CN115819118A - Oxidation-resistant coating, graphite mold containing same and preparation method thereof - Google Patents
Oxidation-resistant coating, graphite mold containing same and preparation method thereof Download PDFInfo
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- CN115819118A CN115819118A CN202211491943.XA CN202211491943A CN115819118A CN 115819118 A CN115819118 A CN 115819118A CN 202211491943 A CN202211491943 A CN 202211491943A CN 115819118 A CN115819118 A CN 115819118A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 243
- 238000000576 coating method Methods 0.000 title claims abstract description 141
- 239000011248 coating agent Substances 0.000 title claims abstract description 140
- 230000003647 oxidation Effects 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 34
- 229910002804 graphite Inorganic materials 0.000 title claims description 182
- 239000010439 graphite Substances 0.000 title claims description 182
- 238000002360 preparation method Methods 0.000 title description 7
- 239000002131 composite material Substances 0.000 claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 60
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 57
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 55
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 55
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 54
- 238000004544 sputter deposition Methods 0.000 claims abstract description 53
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 61
- 229910052710 silicon Inorganic materials 0.000 claims description 60
- 239000010703 silicon Substances 0.000 claims description 60
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 28
- 150000003754 zirconium Chemical class 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 23
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 13
- 238000007747 plating Methods 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- -1 polyoxyethylene, carboxymethyl Polymers 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 6
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005121 nitriding Methods 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 4
- 239000002202 Polyethylene glycol Substances 0.000 claims 2
- 230000000149 penetrating effect Effects 0.000 claims 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 2
- 239000005543 nano-size silicon particle Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 216
- 230000007704 transition Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003963 antioxidant agent Substances 0.000 description 13
- 230000003078 antioxidant effect Effects 0.000 description 13
- 239000011521 glass Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 238000013003 hot bending Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Mold Materials And Core Materials (AREA)
Abstract
An oxidation resistant coating, characterized by: the anti-oxidation coating comprises a diamond-like carbon layer coated on the surface of a carbon substrate, a silicon nitride layer coated on the surface of the diamond-like carbon layer, and a metal oxide layer or a composite coating coated on the surface of the silicon nitride layer; wherein, the silicon nitride layer simultaneously infiltrates into the diamond-like coating and the metal oxide layer (or the composite coating) to form molecular-level links. The invention adopts a sputtering growth mode to generate a uniform and compact film on the surface of the carbonaceous substrate, and the film can effectively isolate the contact of oxygen and the carbonaceous substrate by coating the surface of the carbonaceous substrate at a complete molecular level.
Description
Technical Field
The invention relates to an anti-oxidation technology of a carbon matrix, in particular to an anti-oxidation coating, a graphite mold containing the anti-oxidation coating and a preparation method of the graphite mold, and belongs to the technical field of surface treatment of glass processing molds.
Background
The hot bending glass is curved glass formed by heating and softening plane glass in a mould, in the hot bending process, the mould needs to transfer heat to the glass, and the forming precision of a glass finished product cannot be influenced, so that the mould is required to have the performances of high temperature resistance, high heat conductivity, low expansion rate and high thermal shock resistance, and most of the existing hot bending moulds are made of graphite materials. However, the graphite material has poor oxidation resistance and is easily oxidized at high temperature, so that the precision of the glass is reduced, and meanwhile, the graphite mold has low strength, so that the phenomena of powder falling and edge breakage exist after long-term use, and finally, the service life of the mold is short.
In order to prolong the service life of the graphite mold and reduce the production cost, various methods for adding a coating on the surface of the graphite mold are provided in the prior art so as to enhance the oxidation resistance and other properties of the graphite mold. For example, the graphite mold is soaked in a suspension or a precursor solution containing an inorganic oxide, and then dried and heated, so that the inorganic oxide is attached to the surface of the graphite mold to improve the oxidation resistance of the graphite mold, but the scratch resistance of the graphite mold cannot be improved, the graphite mold cannot be prevented from falling powder, and meanwhile, the bonding force of the graphite mold can be damaged in the soaking process, so that the strength of the mold is reduced, and the mold is cracked and damaged in advance in the using process.
Disclosure of Invention
The invention provides an anti-oxidation coating, a graphite mold containing the anti-oxidation coating and a preparation method thereof, aiming at the problems in the prior art, the invention adopts a ternary system coating, firstly a diamond-like transition layer is sputtered on the surface of the graphite mold through a sputtering process, then a layer of metal silicon is sputtered, finally a layer of metal oxide is sputtered on the metal silicon or a composite coating is coated on the metal silicon, and finally the mold is put into an atmosphere furnace for high-temperature heat treatment to obtain the hot-bending graphite mold containing the anti-oxidation coating on the surface. The anti-oxidation coating obtained by the invention uniformly generates a compact film on the surface of the graphite mold in a sputtering growth mode, and the film can effectively isolate oxygen from contacting graphite and increase the mold strength by completely coating the graphite surface at a molecular level.
According to a first embodiment of the present invention, an oxidation resistant coating is provided.
