CN115322013A - Method for preparing metal carbide coating on surface of graphite device - Google Patents
Method for preparing metal carbide coating on surface of graphite device Download PDFInfo
- Publication number
- CN115322013A CN115322013A CN202210890477.6A CN202210890477A CN115322013A CN 115322013 A CN115322013 A CN 115322013A CN 202210890477 A CN202210890477 A CN 202210890477A CN 115322013 A CN115322013 A CN 115322013A
- Authority
- CN
- China
- Prior art keywords
- coating
- metal
- graphite
- graphite device
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000000576 coating method Methods 0.000 title claims abstract description 96
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 96
- 239000010439 graphite Substances 0.000 title claims abstract description 96
- 239000011248 coating agent Substances 0.000 title claims abstract description 92
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 68
- 239000002184 metal Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 54
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 6
- 230000005684 electric field Effects 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 34
- 229910052786 argon Inorganic materials 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 15
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 4
- 229910003468 tantalcarbide Inorganic materials 0.000 abstract description 24
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000013077 target material Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000004544 sputter deposition Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 23
- 239000007888 film coating Substances 0.000 description 12
- 238000009501 film coating Methods 0.000 description 12
- 229910052735 hafnium Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- -1 argon ions Chemical class 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000002679 ablation Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000870659 Crassula perfoliata var. minor Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5057—Carbides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a method for preparing a metal carbide coating on the surface of a graphite device, which ionizes inert working gas under the action of an electric field to generate high-energy ions to bombard a metal target material, and deposits metal atoms on the surface of the substrate of the graphite device to form a film so as to obtain a compact metal coating; and placing the graphite device covered with the metal coating in inert working gas, heating to a first temperature, preserving heat, and finally cooling along with the furnace to obtain the graphite device with the compact metal carbide coating on the surface. The method combines a magnetron sputtering metal tantalum coating and a high-temperature heating method, utilizes the high-temperature reaction of graphite and a tantalum film to generate the tantalum carbide coating with stronger bonding force, has uniform and controllable coating thickness, does not generate harmful interface reaction, and has short preparation period; and provides a method for preparing the composite coating by double-target sputtering.
Description
Technical Field
The invention belongs to the field of preparation of semiconductors and thin film materials, relates to a method for preparing a coating on a thin film of a graphite device, and particularly relates to a method for preparing a metal carbide coating on the surface of the graphite device, which has the advantages of short preparation period, no harmful interface reaction, uniform and controllable coating thickness and strong bonding force between the coating and a graphite matrix.
Background
Graphite materials are important conductive materials and structural materials in the modern industry due to the advantages of excellent high temperature resistance, excellent structural strength and chemical stability, good corrosion resistance, thermal shock resistance, excellent electric conductivity, thermal conductivity, plasticity and the like. The material has excellent application characteristics in the fields of machinery, electronics, chemical industry, metallurgy, nuclear energy, aerospace industry and the like. However, graphite materials are subject to problems of oxidative ablation, solid particle erosion, chemical corrosion, and molten salt erosion in high temperature environments. The coating material can effectively improve the oxidation resistance, corrosion resistance and wear resistance of the graphite substrate, wherein the tantalum carbide is an ultrahigh-temperature coating material with excellent performance, has the advantages of high melting point (3880 ℃), low thermal conductivity, good thermal shock resistance, stable chemical property and the like, is one of excellent ablation resistance materials, and has good chemical compatibility and mechanical compatibility with the graphite material.
At present, the main methods for preparing tantalum carbide coatings on the surfaces of graphite devices are high-temperature chemical vapor deposition (HCVD), sol-gel methods and the like.
Wherein the high temperature chemical vapor deposition method uses TaC l5 ，C 3 H 6 ，H 2 Ar is a gas phase chemical reaction system, ar is used as a diluting and carrying gas, taC l5 As a source of Ta, C 3 H 6 As a C source, the graphite device was placed in a CVD furnace and the surface reacted to form a TaC coating. The sol-gel process includes mixing TaC powder, adhesive resin, sintering agent and other organic matter to prepare sol, painting the sol on graphite base with a spray gun or a paint brush, and heating to high temperature to form compact tantalum carbide film.
