi alloy target is 99.9 wt.% (Ta: Nb: Ti: 30.8:32.5:36.7 at.%), the power of two direct current targets is 120W, the purity of Cr target is 99.9 wt.%, the power of radio frequency power supply is 60W, the set value of working air pressure is 0.5Pa, the deposition temperature is room temperature, and the rotating speed of the basal disc is 15 r/min.
The thickness of the obtained TaNbTiAl refractory intermediate entropy alloy coating is about 3.0 mu m, the nano indentation hardness of the TaNbTiCr refractory intermediate entropy alloy coating is 9GPa, and the modulus is 130 Gpa.
Example 5
A preparation method of TaNbTAl refractory intermediate entropy alloy coating comprises the following steps:
step 1: and ultrasonically cleaning the single-side polished monocrystalline silicon substrate in acetone and ethanol for 10min respectively, and drying by using a blower.
Step 2: fixing the substrate on a base plate, mechanically and automatically feeding the substrate into a vacuum coating chamber with vacuum degree of the back bottom lower than 4.0 × 10 before deposition -4 Pa, and etching for 5min with the etching power of 200W.
And step 3: the TaNbTiAl refractory intermediate entropy alloy coating is prepared by adopting a magnetron sputtering co-sputtering method.
Wherein, the purity of TaNbTi alloy target is 99.9 wt.% (Ta: Nb: Ti: 30.8:32.5:36.7 at.%), the power of two direct current targets is 100W, the purity of Al target is 99.99 wt.%, the power of radio frequency power supply is 125W, the set value of working air pressure is 0.3Pa, the deposition temperature is room temperature, and the rotating speed of the basal disc is 15 r/min.
And 4, step 4: after deposition, the substrate is naturally cooled in a vacuum coating chamber for 5 hours and then taken out to obtain the TaNbTiAl refractory intermediate entropy alloy coating with the thickness of about 3.00 mu m.
Example 6
A preparation method of TaNbTAl refractory intermediate entropy alloy coating comprises the following steps:
step 1: the single-side polished T91 iron-horse steel substrate is ultrasonically cleaned in acetone and ethanol for 10min respectively and dried by a blower.
Step 2: fixing the substrate on a base plate, mechanically and automatically feeding the substrate into a vacuum coating chamber, wherein the vacuum degree of the back bottom is lower than 4.0 x 10 before deposition -4 Pa, and etching for 5min with the etching power of 200W.
And step 3: the TaNbTiAl refractory intermediate entropy alloy coating is prepared by adopting a magnetron sputtering co-sputtering method.
Wherein, the purity of TaNbTi alloy target is 99.9 wt.% (Ta: Nb: Ti: 30.8:32.5:36.7 at.%), the power of two direct current targets is 100W, the purity of Al target is 99.99 wt.%, the power of radio frequency power supply is 125W, the set value of working air pressure is 0.3Pa, the deposition temperature is room temperature, and the rotating speed of the basal disc is 15 r/min.
And 4, step 4: after deposition, the substrate is naturally cooled in a vacuum coating chamber for 5 hours and then taken out to obtain the TaNbTiAl refractory medium-entropy alloy coating with the thickness of about 3.00 mu m.
Microstructure characterization and mechanical property test are carried out on the prepared TaNbTiAl refractory entropy alloy coating, the microstructure is an amorphous structure, the structure is compact and uniform, the section fracture is in a dimple-shaped pattern appearance, the nano indentation hardness is 8.06GPa, the modulus is 117.55GPa, the roughness is Ra: 0.20 nm.
Example 7
Example 7 differs from example 6 in step 3, the rest being the same, as follows:
and step 3: the TaNbTiAl refractory intermediate entropy alloy coating is prepared by adopting a magnetron sputtering co-sputtering method.
Wherein, the purity of TaNbTi alloy target is 99.9 wt% (Ta: Nb: Ti: 30.8:32.5:36.7 at.%), the power of two direct current targets is 90W, the purity of Al target is 99.99 wt.%, the power of radio frequency power supply is 110W, the set value of working air pressure is 0.4Pa, the deposition temperature is room temperature, and the rotation speed of the basal disc is 15 r/min.
The thickness of the obtained TaNbTiAl refractory entropy alloy coating is about 2.5 mu m, the nano indentation hardness of the TaNbTiAl refractory entropy alloy coating is 8.0GPa, and the modulus is 110.0 GPa.
Example 8
Example 8 differs from example 6 in step 3, the rest being the same, as follows:
and step 3: the TaNbTiAl refractory intermediate entropy alloy coating is prepared by adopting a magnetron sputtering co-sputtering method.