The anti-oxidation coating comprises a diamond-like carbon layer coated on the surface of a carbon substrate, a silicon nitride layer coated on the surface of the diamond-like carbon layer, and a metal oxide layer or a composite coating coated on the surface of the silicon nitride layer. Wherein, the silicon nitride layer simultaneously infiltrates into the diamond-like coating and the metal oxide layer (or the composite coating) to form molecular-level links.
Preferably, the composite coating is prepared by mixing silica sol, aluminum salt, zirconium salt, binder and solvent. Preferably, the weight ratio of silica sol, aluminum salt, zirconium salt, binder and solvent is 0 to 80.
Preferably, the silica sol is one or more of nano silica dispersion liquid, ethyl silicate solution and sodium silicate.
Preferably, the aluminum salt is a soluble aluminum salt, preferably one or more of aluminum chloride, aluminum sulfate and aluminum nitrate.
Preferably, the zirconium salt is a soluble zirconium salt, preferably one or more of zirconium oxide, zirconium oxychloride, zirconium tetrachloride, zirconium phosphate, zirconium nitrate and zirconium sulfate.
Preferably, the binder is one or more of polyvinyl alcohols such as PVA, polyoxyethylene ethers, polyethylene glycols such as PEG, polyoxyethylenes, carboxymethyl celluloses, and the like.
Preferably, the solvent is water or a lower alcohol.
Preferably, the diamond-like layer has a thickness of 30-300nm, preferably 50-200nm, more preferably 80-120nm.
Preferably, the silicon nitride layer has a thickness of 500-2000nm, preferably 800-1500nm, more preferably 1000-1200nm.
Preferably, the metal oxide layer or composite coating has a thickness of 500 to 2000nm, preferably 800 to 1500nm, more preferably 1000 to 1200n.
Preferably, the silicon nitride layer penetrates into the diamond-like coating to a thickness of 5-100nm, preferably 10-50nm.
Preferably, the silicon nitride layer penetrates into the metal oxide layer or composite coating to a thickness of 20-300nm, preferably 50-100nm.
Preferably, the metal oxide layer is selected from one or more of an aluminum oxide layer, a zirconium oxide layer, a titanium oxide layer and a nickel oxide layer.
According to a second embodiment of the present invention, an oxidation resistant graphite mold is provided.
The oxidation-resistant graphite mold comprises a graphite substrate, a diamond-like carbon layer coated on the surface of the graphite substrate, a silicon nitride layer coated on the surface of the diamond-like carbon layer, and a metal oxide layer or a composite coating coated on the surface of the silicon nitride layer. Wherein, the silicon nitride layer simultaneously infiltrates into the diamond-like coating and the metal oxide layer (or the composite coating) to form molecular-level links.
According to a third embodiment of the present invention, a method of preparing an oxygen resistant graphite mold is provided.
A preparation method of an antioxidant graphite mold comprises the following steps:
1) And (4) pretreating the graphite mold.
2) And sputtering a diamond-like carbon layer, a metal silicon layer and a metal oxide layer on the surface of the pretreated graphite mold in sequence to obtain the graphite mold with the precoating on the surface. Or
Firstly, mixing and stirring silica sol, aluminum salt, zirconium salt, a binder and a solvent to obtain a composite coating; and then sputtering a diamond-like carbon layer and a metal silicon layer on the surface of the pretreated graphite mold in sequence and coating composite paint on the surface of the graphite mold to obtain the graphite mold with a precoating or coating on the surface.
3) And (3) placing the graphite mold with the pre-plating layer or the coating on the surface in a nitrogen atmosphere for heat treatment to obtain the antioxidant graphite mold with the antioxidant plating layer.
Or, a preparation method of the antioxidant graphite mold, which comprises the following steps:
1) And (4) pretreating the graphite mold.
2) Firstly, mixing and stirring silica sol, aluminum salt, zirconium salt, a binder and a solvent to obtain a composite coating; and then sputtering a diamond-like carbon layer and a metal silicon layer on the surface of the pretreated graphite mold in sequence and coating composite paint on the surface of the graphite mold to obtain the graphite mold with a precoating or coating on the surface.
3) And (3) placing the graphite mold with the pre-plating layer or the coating on the surface in a nitrogen atmosphere for heat treatment to obtain the oxidation-resistant graphite mold with the oxidation-resistant plating layer.
Preferably, the diamond-like layer has a thickness of 30-300nm, preferably 50-200nm, more preferably 80-120nm.
Preferably, the thickness of the metal silicon layer is 500-2000nm, preferably 800-1500nm, and more preferably 1000-1200nm.
Preferably, the metal oxide layer or composite coating has a thickness of 500 to 2000nm, preferably 800 to 1500nm, more preferably 1000 to 1200nm.
Preferably, the metal oxide layer is selected from one or more of an aluminum oxide layer, a zirconium oxide layer, a titanium oxide layer and a nickel oxide layer.
Preferably, the silica sol is one or more of nano silica dispersion liquid, ethyl silicate solution and sodium silicate.
Preferably, the aluminum salt is a soluble aluminum salt, preferably one or more of aluminum chloride, aluminum sulfate and aluminum nitrate.
