CN115819118B - Antioxidant coating, graphite mold containing antioxidant coating and preparation method of graphite mold - Google Patents
Antioxidant coating, graphite mold containing antioxidant coating and preparation method of graphite mold Download PDFInfo
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- CN115819118B CN115819118B CN202211491943.XA CN202211491943A CN115819118B CN 115819118 B CN115819118 B CN 115819118B CN 202211491943 A CN202211491943 A CN 202211491943A CN 115819118 B CN115819118 B CN 115819118B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 247
- 238000000576 coating method Methods 0.000 title claims abstract description 119
- 239000011248 coating agent Substances 0.000 title claims abstract description 118
- 239000010439 graphite Substances 0.000 title claims description 204
- 229910002804 graphite Inorganic materials 0.000 title claims description 204
- 239000003963 antioxidant agent Substances 0.000 title claims description 30
- 230000003078 antioxidant effect Effects 0.000 title claims description 30
- 238000002360 preparation method Methods 0.000 title description 7
- 239000010410 layer Substances 0.000 claims abstract description 284
- 239000002131 composite material Substances 0.000 claims abstract description 67
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 63
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 56
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 53
- 238000004544 sputter deposition Methods 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 230000003647 oxidation Effects 0.000 claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 239000011247 coating layer Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 55
- 229910052710 silicon Inorganic materials 0.000 claims description 55
- 239000010703 silicon Substances 0.000 claims description 55
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 26
- 150000003754 zirconium Chemical class 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 22
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 238000007747 plating Methods 0.000 claims description 19
- 230000000149 penetrating effect Effects 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 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 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005498 polishing Methods 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 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 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 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 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 5
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 5
- 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 5
- 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 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 239000005543 nano-size silicon particle Substances 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 6
- 230000007704 transition Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000013003 hot bending Methods 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 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
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 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
- 239000002356 single layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 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
Abstract
An oxidation resistant coating, characterized by: the antioxidation coating comprises a diamond-like carbon layer coated on the surface of a carbonaceous 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 is infiltrated into the diamond-like carbon coating layer and the metal oxide layer (or the composite coating layer) simultaneously 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 matrix, and the film can effectively isolate oxygen from contacting the carbonaceous matrix by coating the surface of the carbonaceous matrix in a complete molecular level.
Description
Technical Field
The invention relates to an antioxidation technology of a carbonaceous matrix, in particular to an antioxidation coating, a graphite mold containing the antioxidation coating and a preparation method thereof, and belongs to the technical field of surface treatment of glass processing molds.
Background
The hot bending glass is formed by heating and softening planar glass in a mould, and in the hot bending process, the mould needs to transmit heat to the glass, and the forming precision of a glass finished product cannot be affected, 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 graphite materials are adopted for the most of the hot bending moulds at present. However, the graphite material has poor oxidation resistance and is easy to oxidize at high temperature, so that the glass precision is reduced, meanwhile, the strength of the graphite mold is low, the phenomena of powder falling and edge breakage exist in 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 proposed in the prior art so as to enhance the oxidation resistance and other performances of the graphite mold. For example, the graphite mold is immersed in a suspension or precursor solution containing an inorganic oxide, and then dried and heated to adhere the inorganic oxide to the surface of the graphite mold, so that the oxidation resistance of the graphite mold is improved, but the scratch resistance of the graphite mold cannot be improved, powder falling of the graphite mold cannot be avoided, and meanwhile, the bonding force of the graphite mold per se is 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 use process.
Disclosure of Invention
The invention provides an oxidation-resistant coating, a graphite mold containing the oxidation-resistant coating and a preparation method thereof, aiming at the problems in the prior art. The oxidation-resistant coating obtained by the invention uniformly generates a compact film on the surface of the graphite die in a sputtering growth mode, and the film can effectively isolate oxygen from contact with graphite and increase the strength of the die by completely coating the surface of the graphite in a molecular level.
According to a first embodiment of the present invention, an oxidation resistant coating is provided.
