CN116813386A - Self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating for aluminum electrolysis carbon anode and preparation method thereof - Google Patents
Self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating for aluminum electrolysis carbon anode and preparation method thereof Download PDFInfo
- Publication number
- CN116813386A CN116813386A CN202310786779.3A CN202310786779A CN116813386A CN 116813386 A CN116813386 A CN 116813386A CN 202310786779 A CN202310786779 A CN 202310786779A CN 116813386 A CN116813386 A CN 116813386A
- Authority
- CN
- China
- Prior art keywords
- layer
- resistant
- self
- coating
- healing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 156
- 239000011248 coating agent Substances 0.000 title claims abstract description 149
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 76
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 33
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 48
- 239000011521 glass Substances 0.000 claims abstract description 47
- 230000003647 oxidation Effects 0.000 claims abstract description 46
- 230000007704 transition Effects 0.000 claims abstract description 41
- 238000007789 sealing Methods 0.000 claims abstract description 34
- 230000007797 corrosion Effects 0.000 claims abstract description 33
- 238000005260 corrosion Methods 0.000 claims abstract description 33
- 239000000919 ceramic Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims description 65
- 229910052760 oxygen Inorganic materials 0.000 claims description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 54
- 239000007790 solid phase Substances 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 52
- 239000002002 slurry Substances 0.000 claims description 52
- 230000004888 barrier function Effects 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000440 bentonite Substances 0.000 claims description 30
- 229910000278 bentonite Inorganic materials 0.000 claims description 30
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 30
- 238000005303 weighing Methods 0.000 claims description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000011230 binding agent Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 238000007747 plating Methods 0.000 claims description 20
- 239000007791 liquid phase Substances 0.000 claims description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 18
- 235000019353 potassium silicate Nutrition 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052580 B4C Inorganic materials 0.000 claims description 12
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000008247 solid mixture Substances 0.000 claims description 7
- 230000003064 anti-oxidating effect Effects 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 229920000609 methyl cellulose Polymers 0.000 claims description 6
- 239000001923 methylcellulose Substances 0.000 claims description 6
- 235000010981 methylcellulose Nutrition 0.000 claims description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- 239000006255 coating slurry Substances 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- DZPJVKXUWVWEAD-UHFFFAOYSA-N [C].[N].[Si] Chemical compound [C].[N].[Si] DZPJVKXUWVWEAD-UHFFFAOYSA-N 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 136
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000001680 brushing effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011241 protective layer Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 235000008113 selfheal Nutrition 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/085—Cell construction, e.g. bottoms, walls, cathodes characterised by its non electrically conducting heat insulating parts
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
- C25C3/125—Anodes based on carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses an aluminum electrolysis carbon anode self-healing high-oxygen-resistance high-temperature oxidation-prevention composite coating and a preparation method thereof, and belongs to the technical field of aluminum electrolysis carbon anode oxidation-resistance coatings. The composite coating comprises a bonding transition layer, a self-healing glass oxygen-blocking layer, a sealing layer and a high-temperature-resistant corrosion-resistant ceramic layer; the invention adopts a brushing or spraying method to uniformly coat a plurality of layers of coatings on the surface of the aluminum electrolysis carbon anode in batches under the room temperature condition, and can be solidified at the room temperature; the protective layer is sintered at 400-800 ℃ to form an adhesion transition layer, a self-healing glass oxygen-blocking layer, a sealing layer and a high-temperature-resistant corrosion-resistant ceramic layer in situ. The self-healing high-oxygen-resistance high-temperature oxidation-prevention composite coating prepared by the invention can prolong the anode electrode replacement period by more than 2 days, has low cost of raw materials, is suitable for industrial production, has compact coating, good oxidation resistance effect, can withstand the temperature of more than 900 ℃ for a long time, and has stable physical and chemical properties; has wide application prospect in the field of oxidation resistance of aluminum electrolysis carbon anodes.
Description
Technical Field
The invention relates to the technical field of aluminum electrolysis carbon anode antioxidation coating, in particular to an aluminum electrolysis carbon anode self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating and a preparation method thereof.
Background
In recent years, the aluminum industry in China rapidly develops, and the aluminum yield in China stands in the front of the world. At present, cryolite-alumina fused salt electrolysis method is adopted in the aluminum electrolysis industry, wherein a carbon anode is taken as an indispensable part in the electrolytic aluminum production process, and the production cost of the carbon anode accounts for more than 15% of the total cost, so that the consumption of the anode carbon block is an important production technical index for measuring the electrolytic aluminum production. In the aluminium electrolysis process, 333kg of carbon should be theoretically consumed per ton of aluminium produced, but 460-500 kg is consumed in actual production. In the aluminum electrolysis process, the consumption of the anode carbon block mainly comprises three types of electrochemical consumption, residual carbon consumption and chemical consumption. The electrochemical consumption and the residual carbon consumption are unavoidable in the production process, and the chemical consumption is extra consumption caused by the fact that the carbon anode is easy to generate oxidation reaction with oxygen under the high-temperature condition, so that the consumption can be reduced by an effective means.
Research shows that the preparation of a compact high temperature resistant and oxidation resistant coating on the surface of the carbon anode can prevent oxygen from entering the carbon anode to perform oxidation reaction, and is an effective method for reducing the oxidation consumption of the carbon anode. The paint disclosed by the patent application numbers CN202210070662.0, CN201710041749.4, CN201911310797.4 and CN201911337979.0 has larger thermal expansion coefficient difference between the paint and the carbon anode, generates thermal stress, easily causes cracks on the coating, has poor self-healing performance, cannot cause the self-healing of the cracks, and has poor oxidation resistance effect of the coating due to the existence of the cracks. The paint disclosed in the patent application numbers CN201510442632.8 and CN201710081675.7 is prepared from a large amount of low-melting-point boride and the like, has poor corrosion resistance under high-temperature conditions, can cause the coating to fall off after being corroded, influences the long-term oxidation resistance of the coating, and can introduce new impurities into the electrolyte to influence the electrolyte environment. The paint disclosed in the patent application number 201810363913.8 is prepared from aluminum ash, so that the components of the paint are not easy to control and complex, and the antioxidation effect is poor.