The limitation of the reaction temperature of the high-temperature chemical vapor deposition method leads free carbon on the deposition surface to be accumulated, so that the tantalum carbide coating deviates from the stoichiometric ratio and has low coating density; and, as carbon source, hydrocarbons, acetylenic substances and H 2 When a large amount of the catalyst enters a system, certain danger exists at high temperature; in addition, the deposition process is time consuming and has poor adhesion strength。
The raw materials used by the sol-gel method are expensive, and some raw materials are organic matters and are harmful to health; the overall sol-gel process usually takes a long time, often several days or weeks; the gel has a large number of micropores, and a lot of gas and organic matters can be escaped in the drying process and shrink.
Chinese patent application publication no: CN 105624608A, published 2016, 6, 1, entitled preparation method of a metal coating on the surface of a high-thermal-conductivity graphite film, discloses a method for performing metal coating on the surface of a graphite film by using a PVD method, and can also be popularized to non-metal materials. However, if the tantalum carbide coating is prepared on the graphite device by using the method and the tantalum carbide target is directly bombarded, the obtained coating is not strong in binding property with the graphite substrate and is very easy to fall off.
Disclosure of Invention
The invention provides a method for preparing a metal carbide coating on the surface of a graphite device, aiming at the problems of long consumed time, high material source price, low film quality and the like in the existing method for preparing the tantalum carbide coating on the surface of the graphite device. The method has the most obvious advantages that the method can rapidly prepare the high-quality film with excellent repeatability in a large area in vacuum equipment, has little limitation on materials and has better bonding force between the film and the substrate. In addition, if desired, the composite coating can be prepared using dual targets or even triple targets. The preparation period of the tantalum carbide coating is short, no harmful interface reaction occurs, the thickness of the coating is uniform and controllable, and the binding force between the coating and the graphite substrate is strong.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of producing a metal carbide coating on a surface of a graphitic device, said method comprising: ionizing the inert working gas under the action of an electric field to generate high-energy ions to bombard the metal target, and depositing metal atoms on the surface of the substrate of the graphite device to form a film so as to obtain a compact metal coating; and (3) placing the graphite device covered with the metal coating in inert working gas, heating to a first temperature, preserving heat, and finally cooling along with a furnace to obtain the graphite device with the compact metal coating on the surface.
The invention combines the magnetron sputtering metal tantalum coating and a high-temperature heating method, and utilizes the high-temperature reaction of graphite and a tantalum film to generate a tantalum carbide coating with stronger bonding force; and provides a method for preparing the composite coating by double-target sputtering.
As a preferred scheme of the present invention, the method specifically comprises the steps of:
1) Cleaning the graphite device substrate and drying;
2) Conveying the graphite device substrate obtained in the step 1) into a film coating chamber filled with a metal target, vacuumizing, adjusting the flow of inert working gas, adjusting bias voltage, bombarding the surface of the graphite device substrate for 5-15min, and closing the inert working gas and the bias voltage;
3) Heating the graphite device substrate obtained in the step 2) to a second temperature, and adjusting the magnetic field current, the bias voltage, the inert working gas flow, the coating temperature and the coating time to form a metal film on the graphite device substrate;
4) And (4) after the temperature is reduced to room temperature, placing the graphite device with the surface covered with the metal coating obtained in the step 3) in an environment filled with inert working gas, heating to a first temperature, preserving heat, and cooling along with a furnace to obtain the compact metal film coated graphite device.
In a preferred embodiment of the present invention, the metal target is one or two of a tantalum metal target and a hafnium metal target.
As a preferable scheme of the present invention, in step 1), the graphite device substrate is sequentially placed in acetone, absolute ethyl alcohol and deionized water, cleaned for ten minutes respectively by using ultrasound, taken out, immersed in absolute ethyl alcohol for one minute, taken out, and dried by dry nitrogen.
In a preferred embodiment of the present invention, in step 2), the inert working gas is supplied at a flow rate of 250 to 350sccm and a bias voltage of 750 to 850V.
As a preferable embodiment of the present invention, in step 3), when the metal target is a tantalum metal target, the second temperature is 280-350 ℃, the magnetic field current is 12-16A, the bias voltage is 130-160V, and the inert working gas flow rate is 80-120sccm.
As a preferable scheme of the present invention, in the step 3), when the metal target is a tantalum metal target and a hafnium metal target, the second temperature is 280-350 ℃, the magnetic field current of the tantalum-containing metal target is 10-13A, the bias voltage is 110-130V, the magnetic field current of the hafnium-containing metal target is 15-18A, the bias voltage is 170-190V, and the inert working gas flow rate is 80-120sccm.