The antioxidation coating comprises a diamond-like carbon layer coated on the surface of a carbonaceous 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 is infiltrated into the diamond-like carbon coating layer and the metal oxide layer (or the composite coating layer) simultaneously 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 0-80:0-20:1-10:40-120, preferably 20-50:20-50:5-10:2-5:50-100.
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, polyoxyethylene, carboxymethyl cellulose and the like.
Preferably, the solvent is water or a low alcohol.
Preferably, the diamond-like layer has a thickness of 30 to 300nm, preferably 50 to 200nm, more preferably 80 to 120nm.
Preferably, the silicon nitride layer has a thickness of 500 to 2000nm, preferably 800 to 1500nm, more preferably 1000 to 1200nm.
Preferably, the metal oxide layer or composite coating has a thickness of 500-2000nm, preferably 800-1500nm, more preferably 1000-1200n.
Preferably, the thickness of the silicon nitride layer penetrating into the diamond-like coating is 5 to 100nm, preferably 10 to 50nm.
Preferably, the thickness of the silicon nitride layer penetrating into the metal oxide layer or the composite coating layer is 20 to 300nm, preferably 50 to 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 layer coated on the surface of the graphite substrate, a silicon nitride layer coated on the surface of the diamond-like layer, and a metal oxide layer or a composite coating coated on the surface of the silicon nitride layer. Wherein the silicon nitride layer is infiltrated into the diamond-like carbon coating layer and the metal oxide layer (or the composite coating layer) simultaneously to form molecular-level links.
According to a third embodiment of the present invention, there is provided a method for preparing an antioxidant graphite mold.
The preparation method of the antioxidant graphite mold comprises the following steps:
1) And (5) preprocessing the graphite die.
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 surface provided with the pre-plating layer. Or (b)
Firstly, mixing and stirring silica sol, aluminum salt, zirconium salt, binder and 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 a composite coating to obtain the graphite mold with a pre-plating layer or coating on the surface.
3) And placing the graphite mould with the pre-plating layer or the coating on the surface in a nitrogen atmosphere for heat treatment to obtain the antioxidant graphite mould with the antioxidant plating layer.
Or, a preparation method of an antioxidant graphite mold comprises the following steps:
1) And (5) preprocessing the graphite die.
2) Firstly, mixing and stirring silica sol, aluminum salt, zirconium salt, binder and 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 a composite coating to obtain the graphite mold with a pre-plating layer or coating on the surface.
3) And placing the graphite mould with the pre-plating layer or the coating on the surface in a nitrogen atmosphere for heat treatment to obtain the antioxidant graphite mould with the antioxidant plating layer.
Preferably, the diamond-like layer has a thickness of 30 to 300nm, preferably 50 to 200nm, more preferably 80 to 120nm.
Preferably, the thickness of the metallic silicon layer is 500-2000nm, preferably 800-1500nm, more preferably 1000-1200nm.
Preferably, the metal oxide layer or composite coating has a thickness of 500-2000nm, preferably 800-1500nm, 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.
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, polyoxyethylene, carboxymethyl cellulose and the like.
Preferably, the solvent is water or a low alcohol.
Preferably, the mixing mass ratio of the silica sol, the aluminum salt, the zirconium salt, the binder and the solvent is 0-80:0-20:1-10:40-120, preferably 20-50:20-50:5-10:2-5:50-100.
Preferably, the thickness of the composite coating is 500-2000nm, preferably 800-1500nm, more preferably 1000-1200nm.
Preferably, the step 1) specifically includes: soaking the graphite mold to be treated by adopting 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) specifically includes: and (3) placing the pretreated graphite mould into a vacuum sputtering chamber, sputtering a diamond-like carbon layer by adopting a graphite target, sputtering a metal silicon layer on the surface of the diamond-like carbon layer by adopting a silicon target, and finally sputtering a metal oxide on the surface of the metal silicon layer to obtain the graphite mould with the surface provided with the pre-plating layer.
