CN116516228A - Super-hard wear-resistant refractory high-entropy alloy film and preparation method thereof - Google Patents
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- 239000000956 alloy Substances 0.000 title claims abstract description 90
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 238000004544 sputter deposition Methods 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 15
- 239000013077 target material Substances 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 238000005477 sputtering target Methods 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 239000006104 solid solution Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000713 high-energy ball milling Methods 0.000 claims description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000000498 ball milling Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- 238000005728 strengthening Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 239000003870 refractory metal Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004372 laser cladding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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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
- C23C14/22—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1053—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by induction
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Abstract
The invention belongs to the technical field of wear-resistant alloy materials, and relates to a superhard wear-resistant refractory high-entropy alloy film and a preparation method thereof. The super-hard wear-resistant refractory high-entropy alloy film has the characteristics of super-fine nanocrystalline, super-normal hardness and wear-resistant performance and the like. The preparation method comprises the following steps: preparing an NbMoWTA refractory high-entropy alloy target; the sputtering target is formed by ball milling and mixing Nb, mo, W, ta metal powder and then performing plasma sintering at high temperature; sputtering the refractory high-entropy alloy target material on a silicon substrate by using a magnetron sputtering method to form a film, thereby obtaining the superhard wear-resistant refractory high-entropy alloy film. The preparation process is simple, stable and controllable; the obtained product has fine and uniform crystal grains, excellent mechanical property and wear resistance. This provides a necessary condition for achieving refractory high-entropy alloys in extreme engineering applications.
Description
Technical Field
The invention relates to the technical field of wear-resistant alloy materials, in particular to a superhard wear-resistant refractory high-entropy alloy film and a preparation method thereof.
Background
The high-entropy alloy is formed by mixing four or more than four alloy elements in equimolar ratio or nearly equimolar ratio, and the multi-component of the high-entropy alloy can lead to higher mixed entropy, and the high-entropy alloy presents a high entropy effect in thermodynamics, often forms a single-phase solid solution structure instead of brittle intermetallic compounds, so that the high-entropy alloy shows excellent mechanical and physical-chemical properties such as high strength, radiation resistance, corrosion resistance and the like compared with the traditional alloy. The refractory high-entropy alloy is a high-entropy alloy formed by mixing four or more refractory metal elements (such as Nb, mo, W, ta, V, zr, hf) in equal atomic ratio or near equal atomic ratio, and because the components have the characteristics of high melting point and the like, compared with the traditional nickel-based and cobalt-based high-temperature alloys, the refractory high-entropy alloy has higher tempering resistance and high-temperature softening resistance and is expected to be applied to aviation, aerospace, nuclear energy and other high Wen Keke working conditions.
However, due to the high melting point of the refractory high-entropy alloy, the conventional arc melting method and powder metallurgy method are difficult to prepare the refractory high-entropy alloy with uniform structure and single-phase structure, and the development of the refractory high-entropy alloy is restricted; secondly, the cost of the refractory high-entropy alloy is too high, and the refractory high-entropy alloy is difficult to push to large-scale application, so that the refractory high-entropy alloy film is coated on the surface of the existing part or has greater economic benefit.
At present, the preparation method of the film mainly comprises a magnetron sputtering method, a laser cladding method, a plasma spraying method and other technological methods. The magnetron sputtering technology has the advantages of high deposition speed, capability of depositing on various substrates, high purity, uniformity, compactness, capability of accurately regulating and controlling thickness and the like, and is an ideal technology for pushing the film to actual production and application; on the other hand, the technology only relates to the physical sputtering process of the target material, and does not need to be heated and melted, so that the technology is very suitable for preparing the refractory high-entropy alloy system film.
In addition, due to the different element properties among refractory high-entropy alloy components, the coating material with a special structure is hopefully prepared through reasonable regulation and control of a magnetron sputtering process, so that remarkable mechanical and friction properties are obtained.
Disclosure of Invention
The invention aims to provide a superhard wear-resistant refractory high-entropy alloy film and a preparation method thereof, so as to realize the technical effects proposed in the background technology.