In order to solve the problems of the high-temperature-resistant and oxidation-resistant coating of the carbon anode, a self-healing, high-oxygen-resistant, high-temperature-resistant, corrosion-resistant and oxidation-resistant coating is developed to reduce the oxidation consumption of the carbon anode and reduce CO 2 The emission has larger economic effect and social effect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an aluminum electrolysis carbon anode self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating and a preparation method thereof.
The technical scheme of the invention is as follows: the composite structure of the self-healing high-oxygen-resistant high-temperature oxidation-resistant composite coating comprises a bonding transition layer, a self-healing glass oxygen-resistant layer, a sealing layer and a high-temperature-resistant corrosion-resistant ceramic layer.
Further, the bonding transition layer comprises the following raw materials in percentage by mass: 60-95% of main component, 5-40% of binder and 100% of sum of the components by mass percent.
Further, the self-healing glass oxygen barrier layer comprises the following raw materials in percentage by mass: 60-85% of main component, 15-35% of binder, 5-10% of auxiliary sintering agent and 100% of sum of the components in percentage by mass.
Further, the sealing layer comprises the following raw materials in percentage by mass: 50-70% of main component, 10-35% of binder, 5-15% of auxiliary sintering agent and 100% of sum of the above components by mass percent.
Further, the high-temperature-resistant corrosion-resistant ceramic layer comprises the following raw materials in percentage by mass: 75-90% of main component, 5-20% of binder and 5-10% of auxiliary sintering agent, wherein the sum of the mass percentages of the components is 100%.
Further, the main components of the bonding transition layer are silicon carbide, silicon boride and silicon carbon nitrogen.
Further, the self-healing glass oxygen barrier layer comprises silicon dioxide, aluminum oxide and boron carbide as main components.
Further, the main components of the packing layer are silicon dioxide, aluminum oxide, boron carbide, boron oxide and calcium oxide.
Further, the main components of the high-temperature-resistant corrosion-resistant ceramic layer are silicon dioxide, aluminum oxide and boric acid.
Further, the binder is formed by mixing one or more of polyvinyl alcohol, methyl cellulose, water glass, polyacrylamide, a silane coupling agent and bentonite with water according to the mass ratio of (1-5) to (10-50).
Further, the auxiliary sintering agent is one or two of titanium dioxide and aluminum powder.
The invention provides a preparation method of an aluminum electrolysis carbon anode self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating, which comprises the following specific steps:
(1) Preparation of liquid phase binder: mixing one or more of polyvinyl alcohol, methyl cellulose, water glass, polyacrylamide, a silane coupling agent and bentonite with deionized water, and stirring uniformly after ultrasonic treatment to obtain a liquid-phase binder; wherein the mass fraction of deionized water is 40-90 wt%, and the mass fraction of one or more of polyvinyl alcohol, sodium carboxymethylcellulose, water glass, polyacrylamide, a silane coupling agent and bentonite is 10-60 wt%;
(2) Mixing solid phase powder: sequentially weighing main components and auxiliary sintering agent raw materials according to the bonding transition layer, the self-healing glass oxygen barrier layer, the sealing filling layer and the high-temperature-resistant corrosion-resistant ceramic layer respectively, and uniformly mixing solid powder of each layer of coating through mechanical mixing to obtain respective solid mixture of each layer of coating;
(3) Preparation of the slurry: uniformly dispersing solid mixtures of different coatings in respective liquid phase binders to obtain coating slurry of each layer of coating;
(4) Coating of a composite coating: coating the slurry of the bonding transition layer on the surface of the carbon anode by adopting a slurry brush plating method, and drying in an oven to obtain the bonding transition layer; coating the slurry of the self-healing glass oxygen barrier layer on the surface of the carbon anode with the bonding transition layer by adopting a slurry brush plating method, and drying in an oven to obtain the self-healing glass oxygen barrier layer; coating the slurry of the sealing and filling layer on the surface of the carbon anode with the bonding transition layer and the self-healing glass oxygen barrier layer by adopting a slurry brush plating method, and drying in an oven to obtain the sealing and filling layer; coating the slurry of the high-temperature-resistant corrosion-resistant ceramic layer on the surface of the carbon anode with the bonding transition layer, the self-healing glass oxygen-resistant layer and the sealing layer by adopting a slurry brush plating method, and drying in an oven to obtain the high-temperature-resistant corrosion-resistant ceramic layer;
(5) Curing of the composite coating: continuously curing the composite coating in a constant-temperature drying oven or a drying chamber at 105-120 ℃ for 8-12 h;
(6) Roasting the composite coating: roasting the carbon anode coated with the composite coating, and then cooling along with a furnace; after roasting treatment, the antioxidation coating with a multi-layer structure of a bonding transition layer, a self-healing glass oxygen-blocking layer, a sealing layer and a high-temperature-resistant corrosion-resistant ceramic layer can be formed on the surface of the coating in situ.
Further, the liquid phase binder in the step (1) is prepared by using a magnetic stirrer, wherein the stirring speed is 300-500 rpm, and the stirring time is 0.5-1 h.
Further, the coating slurry in the step (3) is prepared by using a magnetic stirrer, wherein the stirring speed is 100-500 rpm, and the time is 1-3 h.
Further, in the step (4), the drying temperature is 60-90 ℃ and the drying time is 2-4 hours.
Further, the roasting temperature in the step (6) is 400-800 ℃, and the roasting time is 2-4 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. the paint prepared by the invention has good adhesiveness, can be used for coating a coating on the surface of the carbon anode by adopting a brushing or spraying method, and has the advantages of simple preparation process, low raw material price and more excellent economic conditions.
2. The coating prepared by the invention can be sintered at 400-800 ℃ to form a compact antioxidation coating, wherein the oxygen barrier layer can generate a glass layer with good fluidity and compactness in situ, prevent oxygen permeation, prevent carbon anodic oxidation, have good antioxidation effect, and simultaneously can self-heal and repair coating cracks due to the fluidity.