Wherein, the purity of TaNbTi alloy target is 99.9 wt.% (Ta: Nb: Ti: 30.8:32.5:36.7 at.%), the power of two direct current targets is 120W, the purity of Al target is 99.99 wt.%, the power of radio frequency power supply is 130W, the set value of working air pressure is 0.5Pa, the deposition temperature is room temperature, and the rotating speed of the basal disc is 15 r/min.
The thickness of the obtained TaNbTiAl refractory entropy alloy coating is about 3.3 mu m, the nano indentation hardness of the TaNbTiAl refractory entropy alloy coating is 8.5GPa, and the modulus is 120.0 GPa.
FIG. 1 shows a XRD diffraction result diagram of TaNbTi-based refractory medium entropy alloy coating of the invention;
FIG. 2 shows a TEM high resolution image of TaNbTi-based refractory medium entropy alloy coating of the invention;
FIG. 3 shows SEM cross-sectional picture and EDS energy spectrum analysis chart of TaNbTi-based refractory medium entropy alloy coating of the invention;
FIG. 4 shows a chart of nanoindentation hardness results for TaNbTi-based refractory mid-entropy alloy coatings of the present invention;
FIG. 5 shows an AFM micrograph of an entropic alloy coating in a TaNbTi-based refractory of the present invention.
The TaNbTi-based refractory mid-entropy alloy coating has the advantages of uniform and compact structure, extremely small roughness, less defects, uniform distribution of internal alloy elements, high purity and good film-substrate combination. The TaNbTi-based refractory medium-entropy alloy coating disclosed by the invention has excellent mechanical properties, oxidation resistance and corrosion resistance.
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A TaNbTi-based refractory entropy alloy coating is characterized in that the refractory entropy alloy coating is TaNbTiCr or TaNbTiAl, and the microstructure is a disordered amorphous structure.
2. The TaNbTi-based refractory mid-entropy alloy coating as claimed in claim 1, wherein the atomic percentage ratio of elements of TaNbTiCr and TaNbTiAl is 1:1:1: 1.
3. The TaNbTi-based refractory entropy alloy coating is characterized in that a cross-section fracture of the refractory entropy alloy coating is in a dimple-like pattern shape.
4. The TaNbTi-based refractory entropy alloy coating is characterized in that the thickness of the refractory entropy alloy coating is 2.3-3.3 μm.
5. The TaNbTi-based refractory entropy alloy coating is characterized in that the TaNbTiCr refractory entropy alloy coating has the nanoindentation hardness of 8.4-9.0 GPa and the modulus of 120.0-130.0 GPa;
the TaNbTiAl refractory intermediate entropy alloy coating has the nano indentation hardness of 8.0-8.5 GPa and the modulus of 110.0-120.0 GPa.
6. The TaNbTi-based refractory entropy alloy coating as claimed in claim 1, wherein the TaNbTiCr refractory entropy alloy coating has a surface roughness of R a ：0.75nm；
The surface roughness of the TaNbTiAl refractory intermediate entropy alloy coating is R a ：0.20nm。
7. A method for preparing TaNbTi-based refractory entropy amorphous alloy coating in any one of claims 1-6, which comprises the following steps:
depositing and preparing a TaNbTi-based refractory intermediate entropy alloy coating on a substrate by adopting a magnetron sputtering co-sputtering method, and then cooling to room temperature to obtain the TaNbTi-based refractory intermediate entropy alloy coating;
the magnetron sputtering co-sputtering method comprises the following steps:
carrying out co-sputtering by adopting a TaNbTi alloy target and a Cr target or an Al target, wherein the deposition pressure is 0.3-0.5 Pa, the deposition temperature is room temperature, and the rotating speed of a basal disc is generally 15 r/min;
the direct current power of the TaNbTi alloy target is 90-120W, the radio frequency power supply power of the Cr target is 40-60W, the purity of the Al target is 99.99 wt%, and the radio frequency power supply power is 110-130W.
8. The method for preparing the TaNbTi-based refractory mid-entropy amorphous alloy coating according to claim 7, characterized in that a substrate is cleaned and vacuum-etched before magnetron sputtering co-sputtering.
9. The preparation method of the TaNbTi-based refractory entropy amorphous alloy coating of claim 7, wherein the TaNbTi alloy target has an atomic ratio of: ta: Nb: Ti 30.8:32.5:36.7 at.%.
10. The method for preparing the TaNbTi-based refractory mid-entropy amorphous alloy coating according to claim 7, characterized in that two TaNbTi alloy targets are adopted for co-sputtering to prepare the TaNbTi-based refractory mid-entropy alloy coating.
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