Preferably, the zirconium salt is soluble zirconium salt, preferably one or more of zirconium oxide, zirconium oxychloride, zirconium tetrachloride, zirconium phosphate, zirconium nitrate and zirconium sulfate.
Preferably, the binder is one or more of polyvinyl alcohols such as PVA, polyoxyethylene ethers, polyethylene glycols such as PEG, polyoxyethylenes, carboxymethylcellulose, and the like.
Preferably, the solvent is water or a lower alcohol.
Preferably, the mixing mass ratio of the silica sol, the aluminum salt, the zirconium salt, the binder and the solvent is 0-80.
Preferably, the thickness of the composite coating is 500-2000nm, preferably 800-1500nm, more preferably 1000-1200nm.
Preferably, the step 1) is specifically: soaking the graphite mold to be treated in ethanol or distilled water, and ultrasonically cleaning for 0.5-3 h (preferably 1-1.5 h) to obtain the pretreated graphite mold.
Preferably, the step 2) is specifically: and putting the pretreated graphite mold into a vacuum sputtering chamber, sputtering a diamond-like carbon layer by using a graphite target, sputtering a metal silicon layer on the surface of the diamond-like carbon layer by using a silicon target, and sputtering a metal oxide layer on the surface of the metal silicon layer to obtain the graphite mold with a precoating on the surface.
Or, the step 2) is specifically: firstly, adding silica sol, aluminum salt, zirconium salt, a binder and a solvent into a mixer according to a certain proportion, stirring for 1-24 h (preferably 3-15 h), and removing bubbles in vacuum after mixing is finished to obtain the composite coating. And then placing the pretreated graphite mold into a vacuum sputtering chamber, sputtering a diamond-like carbon layer by using a graphite target, sputtering a metal silicon layer on the surface of the diamond-like carbon layer by using a silicon target, finally taking out the graphite mold, and coating a composite coating on the surface of the metal silicon layer to obtain the graphite mold with the coating on the surface.
Preferably, the step 3) is specifically: putting the graphite mold with the pre-plating layer or the coating on the surface into a high-temperature furnace, then introducing nitrogen for heat treatment for 1-10 h (preferably 2-4 h) at the temperature of 1300-1700 ℃ (preferably 1400-1600 ℃), cooling the graphite mold after heat treatment to room temperature after heat treatment, and then polishing the surface of the graphite mold to obtain the oxidation-resistant graphite mold with the oxidation-resistant layer.
Preferably, the metal silicon layer in the graphite mold is converted to a silicon nitride layer after the nitriding heat treatment, and the silicon nitride layer penetrates into the diamond-like coating to a thickness of 5 to 100nm, preferably 10 to 50nm.
Preferably, the silicon nitride layer penetrates into the metal oxide layer or composite coating to a thickness of 20-300nm, preferably 50-100nm.
In the invention, a sputtering growth mode is adopted to generate a uniform and compact film on the surface of the graphite mold, the film can effectively isolate oxygen from contacting graphite by coating the graphite surface at a complete molecular level, and silicon nitride is generated from metal silicon through later-stage heat treatment to harden the surface of the graphite mold, so that the mold strength is increased, and the requirement of prolonging the service life of the graphite mold is met. Compared with the graphite mold prepared by the soaking method in the prior art, the method provided by the invention has the advantages that the sputtering method is adopted, the bonding force of the graphite mold is not damaged, and the mold is cracked and damaged in advance in the use process. Compared with the graphite mould without the coating, the graphite mould with the anti-oxidation function provided by the invention has the advantage that the service life is prolonged by more than three times. In addition, the sandwich structure coating is adopted, all the components have high strength and high binding energy at high temperature, and all the phases can diffuse mutually in the high-temperature nitrogen atmosphere treatment process.
In the present invention, a hard transition layer, preferably a diamond-like carbon layer, is first sputtered onto the surface of a graphite mold. Sp between carbon-carbon atoms of diamond-like carbon layer 3 And sp 2 The mixed form is combined, has the excellent characteristics of diamond and graphite, has high hardness, high resistivity, high temperature resistance and high wear resistance, and can be closely attached to the surface of a graphite mold.
In the invention, metal silicon is sputtered on the surface of the hard transition layer, and the sputtered metal silicon layer is subjected to protective heat treatment at high temperature in a nitrogen atmosphere, so that the metal silicon is converted into silicon nitride with good impact resistance, thermal stability and oxidation resistance. Meanwhile, the metal silicon wets the diamond-like carbon layer and the metal oxide layer (or the composite coating) during sputtering, and melts and permeates the diamond-like carbon layer and the outermost metal oxide layer or the composite coating and generates molecular-level linkage in the process of converting into silicon nitride, so that the hard transition layer, the silicon nitride layer and the outermost metal oxide layer or the composite coating are tightly connected and attached to the surface of the graphite mold through the hard transition layer.