In order to achieve the above purpose, the invention provides the following technical scheme: an ultra-hard wear-resistant refractory high-entropy alloy film comprises the following alloy components in percentage by atom: nb, mo, W, ta.
Preferably, the super-hard wear-resistant refractory high-entropy alloy film has a single-phase BCC solid solution structure, the grain size is not higher than 25nm, and the film thickness is 3.0-3.5 mu m.
Preferably, the original structure of the super-hard wear-resistant refractory high-entropy alloy film shows an amplitude-modulated lamellar decomposition substructure with a periodicity of 5-10 nm.
Preferably, the nanometer pressed hardness of the super-hard wear-resistant refractory high-entropy alloy film is 20-25 GPa, and the wear rate is 1.0x10 -5 ～1.4×10 -5 mm 3 /(N·m)。
The preparation method of the superhard wear-resistant refractory high-entropy alloy film specifically comprises the following steps:
step one: preparing a sputtering target: mixing the metal powder of each simple substance element Nb, mo, W, ta for 24-30 hours by using a high-energy ball milling method according to an equimolar ratio, and then preparing the NbMoWTA refractory high-entropy alloy target material with an equiatomic ratio by adopting a plasma sintering technology at 1500-1700 ℃;
step two: film deposition: and (3) sputtering the alloy target material obtained in the step one on a silicon substrate to form a film by using a magnetron sputtering technology, wherein the sputtering power is 100-120W, and the bias voltage is-80 to-100V, so that the superhard wear-resistant refractory high-entropy alloy film is obtained.
Preferably, the silicon substrate is a single-sided polished monocrystalline silicon substrate which is cleaned by acetone and absolute ethyl alcohol and dried.
Preferably, the deposition rate in the magnetron sputtering technology is 0.19-0.22 nm/s.
Preferably, the magnetron sputtering technology adopts direct current power supply sputtering.
Preferably, the magnetron sputtering technology adopts Ar with purity as high as 99.99% as an ionization gas.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the super-hard wear-resistant refractory high-entropy alloy film has the advantages of high deposition speed, easy process regulation and control, accurate and controllable film thickness, high economic benefit and the like.
2. The super-hard wear-resistant refractory high-entropy alloy film and the preparation method thereof have the advantages that the surface of the prepared super-hard wear-resistant refractory high-entropy alloy film is smooth, the structure is compact, the grain size is not higher than 25nm, the super-hard wear-resistant refractory high-entropy alloy film has the characteristics of super-fine nanocrystalline, the film thickness is 3.0-3.5 mu m, the film base binding force is good, and the service requirements of key wear-resistant parts can be directly met; in addition, through process control, the W, ta element in the refractory alloy element is segregated by adopting specific modes of working air pressure, power supply, deposition rate, matrix rotation, substrate bias, ionized gas protection after deposition and the like, so that an amplitude-modulated layered decomposition substructure with a periodicity of 5-10 nm is formed, and a structural foundation is provided for realizing the super-hard and ultra-wear-resistant properties of the refractory high-entropy alloy.
3. The nanometer pressed hardness of the super-hard wear-resistant refractory high-entropy alloy film is 20-25 GPa, and the wear rate is 1.0x10 -5 ～1.4×10 -5 mm 3 /(NM) wherein the superposition of the solid solution strengthening of the multiple principal elements, the ultra-fine nanocrystalline strengthening effect, the unique amplitude-modulated decomposition lamellar structure strengthening effect and the columnar grain boundary strengthening effect results in an ultra-high hardness; in addition, higher substrate bias results in more ion bombardment of the film during formation, increasing stress in the film, and thus resulting in high hardness of the film. The prepared film is higher than the refractory high-entropy alloy film with the same system studied at the present stage, and has wide application prospect.