Or, the step 2) specifically comprises the following steps: firstly adding silica sol, aluminum salt, zirconium salt, binder and solvent into a mixer according to a certain proportion, stirring for 1-24 h (preferably 3-15 h), and carrying out vacuum defoaming after mixing to obtain the composite coating. And then placing the pretreated graphite mould into a vacuum sputtering chamber, sputtering a diamond-like layer by adopting a graphite target, sputtering a metal silicon layer on the surface of the diamond-like layer by adopting a silicon target, finally taking out the graphite mould, and coating a composite coating on the surface of the metal silicon layer to obtain the graphite mould with the coating on the surface.
Preferably, the step 3) specifically includes: placing the graphite mould with the pre-plating layer or coating on the surface into a high temperature furnace, then introducing nitrogen at the temperature of 1300-1700 ℃ (preferably 1400-1600 ℃) for heat treatment for 1-10 hours (preferably 2-4 hours), cooling the graphite mould after heat treatment to room temperature after heat treatment is completed, and polishing the surface of the graphite mould to obtain the antioxidant graphite mould with the antioxidant layer.
Preferably, after the nitriding heat treatment, the metallic silicon layer in the graphite mold is converted into a silicon nitride layer, and the thickness of the silicon nitride layer penetrating into the diamond-like coating layer is 5 to 100nm, preferably 10 to 50nm.
Preferably, the thickness of the silicon nitride layer penetrating into the metal oxide layer or the composite coating layer is 20 to 300nm, preferably 50 to 100nm.
In the invention, a uniform and compact film is generated on the surface of the graphite mold by adopting a sputtering growth mode, the film can effectively isolate oxygen from contacting graphite by completely coating the surface of the graphite in molecular level, and silicon nitride is generated by metal silicon through later heat treatment, so that the surface of the graphite mold is hardened, 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 invention adopts the sputtering method, so that the bonding force of the graphite mold is not damaged, and the mold is cracked and damaged in advance in the using process. The service life of the graphite mold with the antioxidant function provided by the invention is prolonged by more than three times compared with that of a non-coating graphite mold. In addition, the sandwich structure coating is adopted, the components have high strength at high temperature and high bonding energy, and the phases are mutually diffused in the high-temperature nitrogen atmosphere treatment process.
In the present invention, a hard transition layer, preferably a diamond-like layer, is first sputtered onto the surface of a graphite mold. Sp between carbon and carbon atoms of diamond-like carbon layer 3 And sp (sp) 2 The composite material has excellent properties of diamond and graphite, high hardness, high resistivity, high heat resistance and high wear resistance, and can be closely adhered to the surface of a graphite die.
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 and under 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 layer and the metal oxide layer (or the composite coating) when being sputtered, and can melt and infiltrate the diamond-like layer and the outermost metal oxide layer or the composite coating and produce molecular-level linkage in the process of being converted 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 are adhered to the surface of the graphite mold through the hard transition layer.
In the invention, a metal oxide layer is sputtered on the surface of a metal silicon layer, the metal oxide layer is arranged on the outermost layer of a graphite mold, improves the oxidation resistance of the graphite mold, and is connected with a hard transition layer and the graphite mold through a silicon nitride layer. Or, the composite coating is coated on the surface of the metal silicon layer, and the Si-Al-Zr-CN compound generated by the composite coating after being treated in the high-temperature nitrogen atmosphere is tightly wrapped on the surface of the silicon nitride layer, so that the external environment can be effectively isolated, and the impact resistance and the thermal stability are better. Compared with the metal oxide layer, the composite coating is easy to infiltrate with graphite, the film layer and the graphite form chemical combination, the film base binding force is higher, the film layer can not fall off when being stressed in the use process, and the service life is prolonged.