In the invention, the metal oxide layer is sputtered on the surface of the metal silicon layer and is arranged on the outermost layer of the graphite mold, so that the oxidation resistance of the graphite mold is improved, and the metal oxide layer is connected with the hard transition layer and the graphite mold through the silicon nitride layer. Or, the composite coating is coated on the surface of the metal silicon layer, and a Si-Al-Zr-CN compound generated by the composite coating after high-temperature nitrogen atmosphere treatment is tightly wrapped on the surface of the silicon nitride layer, so that the external environment can be effectively isolated, and the composite coating has better impact resistance and thermal stability. Compared with a metal oxide layer, the composite coating is easy to infiltrate with graphite, the film layer and the graphite form chemical bonding, the film-substrate bonding force is higher, the film layer cannot fall off under stress in the using process, and the service life is prolonged.
In the invention, a sputtering method is adopted to prepare the ternary system coating to obtain the C-SiN-metal oxide (or composite coating) ternary hard coating, and a compact film is generated on the surface of the graphite mold, the film is coated on the graphite surface in a complete molecular level, the three layers of compact coatings can effectively isolate oxygen from contacting graphite, and the mold surface is hardened through later-stage heat treatment, so that the mold strength is increased. The compact coating can effectively isolate oxygen and other oxidation substances. The three substances are sputtered on the surface layer of the graphite mold in sequence, so that the outermost metal oxide layer or the composite coating can effectively isolate oxides such as oxygen from contacting with the graphite when the ternary system coating is tightly attached to the surface of the graphite mold, and the silicon nitride layer and the diamond-like carbon layer have good impact resistance and wear resistance, and can prevent the graphite from falling powder and being scratched.
In the invention, metal silicon is sputtered on the surface of the diamond-like carbon layer, a metal oxide layer or a composite coating is sputtered on the metal silicon layer, and after the sputtering is finished, heat treatment is carried out in a nitrogen atmosphere, so that the metal silicon layer is converted into a silicon nitride layer, and the silicon nitride layer permeates into the diamond-like carbon layer and the metal oxide layer (or the composite coating) along gaps between the diamond-like carbon and a metal oxide compound (or a Si-Al-Zr-CN compound) and generates molecular linkage with the diamond-like carbon layer and the metal oxide layer (or the composite coating), and the permeation thickness is about 20-300 nm. Compared with the method of directly sputtering the silicon nitride layer on the diamond-like carbon, the sputtering of the metal silicon and the transformation of the metal silicon into the silicon nitride can enable the silicon nitride layer to penetrate into the diamond-like carbon layer and the metal oxide layer more, and the silicon nitride layer is combined with the diamond-like carbon layer and the metal oxide layer more firmly.
Compared with the prior art, the invention has the following beneficial effects:
1. the carbon matrix antioxidant coating provided by the invention has better hardness and antioxidant performance, can effectively isolate the external environment and protects the graphite mould.
2. The invention adopts a sputtering growth mode to generate a uniform and compact film on the surface of the graphite mould, and the film can effectively isolate oxygen from contacting graphite by completely coating the surface of the graphite at a molecular level.
3. According to the invention, the C-SiN-metal oxide layer (or composite coating) ternary hard coating is obtained by adopting the sandwich structure coating and performing nitridation treatment, and the silicon nitride, the diamond-like carbon layer and the outermost metal oxide layer (or composite coating) generate molecular-level linkage, so that the surface of the graphite mold is hardened, the strength of the mold is increased, and the requirement of prolonging the service life of the graphite mold is met.
4. The invention has the advantages of easily obtained materials, simple process, environmental protection and good economic benefit.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
According to a first embodiment of the present invention, an oxidation resistant coating is provided.
The anti-oxidation coating comprises a diamond-like carbon layer coated on the surface of a carbon substrate, a silicon nitride layer coated on the surface of the diamond-like carbon layer, and a metal oxide layer or a composite coating coated on the surface of the silicon nitride layer. Wherein, the silicon nitride layer simultaneously infiltrates into the diamond-like coating and the metal oxide layer (or the composite coating) to form molecular-level links.
Preferably, the composite coating is prepared by mixing silica sol, aluminum salt, zirconium salt, binder and solvent. Preferably, the weight ratio of the silica sol, the aluminum salt, the zirconium salt, the binder and the solvent is 0-80.
Preferably, the silica sol is one or more of nano silica dispersion liquid, ethyl silicate solution and sodium silicate.
Preferably, the aluminum salt is a soluble aluminum salt, preferably one or more of aluminum chloride, aluminum sulfate and aluminum nitrate.
Preferably, the zirconium salt is soluble zirconium salt, preferably one or more of zirconium oxide, zirconium oxychloride, zirconium tetrachloride, zirconium phosphate, zirconium nitrate and zirconium sulfate.
Preferably, the binder is one or more of polyvinyl alcohols such as PVA, polyoxyethylene ethers, polyethylene glycols such as PEG, polyoxyethylenes, carboxymethylcellulose, and the like.
Preferably, the solvent is water or a lower alcohol.
Preferably, the diamond-like layer has a thickness of 30-300nm, preferably 50-200nm, more preferably 80-120nm.
Preferably, the silicon nitride layer has a thickness of 500-2000nm, preferably 800-1500nm, more preferably 1000-1200nm.
Preferably, the metal oxide layer or composite coating has a thickness of 500 to 2000nm, preferably 800 to 1500nm, more preferably 1000 to 1200n.