As a preferable scheme of the invention, the first temperature is 1400-1600 ℃, and the heat preservation time is 5-7h.
As a preferable scheme of the invention, in the step 3), the film plating time is 2min-150min.
In a preferred embodiment of the present invention, the inert working gas is argon.
Compared with the prior art, the invention has the following beneficial effects:
1) The tantalum carbide coating prepared by the method has strong bonding force with a graphite substrate, uniform and controllable coating thickness, no harmful interface reaction and short preparation period.
2) The invention combines the magnetron sputtering metal tantalum coating and a high-temperature heating method, and utilizes the high-temperature reaction of graphite and a tantalum film to generate the tantalum carbide coating with stronger bonding force.
3) The invention also provides a method for preparing the composite coating by double-target sputtering.
Drawings
Fig. 1 is a drawing of graphite sheets prepared in accordance with the present invention having tantalum carbide coatings of varying thicknesses.
Fig. 2 is a dual-target metal-coated graphite sheet prepared in accordance with the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the invention can be purchased from the market, and the equipment used in the invention is the existing equipment.
The invention discloses a method for preparing a metal carbide coating on the surface of a graphite device, which comprises the following steps: ionizing the inert working gas under the action of an electric field to generate high-energy ions to bombard the metal target, and depositing metal atoms on the surface of the substrate of the graphite device to form a film so as to obtain a compact metal coating; and (3) placing the graphite device covered with the metal coating in inert working gas, heating to a first temperature, preserving heat, and finally cooling along with the furnace to obtain the graphite device with the compact metal coating on the surface.
The principle of magnetron sputtering is as follows: under the action of an electric field E, electrons flying to the graphite substrate collide with argon atoms to ionize and generate Ar positive ions and new electrons, the Ar positive ions bombard the tantalum target material at high energy under the action of the electric field to sputter the target material, and the sputtered tantalum atoms are deposited on the graphite substrate to form a film. The so-called magnetic control is that a permanent magnet is arranged on the back of a cathode target to generate an orthogonal electromagnetic field, so that secondary electrons emitted from the surface of the target are localized in a plasma region near the surface, the probability of collision between the secondary electrons and working gas molecules is improved, and the ionization efficiency is improved.
The graphite device substrate needs to be ultrasonically cleaned prior to being placed into the loadlock chamber. Then the graphite is put into a sample sending chamber, is sent to a film coating chamber through a transmission rod, is vacuumized, and bombards the surface of the graphite by argon ions to carry out ion cleaning so as to remove chemisorption on the surface. And (4) adjusting various parameters including magnetic field current, bias voltage, argon flow, coating temperature, coating time and the like to perform coating. In the coating process, the graphite device substrate can be properly heated, and the substrate is heated to about 300 ℃ through a heating system, so that the adhesive force of the film can be improved. The heat generated by the tantalum atoms during sputtering can be combined to help the crystallization of the film and the diffusion of the tantalum atoms in the graphite.
After the graphite device substrate is taken out, the graphite device substrate is placed into a high-temperature furnace filled with argon, and high-temperature (1500 ℃) heating is carried out to ensure that tantalum atoms are diffused into the graphite and react with the graphite. The tantalum carbide coating obtained by the reaction has larger bonding force with the graphite device substrate, is more tightly bonded and is not easy to fall off.
It is noted that the method of the present invention can not only prepare tantalum carbide coating, but also perform dual target sputtering using dual targets, such as metal hafnium and metal tantalum targets, and adjust experimental parameters of the two targets to control the atomic number ratio of the two metal sputtering. After obtaining the uniform mixed film of tantalum and hafnium, placing the film in a high-temperature furnace filled with argon atmosphere for heating to obtain Ta 1-x Hf x And C solid solution strengthening coating.
Ta in accordance with the literature "Preparation and analysis properties of Hf (Ta) C co-position coatings for carbon/carbon composites" (corosion Science 66 (2013) 177-182) 1-x Hf x The C solid solution is a coating with better property than TaC, and the thermal shock resistance, the oxidation resistance and the bonding property with graphite base of the coating are far better than that of TaC.