3. The coating prepared by the invention can generate a compact alumina ceramic layer in situ after sintering the high-temperature-resistant corrosion-resistant ceramic layer, can prevent the corrosion of the electrolytic bath environment to the glass layer, protect the stability of the glass layer and prevent the pollution of the coating to electrolyte.
4. The coating prepared by the invention has long-term tolerance temperature of above 900 ℃ and stable physical and chemical properties.
Drawings
FIG. 1 is a schematic structural diagram of a composite coating prepared according to the present invention.
FIG. 2 is a graph showing the weight change of a carbon anode with a composite coating prepared by the invention, oxidized for 96 hours at 900 ℃.
FIG. 3 is a graph of the macroscopic morphology of the carbon anode of the composite coating prepared according to the invention after drying and 96h oxidation, respectively.
Figure 4 is an XRD profile of a composite coating prepared in accordance with the present invention after drying.
FIG. 5 is an XRD plot of a composite coating prepared in accordance with the present invention after 96h of oxidation.
FIG. 6 is an XRD curve of an oxygen barrier layer prepared according to the present invention after firing.
FIG. 7 shows the surface morphology of the oxygen barrier layer prepared by the present invention after baking.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
An aluminum electrolysis carbon anode self-healing high-oxygen-resistance high-temperature oxidation-prevention composite coating and a preparation method thereof, comprising the following steps:
(1) Preparation of liquid phase binder: according to the mass ratio of 1:1:1:45, respectively weighing water glass, polyvinyl alcohol, bentonite and deionized water, carrying out ultrasonic treatment on the water glass, the polyvinyl alcohol and the bentonite, uniformly stirring to obtain a mixture, and then mixing the mixture with the deionized water under the condition that the magnetic stirring speed is 400rpm, and keeping mechanical stirring for 1h to obtain the liquid-phase adhesive.
(2) Mixing solid phase powder: according to the mass ratio of bentonite to silicon carbide of 1:15, weighing silicon carbide to obtain solid phase powder of the bonding transition layer; according to the mass ratio of bentonite to self-healing glass oxygen barrier solid phase powder of 1:15, weighing solid phase powder of the self-healing glass oxygen barrier layer, wherein the solid phase powder comprises the following components in percentage by mass of 35% of silicon dioxide, 5% of aluminum oxide, 50% of boron carbide, 5% of titanium dioxide and 5% of aluminum powder; according to the mass ratio of bentonite to solid phase powder of the sealing layer of 1:6, weighing solid phase powder of the sealing and filling layer, wherein the solid phase powder comprises 55 mass percent of silicon dioxide, 20 mass percent of aluminum oxide, 10 mass percent of boron carbide, 5 mass percent of titanium dioxide and 10 mass percent of aluminum powder; according to the mass ratio of bentonite to the solid phase powder of the high temperature resistant and corrosion resistant ceramic layer of 1:12, weighing solid phase powder of the high temperature resistant and corrosion resistant ceramic layer, wherein the solid phase powder comprises the following components in percentage by mass of 5% of silicon dioxide, 80% of aluminum oxide, 5% of boric acid, 5% of titanium dioxide and 5% of aluminum powder; and uniformly mixing the solid phase powder of each coating to obtain respective solid phase mixture for standby.
(3) Preparation of the slurry: and uniformly dispersing solid mixtures of different coatings in respective liquid phase binders by adopting a magnetic stirrer, wherein the magnetic stirring speed is 500rpm, and the stirring time is 2 hours, so as to obtain the slurry of each coating layer.
(4) Coating of a composite coating: coating the slurry of the bonding transition layer on the surface of the carbon anode by adopting a slurry brush plating method, and drying in an oven at 80 ℃ for 2 hours to obtain the bonding transition layer; coating the slurry of the self-healing glass oxygen barrier layer on the surface of the carbon anode with the bonding transition layer by adopting a slurry brush plating method, and drying in an oven at 80 ℃ for 2 hours to obtain the self-healing glass oxygen barrier layer; coating the sealing layer slurry on the surface of a carbon anode with a bonding transition layer and a self-healing glass oxygen barrier layer by adopting a slurry brush plating method, and drying in an oven at 80 ℃ for 2 hours to obtain a sealing layer; and (3) coating the slurry of the high-temperature-resistant and corrosion-resistant ceramic layer on the surface of the carbon anode with the bonding transition layer, the self-healing glass oxygen-blocking layer and the sealing layer by adopting a slurry brush plating method, and drying in an oven at 80 ℃ for 2 hours to obtain the high-temperature-resistant and corrosion-resistant ceramic layer.
(5) Drying of the composite coating: the composite coating was further dried in a drying oven at 120℃for 10 hours.
(6) Roasting the composite coating: the carbon anode with the dried coating is heated to 700 ℃ at a speed of 5 ℃/min and is kept for 4 hours, and the composite coating is obtained, as shown in figure 1.
And (3) oxidation resistance test: raising the temperature from room temperature to 900 ℃ at a speed of 5 ℃/min, preserving the temperature at 900 ℃ for 24 hours, cooling along with a furnace, taking out and weighing, and repeating the calculation for 3 times to obtain the average value. And after weighing, continuing constant-temperature oxidation at 900 ℃ and accumulating the total oxidation time for 96 hours. The test data are shown in the first curve of FIG. 2, and the weight loss rate of the carbon anode coated with the composite coating after 96h oxidation is only 0.56%.
Fig. 3, a1 and a2, show the macroscopic topography of the resulting composite coating after drying and 96h oxidation, respectively. The coating cracks can self-heal at high temperature and remain intact after 96 hours of oxidation of the coating.
After drying and calcining the resulting composite coating, oxygen barrier slurry, the data obtained are shown in fig. 4, 5 and 6 as curve one using X-ray diffraction test analysis (XRD). The amorphous glass layer is formed after the oxygen barrier layer is baked, so that oxygen can be effectively prevented from entering the carbon anode to react, and the phase of the composite coating is still stable after the composite coating is oxidized for 96 hours.