Preferably, the silicon nitride layer penetrates into the diamond-like coating to a thickness of 5-100nm, preferably 10-50nm.
Preferably, the silicon nitride layer penetrates into the metal oxide layer or composite coating to a thickness of 20-300nm, preferably 50-100nm.
Preferably, the metal oxide layer is selected from one or more of an aluminum oxide layer, a zirconium oxide layer, a titanium oxide layer and a nickel oxide layer.
According to a second embodiment of the present invention, an oxidation resistant graphite mold is provided.
The oxidation-resistant graphite mould comprises a graphite matrix, a diamond-like carbon layer coated on the surface of the graphite matrix, a silicon nitride layer coated on the surface of the diamond-like carbon layer, and a metal oxide layer or a composite coating coated on the surface of the silicon nitride layer. Wherein, the silicon nitride layer simultaneously infiltrates into the diamond-like coating and the metal oxide layer (or the composite coating) to form molecular-level links.
According to a third embodiment of the present invention, a method for preparing an antioxidant graphite mold is provided.
A preparation method of an antioxidant graphite mold comprises the following steps:
1) And (4) pretreating the graphite mold.
2) And sputtering a diamond-like carbon layer, a metal silicon layer and a metal oxide layer on the surface of the pretreated graphite mold in sequence to obtain the graphite mold with the precoating on the surface. Or
Firstly, mixing and stirring silica sol, aluminum salt, zirconium salt, a binder and a solvent to obtain a composite coating; and then sputtering a diamond-like carbon layer and a metal silicon layer on the surface of the pretreated graphite mold in sequence and coating composite paint on the surface of the graphite mold to obtain the graphite mold with a precoating or coating on the surface.
3) And (3) placing the graphite mold with the pre-plating layer or the coating on the surface in a nitrogen atmosphere for heat treatment to obtain the oxidation-resistant graphite mold with the oxidation-resistant plating layer.
Preferably, the diamond-like layer has a thickness of 30-300nm, preferably 50-200nm, more preferably 80-120nm.
Preferably, the thickness of the metal silicon layer is 500-2000nm, preferably 800-1500nm, and more preferably 1000-1200nm.
Preferably, the metal oxide layer or composite coating has a thickness of 500 to 2000nm, preferably 800 to 1500nm, more preferably 1000 to 1200nm.
Preferably, the metal oxide layer is selected from one or more of an aluminum oxide layer, a zirconium oxide layer, a titanium oxide layer and a nickel oxide layer.
Preferably, the silica sol is one or more of nano silica dispersion liquid, ethyl silicate solution and sodium silicate.
Preferably, the aluminum salt is a soluble aluminum salt, preferably one or more of aluminum chloride, aluminum sulfate and aluminum nitrate.
Preferably, the zirconium salt is soluble zirconium salt, preferably one or more of zirconium oxide, zirconium oxychloride, zirconium tetrachloride, zirconium phosphate, zirconium nitrate and zirconium sulfate.
Preferably, the binder is one or more of polyvinyl alcohols such as PVA, polyoxyethylene ethers, polyethylene glycols such as PEG, polyoxyethylenes, carboxymethylcellulose, and the like.
Preferably, the solvent is water or a lower alcohol.
Preferably, the mixing mass ratio of the silica sol, the aluminum salt, the zirconium salt, the binder and the solvent is 0 to 80.
Preferably, the thickness of the composite coating is 500-2000nm, preferably 800-1500nm, more preferably 1000-1200nm.
Preferably, the step 1) is specifically: soaking the graphite mold to be treated in ethanol or distilled water, and ultrasonically cleaning for 0.5-3 h (preferably 1-1.5 h) to obtain the pretreated graphite mold.
Preferably, the step 2) is specifically: and putting the pretreated graphite mold into a vacuum sputtering chamber, sputtering a diamond-like carbon layer by using a graphite target, sputtering a metal silicon layer on the surface of the diamond-like carbon layer by using a silicon target, and sputtering a metal oxide layer on the surface of the metal silicon layer to obtain the graphite mold with a precoating on the surface.
Or, the step 2) is specifically: firstly, adding the silica sol, the aluminum salt, the zirconium salt, the binder and the solvent into a mixer according to a certain proportion, stirring for 1-24 h (preferably 3-15 h), and performing vacuum defoaming after mixing to obtain the composite coating. And then placing the pretreated graphite mold into a vacuum sputtering chamber, sputtering a diamond-like carbon layer by using a graphite target, sputtering a metal silicon layer on the surface of the diamond-like carbon layer by using a silicon target, finally taking out the graphite mold, and coating a composite coating on the surface of the metal silicon layer to obtain the graphite mold with the coating on the surface.
Preferably, the step 3) is specifically: putting the graphite mold with the pre-plating layer or the coating on the surface into a high-temperature furnace, then introducing nitrogen for heat treatment for 1-10 h (preferably 2-4 h) at the temperature of 1300-1700 ℃ (preferably 1400-1600 ℃), cooling the graphite mold after heat treatment to room temperature after heat treatment, and then polishing the surface of the graphite mold to obtain the oxidation-resistant graphite mold with the oxidation-resistant layer.