Example 1
The embodiment provides a method for preparing a metal carbide coating on the surface of a graphite device, which comprises the following steps:
1) Cleaning a graphite device substrate, sequentially putting the substrate into acetone, absolute ethyl alcohol and deionized water, cleaning for ten minutes respectively by using ultrasound, taking out, immersing in the absolute ethyl alcohol for one minute, taking out, and drying the substrate by dry nitrogen.
2) Putting the cleaned graphite device substrate into a sample feeding chamber, feeding the sample into a film coating chamber filled with a tantalum target material through a conveying rod, and vacuumizing to 10 DEG -3 Pa, regulating the argon gas flow to 300sccm, regulating the bias voltage to 800V, controlling the temperature at room temperature, bombarding the graphite surface with argon ions for about ten minutes, performing ion cleaning to remove chemisorption on the surface, and then closing the argon gas flow and the bias voltage.
3) In the embodiment, after the graphite substrate is stabilized to 300 ℃, for sputtering of a single target (tantalum), the set magnetic field current is controlled to be 15A, the bias voltage is controlled to be 150V, and the argon flow is set to be Ar =100sccm, and then the coating is started, wherein tantalum metal films with different thicknesses are coated on the graphite substrate by controlling the coating time (the time is respectively 2min,3min,6min,12min,30min,1.5h, and 2.5h).
4) After the film coating is finished, cooling to room temperature, sampling, then placing in a muffle furnace filled with argon environment, heating to 1500 ℃, preserving heat for 6 hours, and cooling along with the furnace to obtain a compact tantalum carbide film coating.
Example 2
The embodiment provides a method for preparing a metal carbide coating on the surface of a graphite device, which comprises the following steps:
1) Cleaning a graphite device substrate, sequentially putting the substrate into acetone, absolute ethyl alcohol and deionized water, cleaning for ten minutes respectively by using ultrasound, taking out, immersing in the absolute ethyl alcohol for one minute, taking out, and drying the substrate by dry nitrogen.
2) Putting the cleaned graphite device substrate into a sample feeding chamber, feeding the sample into a coating chamber filled with a tantalum target material and a hafnium target material through a conveying rod, and vacuumizing to 10 DEG -3 Pa, regulating the argon gas flow to 300sccm, regulating the bias voltage to 800V, controlling the temperature at room temperature, bombarding the graphite surface with argon ions for about ten minutes, performing ion cleaning to remove chemisorption on the surface, and then closing the argon gas flow and the bias voltage.
3) In the embodiment, after the graphite substrate is stabilized to 300 ℃, the target position magnetic field current with the metal tantalum target material is controlled to be 12A, the bias voltage is set to be 120V, the target position magnetic field current with the metal hafnium target material is controlled to be 18A, the bias voltage is set to be 180V, the argon flow is set to be Ar =100sccm, and at the moment, the coating rates of the two target materials are consistent and are 35nm/min. Then, film coating is started, the film coating time is 45min, and tantalum and hafnium co-plating films with different thicknesses are coated on the graphite substrate.
4) After the film coating is finished, the temperature is reduced to room temperature, the sample is taken, then the sample is placed in a muffle furnace filled with argon environment and heated to 1500 ℃, the temperature is kept for 6 hours, and the sample is cooled along with the furnace, so that the compact tantalum carbide-hafnium carbide coating can be obtained.
Example 3
The embodiment provides a method for preparing a metal carbide coating on the surface of a graphite device, which comprises the following steps:
1) Cleaning a graphite device substrate, sequentially putting the substrate into acetone, absolute ethyl alcohol and deionized water, cleaning for ten minutes respectively by using ultrasound, taking out, immersing in the absolute ethyl alcohol for one minute, taking out, and drying the substrate by dry nitrogen.
2) Putting the cleaned graphite device substrate into a sample feeding chamber, feeding the sample into a coating chamber filled with a tantalum target material through a conveying rod, and vacuumizing to 10 DEG -3 Pa, regulating argon gas flow to 350sccm, regulating bias voltage to 850V, controlling the temperature at room temperature, bombarding the graphite surface with argon ions for about ten minutes, performing ion cleaning to remove chemisorption on the surface, and then closing the argon gas flow and the bias voltage.
3) In the embodiment, after the graphite substrate is stabilized to 350 ℃, the magnitude of the set magnetic field current is controlled to be 16A, the magnitude of the bias voltage is controlled to be 160V, the magnitude of the argon flow is set to be Ar =120sccm for single target (tantalum) sputtering, then the coating is started, the coating time is 1h, and tantalum metal films with different thicknesses are coated on the graphite substrate.