The surface morphology of the baked oxygen barrier layer was observed by Scanning Electron Microscopy (SEM) as shown in fig. 7a, and the coating was dense and continuous without holes and cracks.
Example 2
An aluminum electrolysis carbon anode self-healing high-oxygen-resistance high-temperature oxidation-prevention composite coating and a preparation method thereof, comprising the following steps:
(1) Preparation of liquid phase binder: according to the mass ratio of 1:1:1:45, respectively weighing water glass, methylcellulose, bentonite and deionized water, carrying out ultrasonic treatment on the water glass, the methylcellulose and the bentonite, uniformly stirring to obtain a mixture, and then mixing the mixture with the deionized water under the condition that the magnetic stirring speed is 300rpm, and keeping mechanical stirring for 1h to obtain the liquid-phase binder.
(2) Mixing solid phase powder: according to the mass ratio of bentonite to silicon carbide of 1:15, weighing silicon carbide to obtain solid phase powder of the bonding transition layer; according to the mass ratio of bentonite to self-healing glass oxygen barrier solid phase powder of 1:15, weighing solid phase powder of the self-healing glass oxygen barrier layer, wherein the solid phase powder comprises the following components in percentage by mass of 35% of silicon dioxide, 5% of aluminum oxide, 50% of boron carbide, 5% of titanium dioxide and 5% of aluminum powder; according to the mass ratio of bentonite to solid phase powder of the sealing layer of 1:6, weighing solid phase powder of the sealing and filling layer, wherein the solid phase powder comprises 65 mass percent of silicon dioxide, 10 mass percent of aluminum oxide, 15 mass percent of boron carbide, 5 mass percent of titanium dioxide and 5 mass percent of aluminum powder; according to the mass ratio of bentonite to the solid phase powder of the high temperature resistant and corrosion resistant ceramic layer of 1:12, weighing solid phase powder of the high temperature resistant and corrosion resistant ceramic layer, wherein the solid phase powder comprises the following components in percentage by mass of 5% of silicon dioxide, 80% of aluminum oxide, 5% of boric acid, 5% of titanium dioxide and 5% of aluminum powder; and uniformly mixing the solid phase powder of each coating to obtain respective solid phase mixture for standby.
(3) Preparation of the slurry: and uniformly dispersing solid mixtures of different coatings in respective liquid phase binders by using a magnetic stirrer, wherein the magnetic stirring speed is 300rpm, and the stirring time is 3 hours, so as to obtain the slurry of each coating layer.
(4) Coating of a composite coating: coating the slurry of the bonding transition layer on the surface of the carbon anode by adopting a slurry brush plating method, and drying in an oven at 70 ℃ for 1.5 hours to obtain the bonding transition layer; coating the slurry of the self-healing glass oxygen barrier layer on the surface of the carbon anode with the bonding transition layer by adopting a slurry brush plating method, and drying in an oven at 70 ℃ for 1.5 hours to obtain the self-healing glass oxygen barrier layer; coating the sealing layer slurry on the surface of a carbon anode with a bonding transition layer and a self-healing glass oxygen barrier layer by adopting a slurry brush plating method, and drying in an oven at 70 ℃ for 1.5 hours to obtain a sealing layer; and (3) coating the slurry of the high-temperature-resistant and corrosion-resistant ceramic layer on the surface of the carbon anode with the bonding transition layer, the self-healing glass oxygen-blocking layer and the sealing layer by adopting a slurry brush plating method, and drying in an oven at 70 ℃ for 1.5 hours to obtain the high-temperature-resistant and corrosion-resistant ceramic layer.
(5) Drying of the composite coating: the composite coating was further dried in a drying oven at 120℃for 8 hours.
(6) Roasting the composite coating: the carbon anode after the coating is solidified is heated to 800 ℃ at a speed of 5 ℃/min and is kept for 3 hours, and the composite coating is obtained as shown in figure 1.
And (3) oxidation resistance test: raising the temperature from room temperature to 900 ℃ at a speed of 5 ℃/min, preserving the temperature at 900 ℃ for 24 hours, cooling along with a furnace, taking out and weighing, and repeating the calculation for 3 times to obtain the average value. And after weighing, continuing constant-temperature oxidation at 900 ℃ and accumulating the total oxidation time for 96 hours. The test data are shown in a curve II of FIG. 1, and the weight loss rate of the carbon anode coated with the composite coating after 96h oxidation is only 0.50%.
Fig. 3 shows the macroscopic morphology of the composite coating after drying and 96h oxidation, respectively, as b1 and b 2. The coating cracks can self-heal at high temperature and remain intact after 96 hours of oxidation of the coating.
The resulting composite coating and oxygen barrier layer were dried and calcined in a slurry and analyzed by X-ray diffraction test (XRD) and the resulting data are shown in fig. 4, 5 and 6 as curve two. The amorphous glass layer is formed after the oxygen barrier layer is baked, so that oxygen can be effectively prevented from entering the carbon anode to react, and the phase of the composite coating is still stable after the composite coating is oxidized for 96 hours.
The surface morphology of the baked oxygen barrier layer was observed by Scanning Electron Microscopy (SEM) as shown in fig. 7b, and the coating was dense and continuous without holes and cracks.
Example 3
An aluminum electrolysis carbon anode self-healing high-oxygen-resistance high-temperature oxidation-prevention composite coating and a preparation method thereof, comprising the following steps:
(1) Preparation of liquid phase binder: according to the mass ratio of 1:1:1:45, respectively weighing water glass, a silane coupling agent, bentonite and deionized water, carrying out ultrasonic treatment on the water glass, the silane coupling agent and the bentonite, uniformly stirring to obtain a mixture, and then mixing the mixture with the deionized water under the condition that the magnetic stirring speed is 400rpm, and keeping mechanical stirring for 0.5h to obtain the liquid-phase binder.