Preferably, the metal silicon layer in the graphite mold is converted to a silicon nitride layer after the nitriding heat treatment, and the silicon nitride layer penetrates into the diamond-like coating to a thickness of 5 to 100nm, preferably 10 to 50nm.
Preferably, the silicon nitride layer penetrates into the metal oxide layer or composite coating to a thickness of 20-300nm, preferably 50-100nm.
Example 1
1) Soaking the graphite mold to be treated in distilled water, and cleaning for 1h by using ultrasonic waves to obtain the pretreated graphite mold.
2) And putting the pretreated graphite mold into a vacuum sputtering chamber, and sputtering a diamond-like carbon transition layer with the thickness of 90nm, a metal silicon layer with the thickness of 1100nm and an aluminum oxide layer with the thickness of 1100nm on the surface of the graphite mold in sequence to obtain the graphite mold with the pre-plated layer on the surface.
3) And (3) putting the graphite mold with the pre-plating layer on the surface into a high-temperature nitrogen atmosphere furnace, introducing nitrogen, carrying out heat treatment at 1400 ℃ for 3h, cooling to room temperature, and polishing the surface of the mold to obtain the graphite mold with the antioxidant function.
Example 2
Example 1 was repeated except that the diamond-like transition layer had a thickness of 30nm.
Example 3
Example 2 was repeated except that the diamond-like transition layer had a thickness of 50nm.
Example 4
Example 1 was repeated except that the diamond-like transition layer had a thickness of 130nm.
Example 5
Example 1 was repeated except that the diamond-like transition layer had a thickness of 160nm.
Example 6
Example 1 was repeated except that the thickness of the metal silicon layer was 500nm.
Example 7
Example 1 was repeated except that the thickness of the metal silicon layer was 800nm.
Example 8
Example 1 was repeated except that the thickness of the metal silicon layer was 1500nm.
Example 9
Example 1 was repeated except that the thickness of the metal silicon layer was 2000nm.
Example 10
Example 1 was repeated except that the thickness of the alumina layer was 500nm.
Example 11
Example 1 was repeated except that the thickness of the alumina layer was 800nm.
Example 12
Example 1 was repeated except that the thickness of the alumina layer was 1500nm.
Example 13
Example 1 was repeated except that the thickness of the alumina layer was 2000nm.
Example 14
Example 1 was repeated except that a layer of zirconia having a thickness of 1100nm was sputtered onto the outside of the metallic silicon layer.
Example 15
Example 1 was repeated except that a layer of 1100nm thick titanium oxide was sputtered over the metallic silicon layer.
Example 16
1) Soaking the graphite mold to be treated in distilled water, and cleaning for 1h by using ultrasonic waves to obtain the pretreated graphite mold.
2) Adding 40g of ethyl silicate solution, 40g of aluminum chloride, 10g of zirconium oxide, 5g of PVA binder and 80g of ethanol into a mixer, stirring for 6 hours, and removing bubbles in vacuum after mixing is completed to obtain the composite coating. And putting the pretreated graphite mold into a vacuum sputtering chamber, sequentially sputtering a diamond-like carbon transition layer with the thickness of 90nm and a metal silicon layer with the thickness of 1100nm on the surface of the graphite mold, taking out the graphite mold, and coating 1100nm of composite coating on the surface of the metal silicon layer to obtain the graphite mold with the coating on the surface.
3) And (3) putting the graphite mold with the coating on the surface into a high-temperature nitrogen atmosphere furnace, introducing nitrogen, carrying out heat treatment at 1400 ℃ for 3h, cooling to room temperature, and polishing the surface of the mold to obtain the graphite mold with the antioxidant function.
Example 17
Example 16 was repeated, except that the thickness of the composite coating was 500nm.
Example 18
Example 16 was repeated, except that the thickness of the composite coating was 800nm.
Example 19
Example 16 was repeated, except that the thickness of the composite coating was 1500nm.
Example 20
Example 16 was repeated, except that the thickness of the composite coating was 2000nm.
Comparative example 1
Uncoated graphite molds.
Comparative example 2
And soaking the graphite mold in a suspension of 50nm alumina to prepare the graphite mold with the alumina on the surface.
Comparative example 3
Example 1 was repeated except that the graphite mold was coated with only a diamond-like transition layer having a thickness of 90nm.
Comparative example 4
Example 1 was repeated except that the graphite mold was coated with only an aluminum oxide layer having a thickness of 1100nm.
Comparative example 5
Example 1 was repeated except that the graphite mold was coated with only a silicon metal layer having a thickness of 1100nm.
Comparative example 6
Example 1 was repeated except that the graphite mold was coated with only a metal silicon layer having a thickness of 1100nm and an aluminum oxide layer having a thickness of 1100nm.
Comparative example 7
Example 1 was repeated except that the graphite mold was coated with only a 90nm thick diamond-like transition layer and an 1100nm thick aluminum oxide layer.
Comparative example 8
Example 1 was repeated except that the graphite mold was coated with only a diamond-like transition layer having a thickness of 90nm and a metal silicon layer having a thickness of 1100nm.