According to the invention, a ternary system coating is prepared by adopting a sputtering method, a C-SiN-metal oxide (or composite coating) ternary hard coating is obtained, and a compact film is generated on the surface of a graphite mold, and the film is used for completely coating the surface of the graphite at a molecular level, so that the three layers of compact coatings can effectively isolate oxygen from contacting the graphite, and the surface of the mold is hardened by post heat treatment, so that the strength of the mold is increased. The compact coating can effectively isolate oxidation substances such as oxygen and the like. The three substances are sequentially sputtered on the surface layer of the graphite mold, so that the ternary system coating is tightly adhered to the surface of the graphite mold, the outermost metal oxide layer or the composite coating can effectively isolate oxides such as oxygen from contacting with graphite, and the silicon nitride layer and the diamond-like carbon layer have good impact resistance and wear resistance and can avoid powder falling and scratch of the graphite.
In the invention, metal silicon is sputtered on the surface of the diamond-like layer, a metal oxide layer or a composite coating is sputtered above the metal silicon layer, and after the sputtering is finished, the metal silicon layer is converted into a silicon nitride layer by heat treatment in a nitrogen atmosphere, at the moment, the silicon nitride layer permeates into the diamond-like layer and the metal oxide layer (or the composite coating) along gaps of diamond-like carbon and metal oxide compounds (or Si-Al-Zr-CN compounds) and generates molecular-level linkage with the diamond-like carbon and the metal oxide layer (or the composite coating), and the permeation thickness is about 20-300nm. Compared with the method that the silicon nitride layer is directly sputtered on the diamond-like carbon, the silicon nitride layer can be more infiltrated into the diamond-like carbon layer and the metal oxide layer by sputtering metal silicon and then is converted into silicon nitride, and the combination of the silicon nitride layer and the diamond-like carbon layer and the metal oxide layer is firmer.
Compared with the prior art, the invention has the following beneficial effects:
1. the carbon matrix oxidation-resistant coating provided by the invention has good hardness and oxidation resistance, and can effectively isolate the external environment and protect the graphite die.
2. The invention adopts a sputtering growth mode to generate a uniform and compact film on the surface of the graphite die, and the film can effectively isolate oxygen from graphite contact by coating the surface of graphite in a complete molecular level.
3. According to the invention, a sandwich structure coating is adopted, and a C-SiN-metal oxide layer (or composite coating) ternary hard coating is obtained after nitriding treatment, and silicon nitride is linked with a diamond-like carbon layer and an outermost metal oxide layer (or composite coating) to produce molecular grade, so that the surface of a graphite mold is hardened, the mold strength 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 friendliness and good economic benefit.
Detailed Description
The following examples illustrate the technical aspects of the invention, and the scope of the invention claimed 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 antioxidation coating comprises a diamond-like carbon layer coated on the surface of a carbonaceous 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 is infiltrated into the diamond-like carbon coating layer and the metal oxide layer (or the composite coating layer) simultaneously 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 0-80:0-20:1-10:40-120, preferably 20-50:20-50:5-10:2-5:50-100.
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, polyoxyethylene, carboxymethyl cellulose and the like.
Preferably, the solvent is water or a low alcohol.
Preferably, the diamond-like layer has a thickness of 30 to 300nm, preferably 50 to 200nm, more preferably 80 to 120nm.
Preferably, the silicon nitride layer has a thickness of 500 to 2000nm, preferably 800 to 1500nm, more preferably 1000 to 1200nm.
Preferably, the metal oxide layer or composite coating has a thickness of 500-2000nm, preferably 800-1500nm, more preferably 1000-1200n.
Preferably, the thickness of the silicon nitride layer penetrating into the diamond-like coating is 5 to 100nm, preferably 10 to 50nm.
Preferably, the thickness of the silicon nitride layer penetrating into the metal oxide layer or the composite coating layer is 20 to 300nm, preferably 50 to 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 layer coated on the surface of the graphite substrate, a silicon nitride layer coated on the surface of the diamond-like layer, and a metal oxide layer or a composite coating coated on the surface of the silicon nitride layer. Wherein the silicon nitride layer is infiltrated into the diamond-like carbon coating layer and the metal oxide layer (or the composite coating layer) simultaneously to form molecular-level links.
According to a third embodiment of the present invention, there is provided a method for preparing an antioxidant graphite mold.
The preparation method of the antioxidant graphite mold comprises the following steps:
1) And (5) preprocessing the graphite die.
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 surface provided with the pre-plating layer. Or (b)
Firstly, mixing and stirring silica sol, aluminum salt, zirconium salt, binder and 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 a composite coating to obtain the graphite mold with a pre-plating layer or coating on the surface.
3) And placing the graphite mould with the pre-plating layer or the coating on the surface in a nitrogen atmosphere for heat treatment to obtain the antioxidant graphite mould with the antioxidant plating layer.
Preferably, the diamond-like layer has a thickness of 30 to 300nm, preferably 50 to 200nm, more preferably 80 to 120nm.
Preferably, the thickness of the metallic silicon layer is 500-2000nm, preferably 800-1500nm, more preferably 1000-1200nm.
Preferably, the metal oxide layer or composite coating has a thickness of 500-2000nm, preferably 800-1500nm, 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.
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, polyoxyethylene, carboxymethyl cellulose and the like.
Preferably, the solvent is water or a low alcohol.
Preferably, the mixing mass ratio of the silica sol, the aluminum salt, the zirconium salt, the binder and the solvent is 0-80:0-20:1-10:40-120, preferably 20-50:20-50:5-10:2-5:50-100.
Preferably, the thickness of the composite coating is 500-2000nm, preferably 800-1500nm, more preferably 1000-1200nm.
Preferably, the step 1) specifically includes: soaking the graphite mold to be treated by adopting 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) specifically includes: and (3) placing the pretreated graphite mould into a vacuum sputtering chamber, sputtering a diamond-like carbon layer by adopting a graphite target, sputtering a metal silicon layer on the surface of the diamond-like carbon layer by adopting a silicon target, and finally sputtering a metal oxide on the surface of the metal silicon layer to obtain the graphite mould with the surface provided with the pre-plating layer.
Or, the step 2) specifically comprises the following steps: firstly adding silica sol, aluminum salt, zirconium salt, binder and solvent into a mixer according to a certain proportion, stirring for 1-24 h (preferably 3-15 h), and carrying out vacuum defoaming after mixing to obtain the composite coating. And then placing the pretreated graphite mould into a vacuum sputtering chamber, sputtering a diamond-like layer by adopting a graphite target, sputtering a metal silicon layer on the surface of the diamond-like layer by adopting a silicon target, finally taking out the graphite mould, and coating a composite coating on the surface of the metal silicon layer to obtain the graphite mould with the coating on the surface.
Preferably, the step 3) specifically includes: placing the graphite mould with the pre-plating layer or coating on the surface into a high temperature furnace, then introducing nitrogen at the temperature of 1300-1700 ℃ (preferably 1400-1600 ℃) for heat treatment for 1-10 hours (preferably 2-4 hours), cooling the graphite mould after heat treatment to room temperature after heat treatment is completed, and polishing the surface of the graphite mould to obtain the antioxidant graphite mould with the antioxidant layer.
Preferably, after the nitriding heat treatment, the metallic silicon layer in the graphite mold is converted into a silicon nitride layer, and the thickness of the silicon nitride layer penetrating into the diamond-like coating layer is 5 to 100nm, preferably 10 to 50nm.
Preferably, the thickness of the silicon nitride layer penetrating into the metal oxide layer or the composite coating layer is 20 to 300nm, preferably 50 to 100nm.
Example 1
1) Soaking the graphite mold to be treated by distilled water, and cleaning the graphite mold for 1h by ultrasonic waves to obtain the pretreated graphite mold.
2) And (3) putting the pretreated graphite mould into a vacuum sputtering chamber, and sequentially sputtering a diamond-like 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 mould to obtain the graphite mould with the preplating layer on the surface.
3) And (3) placing the graphite mold with the pre-plating layer on the surface into a high-temperature nitrogen atmosphere furnace, introducing nitrogen, performing heat treatment at 1400 ℃ for 3 hours, cooling to room temperature, and performing polishing treatment on 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 metallic silicon layer was 500nm.
Example 7
Example 1 was repeated except that the thickness of the metallic silicon layer was 800nm.
Example 8
Example 1 was repeated except that the thickness of the metallic silicon layer was 1500nm.
Example 9
Example 1 was repeated except that the thickness of the metallic 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 was sputtered outside the metallic silicon layer to a thickness of 1100nm.
Example 15
Example 1 was repeated except that a titanium oxide layer of 1100nm was sputtered outside the metallic silicon layer.
Example 16
1) Soaking the graphite mold to be treated by distilled water, and cleaning the graphite mold for 1h by ultrasonic waves to obtain the pretreated graphite mold.
2) 40g of ethyl silicate solution, 40g of aluminum chloride, 10g of zirconia, 5g of PVA binder and 80g of ethanol are added into a mixer to be stirred for 6 hours, and vacuum defoaming is carried out after the mixing is completed, so that the composite coating is obtained. And (3) putting the pretreated graphite mould into a vacuum sputtering chamber, sequentially sputtering a diamond-like transition layer with the thickness of 90nm and a metal silicon layer with the thickness of 1100nm on the surface of the graphite mould, taking out the graphite mould, and coating 1100nm of composite coating on the surface of the metal silicon layer to obtain the graphite mould 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, performing heat treatment for 3 hours at 1400 ℃, cooling to room temperature, and performing polishing treatment on 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 mold.
Comparative example 2
And immersing the graphite mold in a suspension of 50nm alumina to obtain the graphite mold with the surface of the alumina.
Comparative example 3
Example 1 was repeated except that the graphite mold was only coated with a diamond-like transition layer having a thickness of 90nm.
Comparative example 4
Example 1 was repeated except that the graphite mold was plated with only an alumina layer having a thickness of 1100nm.
Comparative example 5
Example 1 was repeated except that the graphite mold was plated with only a metallic silicon layer having a thickness of 1100nm.
Comparative example 6
Example 1 was repeated except that the graphite mold was plated 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 plated with only a diamond-like transition layer having a thickness of 90nm and an aluminum oxide layer having a thickness of 1100nm.
Comparative example 8
Example 1 was repeated except that the graphite mold was plated with only a diamond-like transition layer having a thickness of 90nm and a metallic silicon layer having a thickness of 1100nm.
Comparative example 9
Example 16 was repeated except that the graphite mold was coated with only a composite coating layer having a thickness of 1100nm.
Comparative example 10
Example 16 was repeated except that the graphite mold had only a diamond-like transition layer with a thickness of 90nm and a composite coating with a thickness of 1100nm.
Comparative example 11
The graphite mold to be treated is soaked in distilled water and is cleaned with ultrasonic waves for 1h. And (3) putting the pretreated graphite mould into a vacuum sputtering chamber, sequentially sputtering a diamond-like 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 mould, and polishing the surface of the mould after the sputtering is finished to obtain the graphite mould with an antioxidant function.
Comparative example 12
The graphite mold to be treated is soaked in distilled water and is cleaned with ultrasonic waves for 1h. And (3) putting the pretreated graphite mould into a vacuum sputtering chamber, sequentially sputtering a diamond-like transition layer with the thickness of 90nm, a metal silicon layer with the thickness of 1100nm and a zirconia layer with the thickness of 1100nm on the surface of the graphite mould, and polishing the surface of the mould after the sputtering is finished to obtain the graphite mould with an antioxidant function.
Comparative example 13
The graphite mold to be treated is soaked in distilled water and is cleaned with ultrasonic waves for 1h. And (3) putting the pretreated graphite mould into a vacuum sputtering chamber, sequentially sputtering a diamond-like 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 mould, and polishing the surface of the mould after the sputtering is finished to obtain the graphite mould with an antioxidant function.
The graphite molds prepared in examples 1 to 20 and comparative examples 1 to 14 were subjected to performance test, and adhesion test was performed using GB/T9286-88, and the results are shown in Table 1. The thickness of the silicon nitride layer penetrating into the diamond-like layer and the metal oxide layer was tested and the results are shown in table 2.
Table 1:
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table 2:
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according to the experiment, the bonding force of the graphite mold cannot be damaged by adopting a sputtering method, so that the mold is cracked and damaged in advance in the using process. The service life of the graphite mold with the antioxidant function provided by the invention is prolonged by more than three times compared with that of a non-coating graphite mold. In addition, the sandwich structure coating is adopted, the components have high strength at high temperature and high bonding energy, and in the high-temperature nitrogen atmosphere treatment process, the silicon nitride layer diffuses into the diamond-like layer and the metal oxide layer (or the composite coating), compared with the single-layer coating in the prior art, the sandwich structure coating provided by the invention is tightly attached to the surface layer of the graphite mold, the bonding force between the coating and the surface of the graphite mold is improved, the cooperation among the components of the coating is more intimate, the graphite mold has good wear resistance and oxidation resistance, and the service life of the graphite mold is prolonged.
Claims (14)
1. An oxidation resistant graphite mold, characterized in that: the oxidation-resistant graphite mold comprises a graphite substrate, a diamond-like layer coated on the surface of the graphite substrate, a silicon nitride layer coated on the surface of the diamond-like layer, and a metal oxide layer coated on the surface of the silicon nitride layer; wherein, the silicon nitride layer is penetrated into the diamond-like carbon coating layer and the metal oxide layer simultaneously to form molecular-level links;
the antioxidant graphite mold is prepared by the following steps:
1) Pretreating a graphite matrix;
2) Sputtering a diamond-like carbon layer, a metal silicon layer and a metal oxide layer on the surface of the pretreated graphite substrate in sequence to obtain a graphite mold with a pre-plating layer on the surface;
3) Placing a graphite mold with a pre-plating layer on the surface into a high-temperature furnace, then introducing nitrogen at 1300-1700 ℃ for heat treatment for 1-10 h, cooling the heat-treated graphite mold to room temperature after the heat treatment is completed, and then polishing the surface of the graphite mold to obtain an antioxidant graphite mold;
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; the thickness of the diamond-like carbon layer is 30-300nm, the thickness of the silicon nitride layer is 500-2000nm, and the thickness of the metal oxide layer is 500-2000nm.
2. The oxidation resistant graphite mold as set forth in claim 1, wherein: the thickness of the diamond-like carbon layer is 50-200nm; and/or
The thickness of the silicon nitride layer is 800-1500nm; and/or
The thickness of the metal oxide layer is 800-1500nm.
3. The oxidation resistant graphite mold as set forth in claim 1, wherein: the thickness of the diamond-like carbon layer is 80-120nm; and/or
The thickness of the silicon nitride layer is 1000-1200nm; and/or
The thickness of the metal oxide layer is 1000-1200nm.
4. An oxidation resistant graphite mold according to any one of claims 1-3, wherein: the step 1) specifically comprises the following steps: soaking a graphite mold to be treated by adopting ethanol or distilled water, and ultrasonically cleaning for 0.5-3 hours to obtain a pretreated graphite mold; and/or
The step 2) specifically comprises the following steps: and (3) placing the pretreated graphite mould into a vacuum sputtering chamber, sputtering a diamond-like carbon layer by adopting a graphite target, sputtering a metal silicon layer on the surface of the diamond-like carbon layer by adopting a silicon target, and finally sputtering a metal oxide on the surface of the metal silicon layer to obtain the graphite mould with the surface provided with the pre-plating layer.
5. An oxidation resistant graphite mold according to any one of claims 1-3, wherein: the thickness of the silicon nitride layer penetrating into the diamond-like coating is 5-100nm; and/or
The thickness of the silicon nitride layer penetrating into the metal oxide layer is 20-300nm.
6. An oxidation resistant graphite mold according to any one of claims 1-3, wherein: the thickness of the silicon nitride layer penetrating into the diamond-like coating is 10-50nm; and/or
The thickness of the silicon nitride layer penetrating into the metal oxide layer is 50-100nm.
7. An oxidation resistant graphite mold, characterized in that: the oxidation-resistant graphite mold comprises a graphite substrate, a diamond-like layer coated on the surface of the graphite substrate, a silicon nitride layer coated on the surface of the diamond-like layer and a composite coating coated on the surface of the silicon nitride layer; wherein, the silicon nitride layer is simultaneously infiltrated into the diamond-like carbon coating layer and the composite coating layer to form molecular-level links;
the antioxidant graphite mold is prepared by the following steps:
1) Pretreating a graphite matrix;
2) Firstly, mixing and stirring silica sol, aluminum salt, zirconium salt, binder and 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 substrate in sequence and coating a composite coating to obtain a graphite mold with a coating on the surface;
3) Placing a graphite mold with a coating on the surface into a high-temperature furnace, then introducing nitrogen at 1300-1700 ℃ for heat treatment for 1-10 h, 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 antioxidant graphite mold
The composite coating is prepared by mixing silica sol, aluminum salt, zirconium salt, a binder and a solvent; the weight ratio of the silica sol to the aluminum salt to the zirconium salt to the binder to the solvent is 20-50:20-50:5-10:2-5:50-100; the thickness of the diamond-like carbon layer is 30-300nm, the thickness of the silicon nitride layer is 500-2000nm, and the thickness of the composite coating is 500-2000nm.
8. The oxidation resistant graphite mold as set forth in claim 7, wherein: the thickness of the diamond-like carbon layer is 50-200nm; and/or
The thickness of the silicon nitride layer is 800-1500nm; and/or
The thickness of the composite coating is 800-1500nm.
9. The oxidation resistant graphite mold as set forth in claim 7, wherein: the thickness of the diamond-like carbon layer is 80-120nm; and/or
The thickness of the silicon nitride layer is 1000-1200nm; and/or
The thickness of the composite coating is 1000-1200nm.
10. The oxidation resistant graphite mold as set forth in claim 7, wherein: 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; and/or
The zirconium salt is soluble zirconium salt; and/or
The binder is polyvinyl alcohol or polyethylene glycol; and/or
The solvent is water or a low polyol.
11. The oxidation resistant graphite mold as set forth in claim 7, wherein: the aluminum salt is one or more of aluminum chloride, aluminum sulfate and aluminum nitrate; and/or
The zirconium salt is 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 PVA, polyoxyethylene ethers, PEG, polyoxyethylene and carboxymethyl cellulose.
12. The oxidation resistant graphite mold as set forth in any one of claims 7-11, wherein: the step 1) specifically comprises the following steps: soaking a graphite mold to be treated by adopting ethanol or distilled water, and ultrasonically cleaning for 0.5-3 hours to obtain a pretreated graphite mold; and/or
The step 2) specifically comprises the following steps: firstly, adding silica sol, aluminum salt, zirconium salt, binder and solvent into a mixer according to a certain proportion, stirring for 1-24 h, and carrying out vacuum defoaming after mixing to obtain a composite coating; and then placing the pretreated graphite mould into a vacuum sputtering chamber, sputtering a diamond-like layer by adopting a graphite target, sputtering a metal silicon layer on the surface of the diamond-like layer by adopting a silicon target, finally taking out the graphite mould, and coating a composite coating on the surface of the metal silicon layer to obtain the graphite mould with the coating on the surface.
13. The oxidation resistant graphite mold as set forth in any one of claims 7-11, wherein: the thickness of the silicon nitride layer penetrating into the diamond-like coating is 5-100nm; and/or
The thickness of the silicon nitride layer penetrating into the metal oxide layer or the composite coating layer is 20-300nm.
14. The oxidation resistant graphite mold as set forth in any one of claims 7-11, wherein: the thickness of the silicon nitride layer penetrating into the diamond-like coating is 10-50nm; and/or
The thickness of the silicon nitride layer penetrating into the metal oxide layer or the composite coating layer is 50-100nm.
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