(2) Mixing solid phase powder: according to the mass ratio of bentonite to silicon carbide of 1:15, weighing silicon carbide to obtain solid phase powder of the bonding transition layer; according to the mass ratio of bentonite to self-healing glass oxygen barrier solid phase powder of 1:15, weighing solid phase powder of the self-healing glass oxygen barrier layer, wherein the solid phase powder comprises the following components in percentage by mass of 35% of silicon dioxide, 5% of aluminum oxide, 50% of boron carbide, 5% of titanium dioxide and 5% of aluminum powder; according to the mass ratio of bentonite to solid phase powder of the sealing layer of 1:6, weighing solid phase powder of the sealing layer, wherein the solid phase powder comprises 60 mass percent of silicon dioxide, 10 mass percent of aluminum oxide, 15 mass percent of boron carbide, 5 mass percent of calcium oxide, 5 mass percent of titanium dioxide and 5 mass percent of aluminum powder; according to the mass ratio of bentonite to the solid phase powder of the high temperature resistant and corrosion resistant ceramic layer of 1:12, weighing solid phase powder of the high temperature resistant and corrosion resistant ceramic layer, wherein the solid phase powder comprises the following components in percentage by mass of 5% of silicon dioxide, 80% of aluminum oxide, 5% of boric acid, 5% of titanium dioxide and 5% of aluminum powder; and uniformly mixing the solid phase powder of each coating to obtain respective solid phase mixture for standby.
(3) Preparation of the slurry: and uniformly dispersing the solid mixtures of different coatings in the respective liquid phase binders by adopting a magnetic stirrer, wherein the magnetic stirring speed is 400rpm, and the stirring time is 2 hours, so as to obtain the slurry of each coating layer.
(4) Coating of a composite coating: coating the slurry of the bonding transition layer on the surface of the carbon anode by adopting a slurry brush plating method, and drying in an oven at 85 ℃ for 2 hours to obtain the bonding transition layer; coating the slurry of the self-healing glass oxygen barrier layer on the surface of the carbon anode with the bonding transition layer by adopting a slurry brush plating method, and drying in an oven at 85 ℃ for 2 hours to obtain the self-healing glass oxygen barrier layer; coating the sealing layer slurry on the surface of a carbon anode with a bonding transition layer and a self-healing glass oxygen barrier layer by adopting a slurry brush plating method, and drying in an oven at 85 ℃ for 2 hours to obtain a sealing layer; and (3) coating the slurry of the high-temperature-resistant and corrosion-resistant ceramic layer on the surface of the carbon anode with the bonding transition layer, the self-healing glass oxygen-blocking layer and the sealing layer by adopting a slurry brush plating method, and drying in an oven at 85 ℃ for 2 hours to obtain the high-temperature-resistant and corrosion-resistant ceramic layer.
(5) Drying of the composite coating: the composite coating was further dried in a drying oven at 120℃for 12 hours.
(6) Roasting the composite coating: the carbon anode after the coating is solidified is heated to 850 ℃ at a speed of 5 ℃/min, and is kept for 4 hours, so that the composite coating is obtained, and the composite coating is shown in figure 1.
And (3) oxidation resistance test: raising the temperature from room temperature to 900 ℃ at a speed of 5 ℃/min, preserving the temperature at 900 ℃ for 24 hours, cooling along with a furnace, taking out and weighing, and repeating the calculation for 3 times to obtain the average value. And after weighing, continuing constant-temperature oxidation at 900 ℃ and accumulating the total oxidation time for 96 hours. The obtained test data are shown as a curve III in FIG. 1, and the weight loss rate of the carbon anode coated with the composite coating after 96h oxidation is only 0.58%.
Fig. 3, c1 and c2, show the macroscopic topography of the resulting composite coating after drying and 96h oxidation, respectively. The coating cracks can self-heal at high temperature and remain intact after 96 hours of oxidation of the coating.
The resulting composite coating and oxygen barrier layer were dried and calcined in a slurry and analyzed by X-ray diffraction test (XRD) and the resulting data are shown in curve three in fig. 4, 5 and 6. The amorphous glass layer is formed after the oxygen barrier layer is baked, so that oxygen can be effectively prevented from entering the carbon anode to react, and the phase of the composite coating is still stable after the composite coating is oxidized for 96 hours.
The surface morphology of the baked oxygen barrier layer was observed by Scanning Electron Microscopy (SEM) as shown in fig. 7c, and the coating was dense and continuous without holes and cracks.
Example 4
An aluminum electrolysis carbon anode self-healing high-oxygen-resistance high-temperature oxidation-prevention composite coating and a preparation method thereof, comprising the following steps:
(1) Preparation of liquid phase binder: according to the mass ratio of 1:1:1:45, respectively weighing water glass, polyacrylamide, bentonite and deionized water, carrying out ultrasonic treatment on the water glass, the polyacrylamide and the bentonite, uniformly stirring to obtain a mixture, and then mixing the mixture with the deionized water under the condition that the magnetic stirring speed is 350rpm, and keeping mechanical stirring for 1h to obtain the liquid-phase adhesive.
(2) Mixing solid phase powder: according to the mass ratio of bentonite to silicon carbide of 1:15, weighing silicon carbide to obtain solid phase powder of the bonding transition layer; according to the mass ratio of bentonite to self-healing glass oxygen barrier solid phase powder of 1:15, weighing solid phase powder of the self-healing glass oxygen barrier layer, wherein the solid phase powder comprises 40 mass percent of silicon dioxide, 5 mass percent of aluminum oxide, 45 mass percent of boron carbide, 5 mass percent of titanium dioxide and 5 mass percent of aluminum powder; according to the mass ratio of bentonite to solid phase powder of the sealing layer of 1:6, weighing solid phase powder of the sealing layer, wherein the solid phase powder comprises 60 mass percent of silicon dioxide, 5 mass percent of aluminum oxide, 10 mass percent of boron carbide, 15 mass percent of boron oxide, 5 mass percent of titanium dioxide and 5 mass percent of aluminum powder; according to the mass ratio of bentonite to the solid phase powder of the high temperature resistant and corrosion resistant ceramic layer of 1:12, weighing solid phase powder of the high temperature resistant and corrosion resistant ceramic layer, wherein the solid phase powder comprises the following components in percentage by mass of 5% of silicon dioxide, 80% of aluminum oxide, 5% of boric acid, 5% of titanium dioxide and 5% of aluminum powder; and uniformly mixing the solid phase powder of each coating to obtain respective solid phase mixture for standby.