Comparative example 9
Example 16 was repeated except that the graphite mold was coated with only the composite coating, which had a thickness of 1100nm.
Comparative example 10
Example 16 was repeated except that only the composite diamond transition layer having a thickness of 90nm and the composite coating having a thickness of 1100nm were present on the graphite mold.
Comparative example 11
Soaking the graphite mold to be treated in distilled water, and cleaning for 1h by ultrasonic waves. And putting the pretreated graphite mold into a vacuum sputtering chamber, sequentially sputtering a diamond-like carbon transition layer with the thickness of 90nm, a metal silicon layer with the thickness of 1100nm and an aluminum oxide layer with the thickness of 1100nm on the surface of the graphite mold, and polishing the surface of the mold after sputtering is finished to obtain the graphite mold with the antioxidant function.
Comparative example 12
Soaking the graphite mold to be treated in distilled water, and cleaning for 1h by ultrasonic waves. And putting the pretreated graphite mold into a vacuum sputtering chamber, sequentially sputtering a diamond-like carbon transition layer with the thickness of 90nm, a metal silicon layer with the thickness of 1100nm and a zirconium oxide layer with the thickness of 1100nm on the surface of the graphite mold, and polishing the surface of the mold after sputtering is finished to obtain the graphite mold with the antioxidant function.
Comparative example 13
Soaking the graphite mold to be treated in distilled water, and cleaning for 1h by ultrasonic waves. And putting the pretreated graphite mold into a vacuum sputtering chamber, sequentially sputtering a diamond-like carbon transition layer with the thickness of 90nm, a metal silicon layer with the thickness of 1100nm and a titanium oxide layer with the thickness of 1100nm on the surface of the graphite mold, and polishing the surface of the mold after sputtering is finished to obtain the graphite mold with the antioxidant function.
The graphite molds prepared in examples 1 to 20 and comparative examples 1 to 14 were subjected to a performance test, and an adhesion test was carried out using GB/T9286-88, with the results shown in Table 1. The penetration of the silicon nitride layer into the diamond-like carbon layer and the metal oxide layer was measured for thickness and the results are shown in table 2.
Table 1:
table 2:
the experiment proves that the sputtering method does not damage the binding force of the graphite die, so that the die is cracked and damaged in advance in the using process. Compared with the graphite die without the coating, the graphite die with the oxidation resistance provided by the invention has the advantage that the service life is prolonged by more than three times. In addition, the sandwich structure coating is adopted, all the components have high strength and high bonding energy at high temperature, and the silicon nitride layer is diffused into the diamond-like carbon layer and the metal oxide layer (or the composite coating) in the high-temperature nitrogen atmosphere treatment process.
Claims (10)
1. An oxidation resistant coating characterized by: the anti-oxidation coating comprises a diamond-like carbon layer coated on the surface of a carbon substrate, a silicon nitride layer coated on the surface of the diamond-like carbon layer, and a metal oxide layer or a composite coating coated on the surface of the silicon nitride layer; wherein, the silicon nitride layer simultaneously infiltrates into the diamond-like coating and the metal oxide layer (or the composite coating) to form molecular-level links.
2. The oxidation-resistant coating of claim 1, wherein: the composite coating is prepared by mixing silica sol, aluminum salt, zirconium salt, a binder and a solvent; preferably, the weight ratio of the silica sol, the aluminum salt, the zirconium salt, the binder and the solvent is 0-80;
preferably, the silica sol is one or more of nano-silica dispersion liquid, ethyl silicate solution and sodium silicate; and/or
The aluminum salt is soluble aluminum salt, preferably one or more of aluminum chloride, aluminum sulfate and aluminum nitrate; and/or
The zirconium salt is soluble zirconium salt, preferably one or more of zirconium oxide, zirconium oxychloride, zirconium tetrachloride, zirconium phosphate, zirconium nitrate and zirconium sulfate; and/or
The binder is one or more of polyvinyl alcohol such as PVA, polyoxyethylene ether, polyethylene glycol such as PEG, polyoxyethylene, carboxymethyl cellulose, etc.; and/or
The solvent is water or lower alcohol.
3. The oxidation-resistant coating according to claim 1 or 2, characterized in that: the thickness of the diamond-like carbon layer is 30-300nm, preferably 50-200nm, more preferably 80-120nm; and/or
The thickness of the silicon nitride layer is 500-2000nm, preferably 800-1500nm, and more preferably 1000-1200nm; and/or
The thickness of the metal oxide layer or the composite coating is 500-2000nm, preferably 800-1500nm, and more preferably 1000-1200nm;
preferably, the silicon nitride layer penetrates into the diamond-like coating to a thickness of 5-100nm, preferably 10-50nm; and/or
The thickness of the silicon nitride layer penetrating into the metal oxide layer or the composite coating is 20-300nm, preferably 50-100nm;
preferably, the metal oxide layer is selected from one or more of an aluminum oxide layer, a zirconium oxide layer, a titanium oxide layer and a nickel oxide layer.
4. An anti-oxidation graphite mold is characterized in that: the oxidation-resistant graphite mould comprises a graphite matrix, a diamond-like carbon layer coated on the surface of the graphite matrix, a silicon nitride layer coated on the surface of the diamond-like carbon layer, and a metal oxide layer or a composite coating coated on the surface of the silicon nitride layer; wherein, the silicon nitride layer simultaneously infiltrates into the diamond-like coating and the metal oxide layer (or the composite coating) to form molecular-level links.
5. A method of preparing an oxidation resistant graphite mold or a method of preparing the oxidation resistant graphite mold of claim 4, characterized in that: the method comprises the following steps:
1) Pretreating the graphite mold;
2) Sputtering a diamond-like carbon layer, a metal silicon layer and a metal oxide layer on the surface of the pretreated graphite mold in sequence to obtain the graphite mold with a precoating on the surface; or
Firstly, mixing and stirring silica sol, aluminum salt, zirconium salt, a binder and a solvent to obtain a composite coating; then sputtering a diamond-like carbon layer and a metal silicon layer on the surface of the pretreated graphite mold in sequence and coating a composite coating to obtain the graphite mold with a pre-coating or coating on the surface;
3) And (3) placing the graphite mold with the pre-plating layer or the coating on the surface in a nitrogen atmosphere for heat treatment to obtain the oxidation-resistant graphite mold with the oxidation-resistant plating layer.
6. The method of claim 5, wherein: the thickness of the diamond-like layer is 30-300nm, preferably 50-200nm, more preferably 80-120nm; and/or
The thickness of the metal silicon layer is 500-2000nm, preferably 800-1500nm, and more preferably 1000-1200nm; and/or
The thickness of the metal oxide layer or the composite coating is 500-2000nm, preferably 800-1500nm, and more preferably 1000-1200nm;
preferably, the metal oxide layer is selected from one or more of an aluminum oxide layer, a zirconium oxide layer, a titanium oxide layer and a nickel oxide layer.
7. The method according to claim 5 or 6, characterized in that: the silica sol is one or more of nano silicon dioxide dispersion liquid, ethyl silicate solution and sodium silicate; and/or
The aluminum salt is soluble aluminum salt, preferably one or more of aluminum chloride, aluminum sulfate and aluminum nitrate; and/or
The zirconium salt is soluble zirconium salt, preferably one or more of zirconium oxide, zirconium oxychloride, zirconium tetrachloride, zirconium phosphate, zirconium nitrate and zirconium sulfate; and/or
The binder is one or more of polyvinyl alcohol such as PVA, polyoxyethylene ether, polyethylene glycol such as PEG, polyoxyethylene, carboxymethyl cellulose, etc.; and/or
The solvent is water or lower alcohol;
preferably, the mixing mass ratio of the silica sol, the aluminum salt, the zirconium salt, the binder and the solvent is 0 to 80;
the thickness of the composite coating is 500-2000nm, preferably 800-1500nm, and more preferably 1000-1200nm.
8. The method according to any one of claims 5-7, wherein: the step 1) is specifically as follows: soaking a graphite mold to be treated in ethanol or distilled water, and ultrasonically cleaning for 0.5-3 h (preferably 1-1.5 h) to obtain a pretreated graphite mold; and/or
The step 2) is specifically as follows: placing the pretreated graphite mold into a vacuum sputtering chamber, sputtering a diamond-like carbon layer by using a graphite target, then sputtering a metal silicon layer on the surface of the diamond-like carbon layer by using a silicon target, and finally sputtering a metal oxide layer on the surface of the metal silicon layer to obtain the graphite mold with a precoating on the surface;
or, the step 2) is specifically: firstly, adding silica sol, aluminum salt, zirconium salt, a binder and a solvent into a mixer according to a certain proportion, stirring for 1-24 h (preferably 3-15 h), and removing bubbles in vacuum after mixing is finished to obtain a composite coating; and then placing the pretreated graphite mold into a vacuum sputtering chamber, sputtering a diamond-like carbon layer by using a graphite target, sputtering a metal silicon layer on the surface of the diamond-like carbon layer by using a silicon target, finally taking out the graphite mold, and coating a composite coating on the surface of the metal silicon layer to obtain the graphite mold with the coating on the surface.
9. The method of claim 8, wherein: the step 3) is specifically as follows: putting the graphite mold with the pre-plating layer or the coating on the surface into a high-temperature furnace, then introducing nitrogen for heat treatment for 1-10 h (preferably 2-4 h) at the temperature of 1300-1700 ℃ (preferably 1400-1600 ℃), cooling the graphite mold after heat treatment to room temperature after heat treatment, and then polishing the surface of the graphite mold to obtain the oxidation-resistant graphite mold with the oxidation-resistant layer.
10. The method according to any one of claims 5-9, wherein: after nitriding heat treatment, the metal silicon layer in the graphite mould is converted into a silicon nitride layer, and the thickness of the silicon nitride layer penetrating into the diamond-like coating is 5-100nm, preferably 10-50nm; and/or
The silicon nitride layer penetrates into the metal oxide layer or the composite coating to a thickness of 20-300nm, preferably 50-100nm.
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