Drawings
FIG. 1 is an XRD pattern of a NbMoWTA refractory high-entropy alloy film prepared in accordance with the present invention;
FIG. 2 is a cross-sectional image of a NbMoWTA refractory high-entropy alloy film prepared in accordance with the present invention; (a) a scanning electron microscope; (b) a transmission electron microscope;
FIG. 3 is a graph of the distribution of substructure elements of a NbMoWTA refractory high-entropy alloy film prepared according to the present invention;
FIG. 4 is a graph showing the hardness and wear resistance of a NbMoWTA refractory high-entropy alloy film prepared by the invention compared with the hardness and wear resistance of a refractory metal simple substance, refractory high-entropy alloy studied at the present stage: (a) hardness comparison; (b) wear rate comparison.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
a preparation method of a superhard wear-resistant refractory high-entropy alloy film comprises the following steps:
1) Mixing the metal powder of each simple substance element Nb, mo, W, ta for 24 hours by using a high-energy ball milling method according to an equimolar ratio, and then preparing the NbMoWTA refractory high-entropy alloy target material with the equimolar ratio by adopting a plasma sintering technology at 1700 ℃;
2) Sequentially ultrasonically cleaning a silicon substrate in acetone and absolute ethyl alcohol for 20min, and then drying the silicon substrate by using an electric hair drier to ensure that oil stains and water on the surface of the silicon substrate are removed;
3) Placing a silicon substrate and an alloy target material into a substrate table and a sputtering target table in a magnetron sputtering furnace respectively, adjusting the sputtering angle to be 30-45 degrees, fixing the sputtering angle to ensure that sputtered atoms can hit the center of a silicon wafer, starting a mechanical pump and a molecular pump in sequence, and vacuumizing the sputtering furnace to 4 multiplied by 10 -5 Pa, preparing a coating film;
4) Introducing high-purity Ar gas, ensuring the air pressure in the furnace to be 0.2Pa so as to ensure normal glow discharge and good coating quality, connecting a target table to a power supply of equipment, setting the sputtering power to be 100W, setting the bias voltage to be-80V, starting the power supply and starting pre-sputtering for 10min;
5) And (3) opening the target baffle and the substrate table to rotate, starting sputtering, sequentially closing the target baffle, a power supply and bias voltage after sputtering for 4 hours, and keeping the Ar gas introduced, so that the film finished product and the silicon substrate are cooled in Ar atmosphere for 1.5 hours, the phenomenon that the film surface stress is overlarge to cause fragmentation is avoided, then stopping ventilation, and taking out after vacuum withdrawal, thereby obtaining a superhard wear-resistant refractory high-entropy alloy film deposited on the silicon substrate.
Example 2:
a preparation method of a superhard wear-resistant refractory high-entropy alloy film comprises the following steps:
1) Mixing the metal powder of each simple substance element Nb, mo, W, ta for 24 hours by using a high-energy ball milling method according to an equimolar ratio, and then preparing the NbMoWTA refractory high-entropy alloy target material with the equimolar ratio by adopting a plasma sintering technology at 1700 ℃;
2) Sequentially ultrasonically cleaning a silicon substrate in acetone and absolute ethyl alcohol for 20min, and then drying the silicon substrate by using an electric hair drier to ensure that oil stains and water on the surface of the silicon substrate are removed;
3) Placing a silicon substrate and an alloy target material into a substrate table and a sputtering target table in a magnetron sputtering furnace respectively, adjusting the sputtering angle to be 30-45 degrees, fixing the sputtering angle to ensure that sputtered atoms can hit the center of a silicon wafer, starting a mechanical pump and a molecular pump in sequence, and vacuumizing the sputtering furnace to 4 multiplied by 10 -5 Pa，Preparing a coating film;
4) Introducing high-purity Ar gas, ensuring the air pressure in the furnace to be 0.3Pa so as to ensure normal glow discharge and good coating quality, connecting a target table to a power supply of equipment, setting the sputtering power to be 110W, setting the bias voltage to be-90V, starting the power supply and starting pre-sputtering for 10min;
5) And (3) opening the target baffle and the substrate table to rotate, starting sputtering, sequentially closing the target baffle, a power supply and bias voltage after sputtering for 4 hours, and keeping the Ar gas introduced, so that the film finished product and the silicon substrate are cooled in Ar atmosphere for 1.5 hours, the phenomenon that the film surface stress is overlarge to cause fragmentation is avoided, then stopping ventilation, and taking out after vacuum withdrawal, thereby obtaining a superhard wear-resistant refractory high-entropy alloy film deposited on the silicon substrate.