(6) Roasting the composite coating: the carbon anode after the coating is solidified is heated to 750 ℃ at a speed of 5 ℃/min and is kept for 4 hours, and the composite coating is obtained, as shown in figure 1.
And (3) oxidation resistance test: raising the temperature from room temperature to 900 ℃ at a speed of 5 ℃/min, preserving the temperature at 900 ℃ for 24 hours, cooling along with a furnace, taking out and weighing, and repeating the calculation for 3 times to obtain the average value. And after weighing, continuing constant-temperature oxidation at 900 ℃ and accumulating the total oxidation time for 96 hours. The test data are shown as curve IV in FIG. 1, and the weight loss rate of the carbon anode coated with the composite coating after 96h oxidation is only 0.52%.
The d1 and d2 graphs in FIG. 3 are the macroscopic topography of the resulting composite coating after drying and 96h oxidation, respectively. The coating cracks can self-heal at high temperature and remain intact after 96 hours of oxidation of the coating.
The resulting composite coating and oxygen barrier layer were dried and calcined in a slurry and analyzed by X-ray diffraction test (XRD) and the resulting data are shown as curve four in fig. 4, 5 and 6. The amorphous glass layer is formed after the oxygen barrier layer is baked, so that oxygen can be effectively prevented from entering the carbon anode to react, and the phase of the composite coating is still stable after the composite coating is oxidized for 96 hours.
The surface morphology of the baked oxygen barrier layer was observed by Scanning Electron Microscopy (SEM) as shown in fig. 7d, the coating was dense and continuous, and no holes or cracks were formed.
The above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or simple substitutions that do not undergo the inventive work should be covered in the scope of the present invention.
Claims (10)
1. The self-healing high-oxygen-resistance high-temperature oxidation-prevention composite coating for the aluminum electrolysis carbon anode and the preparation method thereof are characterized in that the composite coating comprises a bonding transition layer, a self-healing glass oxygen-resistance layer, a sealing layer and a high-temperature-resistance corrosion-resistance ceramic layer; the bonding transition layer comprises the following raw materials in percentage by mass: 60-95% of main components, 5-40% of binder, and 100% of the total mass percentage of the components; the self-healing glass oxygen barrier layer comprises the following raw materials in percentage by mass: 60-85% of main components, 15-35% of binder, 5-10% of auxiliary sintering agent, and 100% of the total mass percentage of the components; the sealing layer comprises the following raw materials in percentage by mass: 50-70% of main components, 10-35% of binder, 5-15% of auxiliary sintering agent, and 100% of the total mass percentage of the above components; the high-temperature-resistant corrosion-resistant ceramic layer comprises the following raw materials in percentage by mass: 75-90% of main component, 5-20% of binder and 5-10% of auxiliary sintering agent, wherein the sum of the mass percentages of the components is 100%.
2. The self-healing high-oxygen-resistant high-temperature oxidation-resistant composite coating for an aluminum electrolysis carbon anode according to claim 1, wherein the main components of the bonding transition layer are silicon carbide, silicon boride and silicon carbon nitrogen.
3. The self-healing high-oxygen-resistant high-temperature oxidation-resistant composite coating for the aluminum electrolysis carbon anode according to claim 1, wherein the self-healing glass oxygen-resistant layer is mainly composed of silicon dioxide, aluminum oxide and boron carbide.
4. The self-healing high-oxygen-resistant high-temperature oxidation-resistant composite coating for the aluminum electrolysis carbon anode according to claim 1, wherein the main components of the sealing layer are silicon dioxide, aluminum oxide, boron carbide, boron oxide and calcium oxide.
5. The self-healing high-oxygen-resistant high-temperature oxidation-resistant composite coating for the aluminum electrolysis carbon anode according to claim 1, wherein the main components of the high-temperature-resistant corrosion-resistant ceramic layer are silicon dioxide, aluminum oxide and boric acid.
6. The self-healing high-oxygen-resistant high-temperature oxidation-resistant composite coating for the aluminum electrolysis carbon anode according to claim 1, wherein the binder is formed by mixing one or more of polyvinyl alcohol, methyl cellulose, water glass, polyacrylamide, a silane coupling agent and bentonite with water according to the mass ratio of (1-5) (10-50).
7. The self-healing high-oxygen-resistant high-temperature oxidation-resistant composite coating for the aluminum electrolysis carbon anode according to claim 1, wherein the auxiliary sintering agent is one or two of titanium dioxide and aluminum powder.
8. The preparation method of the self-healing high-oxygen-resistant high-temperature oxidation-resistant composite coating of the aluminum electrolysis carbon anode according to any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) Preparation of liquid phase binder: mixing one or more of polyvinyl alcohol, methyl cellulose, water glass, polyacrylamide, a silane coupling agent and bentonite with deionized water, and stirring uniformly after ultrasonic treatment to obtain a liquid-phase binder; wherein the mass fraction of deionized water is 40-90 wt%, and the mass fraction of one or more of polyvinyl alcohol, sodium carboxymethylcellulose, water glass, polyacrylamide, a silane coupling agent and bentonite is 10-60 wt%;
(2) Mixing solid phase powder: sequentially weighing main components and auxiliary sintering agent raw materials according to the bonding transition layer, the self-healing glass oxygen barrier layer, the sealing filling layer and the high-temperature-resistant corrosion-resistant ceramic layer respectively, and uniformly mixing solid powder of each layer of coating through mechanical mixing to obtain respective solid mixture of each layer of coating;
(3) Preparation of the slurry: uniformly dispersing solid mixtures of different coatings in respective liquid phase binders to obtain coating slurry of each layer of coating;
(4) Coating of a composite coating: coating the slurry of the bonding transition layer on the surface of the carbon anode by adopting a slurry brush plating or spraying method, and drying in an oven to obtain the bonding transition layer; coating the self-healing glass oxygen barrier layer slurry on the surface of the carbon anode with the bonding transition layer by adopting a slurry brush plating or spraying method, and drying in an oven to obtain the self-healing glass oxygen barrier layer; coating the sealing layer slurry on the surface of the carbon anode with the bonding transition layer and the self-healing glass oxygen barrier layer by adopting a slurry brush plating or spraying method, and drying in an oven to obtain the sealing layer; coating the slurry of the high-temperature-resistant corrosion-resistant ceramic layer on the surface of the carbon anode with the bonding transition layer, the self-healing glass oxygen-resistant layer and the sealing layer by adopting a slurry brush plating or spraying method, and drying in an oven to obtain the high-temperature-resistant corrosion-resistant ceramic layer;
(5) Curing of the composite coating: continuously curing the composite coating in a constant-temperature drying oven or a drying chamber at 105-120 ℃ for 8-12 h;
(6) Preparation of the composite coating: roasting the carbon anode coated with the composite coating, and then cooling along with a furnace; after roasting treatment, the antioxidation coating with a multi-layer structure of a bonding transition layer, a self-healing glass oxygen-blocking layer, a sealing layer and a high-temperature-resistant corrosion-resistant ceramic layer can be formed on the surface of the coating in situ.