4) After the film coating is finished, cooling to room temperature, sampling, then placing in a muffle furnace filled with argon atmosphere, heating to 1600 ℃, preserving heat for 7 hours, and cooling along with the furnace to obtain a compact tantalum carbide film coating.
Example 4
The embodiment provides a method for preparing a metal carbide coating on the surface of a graphite device, which comprises the following steps:
1) Cleaning a graphite device substrate, sequentially putting the substrate into acetone, absolute ethyl alcohol and deionized water, cleaning for ten minutes respectively by using ultrasound, taking out, immersing in the absolute ethyl alcohol for one minute, taking out, and drying the substrate by dry nitrogen.
2) Putting the cleaned graphite device substrate into a sample feeding chamber, feeding the sample into a coating chamber filled with a tantalum target material through a conveying rod, and vacuumizing to 10 DEG -3 Pa, regulating the argon gas flow to 250sccm, regulating the bias voltage to 750V, controlling the temperature at room temperature, bombarding the graphite surface with argon ions for about ten minutes, performing ion cleaning to remove chemisorption on the surface, and then closing the argon gas flow and the bias voltage.
3) In the embodiment, after the graphite substrate is stabilized to 280 ℃, the magnitude of the set magnetic field current is controlled to be 12A, the magnitude of the bias voltage is controlled to be 130V, the magnitude of the argon flow is set to be Ar =800sccm for single target (tantalum) sputtering, then the coating is started, the coating time is 30min, and tantalum metal films with different thicknesses are coated on the graphite substrate.
4) And after the film coating is finished, cooling to room temperature, sampling, placing in a muffle furnace filled with argon environment, heating to 1400 ℃, preserving the heat for 5 hours, and cooling along with the furnace to obtain the compact tantalum carbide film coating.
Referring to fig. 1, fig. 1 is a graph of a graphite flake real object after metal tantalum thin films with different thicknesses are obtained by the method of example 1 and heated to 1500 ℃ in a high temperature furnace for 6 hours, the thickness of the metal tantalum thin film is controlled by controlling the magnetron sputtering coating time, from left to right, the thickness of the coating metal tantalum thin film is 50nm,100nm,200nm,400nm,1 μm,3 μm and 5 μm in sequence, and the coating time is respectively 2min,3min,6min,12min,30min,1.5h and 2.5h. As shown in the figure, after coating a metal tantalum film with the thickness of more than 3 mu m and heating at high temperature, a very compact tantalum carbide coating can be obtained.
Referring to fig. 2, fig. 2 shows that a purple dense tantalum carbide-hafnium carbide coating can be obtained by placing the obtained 3 μm thick tantalum and hafnium co-coated graphite sheet into a high temperature furnace to be heated to 1500 ℃ and preserving the temperature for 6 hours after the double-target (tantalum and hafnium) sputtering is carried out for 45 minutes.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalents to the disclosed technology without departing from the spirit and scope of the present invention, and all such changes, modifications and equivalents are intended to be included therein as equivalents of the present invention; meanwhile, any equivalent changes, modifications and evolutions of the above embodiments according to the essential technology of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. A method of producing a metal carbide coating on a surface of a graphite device, the method comprising: ionizing the inert working gas under the action of an electric field to generate high-energy ions to bombard the metal target, and depositing metal atoms on the surface of the substrate of the graphite device to form a film so as to obtain a compact metal coating; and placing the graphite device covered with the metal coating in inert working gas, heating to a first temperature, preserving heat, and finally cooling along with the furnace to obtain the graphite device with the compact metal carbide coating on the surface.
2. The method for preparing the metal carbide coating on the surface of the graphite device according to claim 1, which comprises the following steps:
1) Cleaning the graphite device substrate and drying;
2) Conveying the graphite device substrate obtained in the step 1) into a coating chamber filled with a metal target, vacuumizing, adjusting the flow of inert working gas, adjusting bias voltage, bombarding the surface of the graphite device substrate for 5-15min, and closing the inert working gas and the bias voltage;
3) Heating the graphite device substrate obtained in the step 2) to a second temperature, and adjusting the magnetic field current, the bias voltage, the inert working gas flow, the coating temperature and the coating time to form a metal film on the graphite device substrate;
4) And (3) after the temperature is reduced to room temperature, placing the graphite device with the surface covered with the metal coating obtained in the step 3) in an environment filled with inert working gas, heating to a first temperature, preserving heat, and cooling along with a furnace to obtain the graphite device with the compact metal carbide coating.
3. The method for preparing a metal carbide coating on the surface of a graphite device according to claim 1 or 2, wherein the metal target is one or both of a tantalum metal target and a hafnium metal target.
4. The method of claim 2, wherein in step 1), the graphite device substrate is sequentially placed in acetone, absolute ethyl alcohol and deionized water, washed with ultrasound for ten minutes each, taken out, immersed in absolute ethyl alcohol for one minute, taken out, and the substrate is dried with dry nitrogen.
5. The method for preparing a metal carbide coating on the surface of a graphite device as claimed in claim 2, wherein the inert working gas is supplied at a flow rate of 250 to 350sccm and a bias voltage of 750 to 850V in step 2).
6. The method of claim 3, wherein in step 3), when the metal target is a tantalum target, the second temperature is 280-350 ℃, the magnetic field current is 12-16A, the bias voltage is 130-160V, and the inert working gas flow rate is 80-120sccm.
7. The method of claim 3, wherein in the step 3), when the metal targets are tantalum metal target and hafnium metal target, the second temperature is 280-350 ℃, the magnetic field current of the tantalum metal target is 10-13A, the bias voltage is 110-130V, the magnetic field current of the hafnium metal target is 15-18A, the bias voltage is 170-190V, and the inert working gas flow rate is 80-120sccm.
8. The method of claim 1 or 2, wherein the first temperature is 1400-1600 ℃ and the holding time is 5-7 hours.
9. The method for preparing the metal carbide coating on the surface of the graphite device as claimed in claim 2, wherein in the step 3), the coating time is 2min-150min.
10. A method of forming a metal carbide coating on a surface of a graphitic part according to claim 1 or 2 wherein the inert working gas is argon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210890477.6A CN115322013A (en) | 2022-07-27 | 2022-07-27 | Method for preparing metal carbide coating on surface of graphite device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210890477.6A CN115322013A (en) | 2022-07-27 | 2022-07-27 | Method for preparing metal carbide coating on surface of graphite device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115322013A true CN115322013A (en) | 2022-11-11 |
Family
ID=83919384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210890477.6A Pending CN115322013A (en) | 2022-07-27 | 2022-07-27 | Method for preparing metal carbide coating on surface of graphite device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115322013A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116444296A (en) * | 2023-05-04 | 2023-07-18 | 中南大学 | Method for preparing tantalum carbide coating on graphite substrate by molten salt method |
| CN117535640A (en) * | 2023-11-22 | 2024-02-09 | 湖州幄肯中欣新能源科技有限公司 | Special-shaped piece |
| CN117587361A (en) * | 2023-11-28 | 2024-02-23 | 苏州清研半导体科技有限公司 | Preparation method of tantalum carbide coating |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041476A (en) * | 2010-12-30 | 2011-05-04 | 陕西科技大学 | Method for preparing cobalt titanate film by dual-target magnetron sputtering method |
| CN102373417A (en) * | 2011-11-08 | 2012-03-14 | 陕西科技大学 | Method for preparing antioxidant SiC coating on surface of graphite material |
| CN105624608A (en) * | 2015-12-29 | 2016-06-01 | 上海交通大学 | Preparation method of metal coating on surface of high-thermal-conductivity graphite film |
| CN107058962A (en) * | 2017-03-29 | 2017-08-18 | 浙江大学 | A kind of method that low temperature magnetic sputtering prepares low-resistivity titanium nitride membrane |
| CN108411266A (en) * | 2018-04-04 | 2018-08-17 | 中国航发北京航空材料研究院 | A kind of method of metal surface growth metal carbides |
| CN113265647A (en) * | 2021-05-28 | 2021-08-17 | 浙江大学杭州国际科创中心 | Preparation method of two-dimensional material |
-
2022
- 2022-07-27 CN CN202210890477.6A patent/CN115322013A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041476A (en) * | 2010-12-30 | 2011-05-04 | 陕西科技大学 | Method for preparing cobalt titanate film by dual-target magnetron sputtering method |