Example 3:
a preparation method of a superhard wear-resistant refractory high-entropy alloy film comprises the following steps:
1) Mixing the metal powder of each simple substance element Nb, mo, W, ta for 24 hours by using a high-energy ball milling method according to an equimolar ratio, and then preparing the NbMoWTA refractory high-entropy alloy target material with the equimolar ratio by adopting a plasma sintering technology at 1700 ℃;
2) Sequentially ultrasonically cleaning a silicon substrate in acetone and absolute ethyl alcohol for 20min, and then drying the silicon substrate by using an electric hair drier to ensure that oil stains and water on the surface of the silicon substrate are removed;
3) Placing a silicon substrate and an alloy target material into a substrate table and a sputtering target table in a magnetron sputtering furnace respectively, adjusting the sputtering angle to be 30-45 degrees, fixing the sputtering angle to ensure that sputtered atoms can hit the center of a silicon wafer, starting a mechanical pump and a molecular pump in sequence, and vacuumizing the sputtering furnace to 4 multiplied by 10 -5 Pa, preparing a coating film;
4) Introducing high-purity Ar gas, ensuring the air pressure in the furnace to be 0.2Pa so as to ensure normal glow discharge and good coating quality, connecting a target table to a power supply of equipment, setting the sputtering power to be 120W, setting the bias voltage to be-100V, starting the power supply and starting pre-sputtering for 10min;
5) And (3) opening the target baffle and the substrate table to rotate, starting sputtering, sequentially closing the target baffle, a power supply and bias voltage after sputtering for 4 hours, and keeping the Ar gas introduced, so that the film finished product and the silicon substrate are cooled in Ar atmosphere for 1.5 hours, the phenomenon that the film surface stress is overlarge to cause fragmentation is avoided, then stopping ventilation, and taking out after vacuum withdrawal, thereby obtaining a superhard wear-resistant refractory high-entropy alloy film deposited on the silicon substrate.
Since the properties of the superhard wear-resistant refractory high-entropy alloy films prepared in examples 1 to 3 are substantially the same, the superhard wear-resistant refractory high-entropy alloy film prepared in example 1 will be described below as an example.
FIG. 1 is an XRD pattern of a NbMoWTA refractory high-entropy alloy film prepared by the invention, and it can be seen that the film exhibits a single body-centered cubic solid solution structure and has a preferred orientation of the (110) crystal face, and the intensity of the diffraction peak is attributed to fine crystal grains therein.
FIG. 2 is a cross-sectional scanning electron microscope and transmission electron microscope image of a NbMoWTA refractory high-entropy alloy film prepared by the present invention, showing that the grains grow columnar perpendicular to the silicon substrate; the crystal grain size is extremely small and the average size is not more than 25nm as can be seen by a transmission electron microscope with higher magnification.
FIG. 3 is an image of the distribution of the substructure elements of a NbMoWTA refractory high-entropy alloy prepared by the present invention, where the W, ta element distribution is seen to be non-uniform, exhibiting amplitude modulated decomposition substructure with periodicity of 5-10 nm. The amplitude modulation decomposition of the superfine nanocrystalline and the alloy element provides a structural basis for the excellent mechanical and wear-resistant properties of the film.
FIG. 4 is a graph comparing the hardness and wear resistance of the refractory high-entropy alloy film of NbMoWTA prepared by the invention with those of the refractory metal simple substance and the refractory high-entropy alloy studied in the prior art, and it can be seen that the refractory high-entropy alloy film of NbMoWTA prepared by the invention has the hardness exceeding 20GPa, which is superior to those of the refractory high-entropy alloy and the refractory metal simple substance of NbMoWTA series reported in the prior documents 1-4, and shows super-hard characteristics; the wear resistance is greatly superior to TiZrHfNb series, tiZrHfNbTa series and block NbMoWTA series refractory high-entropy alloy, and the wear rate level is 1.0 multiplied by 10 -5 ～1.4×10 -5 mm 3 And/(n·m), exhibiting super wear resistance.