9. The method for preparing the self-healing high-oxygen-resistant high-temperature oxidation-resistant composite coating for the aluminum electrolysis carbon anode, which is disclosed in claim 8, is characterized in that the mixing preparation of the liquid-phase binder in the step (1) is mechanical stirring, the stirring speed is 300-500 rpm, and the time is 0.5-1 h; the coating slurry in the step (3) is prepared by mechanical stirring, wherein the stirring speed is 100-500 rpm, and the time is 1-3 h.
10. The method for preparing the self-healing high-oxygen-resistant high-temperature oxidation-resistant composite coating for the aluminum electrolysis carbon anode, which is disclosed in claim 8, is characterized in that the drying temperature in the step (4) is 60-90 ℃, and the drying time is 2-4 hours; the roasting temperature in the step (6) is 400-800 ℃, and the roasting time is 2-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310786779.3A CN116813386B (en) | 2023-06-30 | 2023-06-30 | Self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating for aluminum electrolysis carbon anode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310786779.3A CN116813386B (en) | 2023-06-30 | 2023-06-30 | Self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating for aluminum electrolysis carbon anode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116813386A true CN116813386A (en) | 2023-09-29 |
| CN116813386B CN116813386B (en) | 2024-08-09 |
Family
ID=88128869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310786779.3A Active CN116813386B (en) | 2023-06-30 | 2023-06-30 | Self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating for aluminum electrolysis carbon anode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116813386B (en) |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316718A (en) * | 1991-06-14 | 1994-05-31 | Moltech Invent S.A. | Composite electrode for electrochemical processing having improved high temperature properties and method for preparation by combustion synthesis |
| CN101250722A (en) * | 2007-11-16 | 2008-08-27 | 广西师范大学 | Carbon element anode oxidation resistance layer for aluminium electrolysis and coating method thereof |
| CN101386995A (en) * | 2008-10-22 | 2009-03-18 | 中国铝业股份有限公司 | Aluminum electrolysis carbon anode oxidation coating and coating method thereof |
| WO2011012819A1 (en) * | 2009-07-30 | 2011-02-03 | Snecma | Method for manufacturing a thermal barrier |
| CN102503581A (en) * | 2011-09-22 | 2012-06-20 | 中南大学 | Long-term high-temperature oxidation-resistant multi-element composite ceramic coating for carbon/carbon composite material and preparation and application methods thereof |
| CN103173790A (en) * | 2013-04-17 | 2013-06-26 | 湖南创元铝业有限公司 | Carbon anode coating, carbon anode by using same, and preparation method of same |
| CN103741167A (en) * | 2013-12-25 | 2014-04-23 | 中国矿业大学 | Method for improving oxidization resistance of carbon anode for electrolyzing aluminum |
| CN104230367A (en) * | 2014-09-10 | 2014-12-24 | 武汉科技大学 | SiC-ZrC-ZrB2 nano complex phase ceramic modified C/C composite material and preparation method thereof |
| CN106702431A (en) * | 2015-07-24 | 2017-05-24 | 沈阳铸造研究所 | Anti-oxidation coating for carbon anodes in aluminum electrolysis |
| CN106892642A (en) * | 2015-12-17 | 2017-06-27 | 高伟 | A kind of anode carbon block ORC |
| CN107057412A (en) * | 2017-02-15 | 2017-08-18 | 江西省科学院应用化学研究所 | A kind of self-curing electrolgtic aluminium carbon anode high temperature anti-oxidation coating |
| CN113563056A (en) * | 2021-07-15 | 2021-10-29 | 河南和成无机新材料股份有限公司 | Coating material for high-temperature oxidation resistance of carbon anode |
| CN113716977A (en) * | 2021-06-10 | 2021-11-30 | 西北工业大学 | Wide-temperature-range composite anti-oxidation coating on surface of carbon/carbon composite material and preparation method thereof |
| CN114315356A (en) * | 2022-01-21 | 2022-04-12 | 东北大学 | Aluminum electrolysis carbon anode oxidation resistant coating and preparation method thereof |
| CN115312521A (en) * | 2021-05-07 | 2022-11-08 | 爱思开海力士有限公司 | Semiconductor device and method for manufacturing the same |
| CN115528221A (en) * | 2022-07-12 | 2022-12-27 | 天津巴莫科技有限责任公司 | Composite coated high-nickel polycrystalline positive electrode material and preparation method thereof |
-
2023
- 2023-06-30 CN CN202310786779.3A patent/CN116813386B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316718A (en) * | 1991-06-14 | 1994-05-31 | Moltech Invent S.A. | Composite electrode for electrochemical processing having improved high temperature properties and method for preparation by combustion synthesis |
| CN101250722A (en) * | 2007-11-16 | 2008-08-27 | 广西师范大学 | Carbon element anode oxidation resistance layer for aluminium electrolysis and coating method thereof |
| CN101386995A (en) * | 2008-10-22 | 2009-03-18 | 中国铝业股份有限公司 | Aluminum electrolysis carbon anode oxidation coating and coating method thereof |
| WO2011012819A1 (en) * | 2009-07-30 | 2011-02-03 | Snecma | Method for manufacturing a thermal barrier |
| CN102503581A (en) * | 2011-09-22 | 2012-06-20 | 中南大学 | Long-term high-temperature oxidation-resistant multi-element composite ceramic coating for carbon/carbon composite material and preparation and application methods thereof |