| CN102373417A (en) * | 2011-11-08 | 2012-03-14 | 陕西科技大学 | Method for preparing antioxidant SiC coating on surface of graphite material |
| CN105624608A (en) * | 2015-12-29 | 2016-06-01 | 上海交通大学 | Preparation method of metal coating on surface of high-thermal-conductivity graphite film |
| CN107058962A (en) * | 2017-03-29 | 2017-08-18 | 浙江大学 | A kind of method that low temperature magnetic sputtering prepares low-resistivity titanium nitride membrane |
| CN108411266A (en) * | 2018-04-04 | 2018-08-17 | 中国航发北京航空材料研究院 | A kind of method of metal surface growth metal carbides |
| CN113265647A (en) * | 2021-05-28 | 2021-08-17 | 浙江大学杭州国际科创中心 | Preparation method of two-dimensional material |
Non-Patent Citations (1)
| Title |
|---|
| YA-LEI WANG等: "Preparation and ablation properties of Hf(Ta)C co-deposition coating for carbon/carbon composites" * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116444296A (en) * | 2023-05-04 | 2023-07-18 | 中南大学 | Method for preparing tantalum carbide coating on graphite substrate by molten salt method |
| CN116444296B (en) * | 2023-05-04 | 2024-02-02 | 中南大学 | Method for preparing tantalum carbide coating on graphite substrate by molten salt method |
| CN117535640A (en) * | 2023-11-22 | 2024-02-09 | 湖州幄肯中欣新能源科技有限公司 | Special-shaped piece |
| CN117535640B (en) * | 2023-11-22 | 2024-09-06 | 湖州幄肯中欣新能源科技有限公司 | Special-shaped piece |
| CN117587361A (en) * | 2023-11-28 | 2024-02-23 | 苏州清研半导体科技有限公司 | Preparation method of tantalum carbide coating |
| CN117587361B (en) * | 2023-11-28 | 2024-06-11 | 苏州清研半导体科技有限公司 | Preparation method of tantalum carbide coating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115322013A (en) | Method for preparing metal carbide coating on surface of graphite device | |
| CN107620033B (en) | Preparation method of high-purity strong dense MAX phase coating | |
| CN103668095B (en) | A kind of high power pulse plasma enhancing combined magnetic-controlled sputter deposition apparatus and using method thereof | |
| CN102409293A (en) | Preparation method of alumina film | |
| CN105908131B (en) | It is a kind of can thermally grown oxide aluminium film TiAl coatings and preparation method thereof | |
| CN113652644B (en) | TiAl coating capable of improving high-temperature oxidation resistance of titanium alloy and preparation method thereof | |
| CN107937873A (en) | Transition metal boride coating, carbon transition metal boride composite coating, preparation method and application and the cutting element of carbon doping | |
| CN113684453B (en) | Film with low secondary electron emission coefficient and preparation method thereof | |
| CN113913751A (en) | Cu-high-entropy alloy film and preparation method thereof | |
| CN111575652A (en) | Vacuum coating equipment and vacuum coating method | |
| CN103469164B (en) | Device and method for realizing plasma activation electron beam physical vapor deposition | |
| CN103173727A (en) | Preparation method of high-heat-conduction aluminum nitride thick film | |
| KR20130074647A (en) | Coated steel sheet and method for manufacturing the same | |
| CN115044879B (en) | Microporous coating device and coating method | |
| CN114540779B (en) | Composite cathode, magnetron sputtering coating equipment and coating method | |
| KR20130070433A (en) | Method of manufacturing max phase thin film | |
| WO2017020534A1 (en) | Silver/aluminium alloy crystal oscillation plate coating process | |
| WO2017020535A1 (en) | Copper/aluminium alloy crystal oscillation plate coating process | |
| Beilis et al. | Metallic film deposition using a vacuum arc plasma source with a refractory anode | |
| CN108411266A (en) | A kind of method of metal surface growth metal carbides | |
| US20210050192A1 (en) | Magnetron sputtering device | |
| CN109957757B (en) | Method for preparing ultra-thick Ti-Al-C ternary coating by two-step PVD (physical vapor deposition) technology | |
| CN106637116A (en) | Simple preparation of secondary electron emission film | |
| Swaroop et al. | Ion-Plated Copper—Steel Graded Interface | |
| KR20110117528A (en) | Method for coating aluninum on steel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221111 |