The solid solution strengthening of multiple principal elements, the strengthening effect of superfine nano crystals, the strengthening effect of unique amplitude modulation decomposition substructure and the superposition effect of columnar crystal boundary strengthening lead to the film to obtain ultra-high hardness; in addition, higher substrate bias results in more ion bombardment of the film during the forming process, which increases internal stress in the film, and is one of the reasons for high hardness and abrasion resistance of the film.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (9)
1. The super-hard wear-resistant refractory high-entropy alloy film is characterized in that: comprises the following alloy components in percentage by atom: nb, mo, W, ta.
2. A superhard wear resistant refractory high entropy alloy film as claimed in claim 1, wherein: the superhard wear-resistant refractory high-entropy alloy film has a single-phase BCC solid solution structure, the grain size is not higher than 25nm, and the film thickness is 3.0-3.5 mu m.
3. A superhard wear resistant refractory high entropy alloy film as claimed in claim 1, wherein: the original structure of the super-hard wear-resistant refractory high-entropy alloy film shows an amplitude-modulated lamellar decomposition substructure with a periodicity of 5-10 nm.
4. A superhard wear resistant refractory high entropy alloy film as claimed in claim 1, wherein: the nanometer pressed hardness of the super-hard wear-resistant refractory high-entropy alloy film is 20-25 GPa, and the wear rate is 1.0x10 -5 ～1.4×10 -5 mm 3 /(N·m)。
5. A preparation method of a superhard wear-resistant refractory high-entropy alloy film is characterized by comprising the following steps: the method specifically comprises the following steps:
step one: preparing a sputtering target: mixing the metal powder of each simple substance element Nb, mo, W, ta for 24-30 hours by using a high-energy ball milling method according to an equimolar ratio, and then preparing the NbMoWTA refractory high-entropy alloy target material with an equiatomic ratio by adopting a plasma sintering technology at 1500-1700 ℃;
step two: film deposition: and (3) sputtering the alloy target material obtained in the step one on a silicon substrate to form a film by using a magnetron sputtering technology, wherein the sputtering power is 100-120W, and the bias voltage is-80 to-100V, so that the superhard wear-resistant refractory high-entropy alloy film is obtained.
6. The method for preparing the super-hard wear-resistant refractory high-entropy alloy film according to claim 5, which is characterized by comprising the following steps: the silicon substrate is a single-sided polished monocrystalline silicon substrate which is cleaned by acetone and absolute ethyl alcohol and dried.
7. The method for preparing the super-hard wear-resistant refractory high-entropy alloy film according to claim 5, which is characterized by comprising the following steps: the deposition rate in the magnetron sputtering technology is 0.19-0.22 nm/s.
8. The method for preparing the super-hard wear-resistant refractory high-entropy alloy film according to claim 5, which is characterized by comprising the following steps: the magnetron sputtering technology adopts direct current power supply sputtering.
9. The method for preparing the super-hard wear-resistant refractory high-entropy alloy film according to claim 5, which is characterized by comprising the following steps: the magnetron sputtering technology adopts Ar with purity up to 99.99% as an ionization gas.
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| CN110106490A (en) * | 2019-06-12 | 2019-08-09 | 大连理工大学 | A kind of high temperature resistant high-entropy alloy NbMoTaWV film and preparation method thereof |
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| KR20170027520A (en) * | 2015-09-02 | 2017-03-10 | 한국과학기술원 | Hight-entropy multioelement alloy with single phase and process for preparing the same |
| CN110106490A (en) * | 2019-06-12 | 2019-08-09 | 大连理工大学 | A kind of high temperature resistant high-entropy alloy NbMoTaWV film and preparation method thereof |
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