| CN103173790A (en) * | 2013-04-17 | 2013-06-26 | 湖南创元铝业有限公司 | Carbon anode coating, carbon anode by using same, and preparation method of same |
| CN103741167A (en) * | 2013-12-25 | 2014-04-23 | 中国矿业大学 | Method for improving oxidization resistance of carbon anode for electrolyzing aluminum |
| CN104230367A (en) * | 2014-09-10 | 2014-12-24 | 武汉科技大学 | SiC-ZrC-ZrB2 nano complex phase ceramic modified C/C composite material and preparation method thereof |
| CN106702431A (en) * | 2015-07-24 | 2017-05-24 | 沈阳铸造研究所 | Anti-oxidation coating for carbon anodes in aluminum electrolysis |
| CN106892642A (en) * | 2015-12-17 | 2017-06-27 | 高伟 | A kind of anode carbon block ORC |
| CN107057412A (en) * | 2017-02-15 | 2017-08-18 | 江西省科学院应用化学研究所 | A kind of self-curing electrolgtic aluminium carbon anode high temperature anti-oxidation coating |
| CN115312521A (en) * | 2021-05-07 | 2022-11-08 | 爱思开海力士有限公司 | Semiconductor device and method for manufacturing the same |
| CN113716977A (en) * | 2021-06-10 | 2021-11-30 | 西北工业大学 | Wide-temperature-range composite anti-oxidation coating on surface of carbon/carbon composite material and preparation method thereof |
| CN113563056A (en) * | 2021-07-15 | 2021-10-29 | 河南和成无机新材料股份有限公司 | Coating material for high-temperature oxidation resistance of carbon anode |
| CN114315356A (en) * | 2022-01-21 | 2022-04-12 | 东北大学 | Aluminum electrolysis carbon anode oxidation resistant coating and preparation method thereof |
| CN115528221A (en) * | 2022-07-12 | 2022-12-27 | 天津巴莫科技有限责任公司 | Composite coated high-nickel polycrystalline positive electrode material and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| "文摘", 炭素技术, no. 01, 28 February 2017 (2017-02-28) * |
| LIU, JINYUN等: "A Self-Healing Flexible Quasi-Solid Zinc-Ion Battery Using All-In-One Electrodes", ADVANCED SCIENCE, 30 April 2021 (2021-04-30) * |
| 张勇, 周声劢, 夏金童: "炭/炭复合材料高温抗氧化研究进展", 炭素技术, no. 04, 30 August 2004 (2004-08-30) * |
| 李玲;尹绍奎;高天娇;黄旦忠;刘加军;李延海;: "铝电解炭素阳极用防氧化保护涂料的研究", 轻金属, no. 11, 20 November 2016 (2016-11-20) * |
| 穆小宝: "碳素材料抗氧化防护及碳/碳复合材料制备", 中国优秀硕士学位论文全文数据库 工程科技I辑, 15 September 2014 (2014-09-15) * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116813386B (en) | 2024-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0306102B1 (en) | Molten salt electrolysis with non-consumable anode | |
| CN101386995B (en) | Aluminum electrolysis carbon anode oxidation coating and coating method thereof | |
| Pawlek | Wettable cathodes: an update | |
| CN113149439B (en) | High-temperature corrosion resistant enamel coating and preparation method thereof | |
| CN104805345A (en) | Magnesium alloy surface treatment method | |
| CN113563056B (en) | Coating material for high-temperature oxidation resistance of carbon anode | |
| CN1280451C (en) | Antioxygenation of carbon anodes for aluminum electrolysis, deep antioxygenating layer and its coating method | |
| CN116813386B (en) | Self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating for aluminum electrolysis carbon anode and preparation method thereof | |
| CN114806231B (en) | Prebaked anode anti-oxidation coating capable of reducing energy consumption of aluminum electrolysis cell and preparation and application methods thereof | |
| CN112194471A (en) | Ultralow-porosity high-alumina brick and preparation process thereof | |
| CN103936333B (en) | A kind of aluminium electrolysis cathode roasting and start-up course high-temperature oxidation resistant coating and preparation method thereof | |
| CN100582309C (en) | Thermal insulation coating material for aluminum electrolysis inertia anode preheating-replacing and preparation method thereof | |
| US6365018B1 (en) | Surface coated non-carbon metal-based anodes for aluminium production cells | |
| US6425992B1 (en) | Surface coated non-carbon metal-based anodes | |
| CN1272472C (en) | Preparation of composite titanium boride cathode for guide aluminium eledrolyzing tank | |
| WO2021061014A1 (en) | Method for protecting cathode blocks of aluminium electrolyzers having prebaked anodes, protective composition and coating | |
| CN114672755A (en) | Non-wetting coating suitable for resisting high-temperature aluminum penetration and preparation method thereof | |
| CN108147831A (en) | A kind of preparation method of C/C composite materials high-temperature oxidation resistant coating | |
| CN111171692A (en) | High-temperature corrosion resistant silicon carbide coating and preparation method thereof | |
| CA2269550A1 (en) | Slurry and method for producing refractory boride bodies and coatings for use in aluminium electrowinning cells | |
| CN113354424B (en) | High-spalling-resistance oxygen lance brick and preparation method thereof | |
| CN116874286B (en) | Transition metal-based ceramic coating and preparation method thereof | |
| EP1049815B1 (en) | Method for producing surface coated non-carbon metal-based anodes for aluminium production cells | |
| US6783655B2 (en) | Slurry and method for producing refractory boride bodies and coatings for use in aluminium electrowinning cells | |
| CN219796007U (en) | Ceramic coating structure of gear for aviation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |