CN102716849B - Protection method applied to aluminum alloy in vanadium battery solution - Google Patents
Protection method applied to aluminum alloy in vanadium battery solution Download PDFInfo
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Abstract
The invention relates to a surface protection technology for an aluminum alloy material, in particular to a protection method applied to an aluminum alloy in a vanadium battery solution. Firstly, the aluminum alloy is unoiled and descaled; then a layer of super-corrosion-resistance and acid-and-alkaline resistant ceramic coating is coated on the surface of the aluminum alloy, the coating is cured at the room temperature for 20-30 hours to form a ceramic coating layer whose thickness if 10-70um; and then a layer of nano modified organic coating is further coated and cured to form an organic coating layer whose thickness is 7-50um. The protection method aims at the problem that the current aluminum alloy is seriously corroded in the vanadium battery solution and certain protection technology cannot meet the use requirements of the aluminum alloy in strong acid, strong alkaline and oxidized environments. The organic/inorganic composite coating layer is used to protect the surface of the aluminum alloy, so that the practical application problems of the aluminum alloy in the vanadium battery solution are solved.
Description
Technical field
The present invention relates to the surface protection technique of aluminum alloy materials, be specially a kind of means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery.
Background technology
Aluminium is one of the six large metals the most widely that distribute on the earth, and have many good performances: its proportion is lower; Can obtain high mechanical strength after suitable alloying and heat treatment; Pure metallic aluminum has higher corrosion resistance.In addition, aluminium has good electric conductivity, thermal conductivity and reflectivity; So the strong processing charges of its ductility is low; Aluminium is nonmagnetic, waste recovery value is high, its corrosion product non-toxic, colorless.Therefore, it is widely used in the many aspects such as communications and transportation, packing container, space flight and aviation, machine-building, household electrical appliance, building decoration, telecommunications, becomes use amount maximum, the widest metal material of application surface in non-ferrous metal.
But aluminium and alloy material hardness thereof is low, wear no resistance, easily produce intercrystalline corrosion, and application is restricted.Aluminium surface under field conditions (factors) forms layer oxide film, and this film is very thin, cracky, especially, under acid (alkali) property condition, dissolves rapidly, greatly reduces its resistance to corrosion.Therefore, the researcher uses the whole bag of tricks to carry out surface treatment to it both at home and abroad, to improve its combination property, it is more widely used.At present, aluminum alloy surface is processed mainly and launched from following fermentation: 1) oxidation processes is mainly anodic oxidation, chemical oxidation, differential arc oxidation; 2) electroplating chemical plating; 3) face coat is mainly laser melting coating and composite coating; 4) rare-earth conversion coatings.Although these surface treatments have met some high requests, high-level application.But apply and still be restricted under the environment of strong acid, strong oxidation, especially current just in the application of the vanadium flow battery of develop rapidly, still do not have a kind of protection system can meet the application of its aluminium alloy.
So, a kind ofly requires between coating system, adhesion is preferably arranged between system and matrix, and the aluminum alloy surface composite coating that can use for a long time in the environment of strong acid, strong oxidation has to be developed.
Summary of the invention:
The objective of the invention is can't to meet aluminium alloy for current surface treatment applies in the vanadium flow battery of strong acid, strong oxidation, a kind of means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery is provided, adopt inorganic/organic composite coating protection system, thereby solved the practical application of aluminium alloy in electrolyte of vanadium redox battery, and adhesion is arranged guaranteeing between coating system, between system and matrix preferably, do not affect under the prerequisite of vanadium flow battery normal operation, improved largely anti-strong acid, the strong oxidizing property energy of coating.
The present invention realizes by the following technical solutions:
A kind of means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery, at first to aluminium alloy oil removing, descale; Then apply the super anticorrosion acid and alkali-resistance ceramic coating of one deck in aluminum alloy surface, cold curing 20～30h, form ceramic coating, and the thickness of ceramic coating is 10～70 μ m (being preferably 30～60 μ m); Apply afterwards one deck nano modification organic coating, the thickness that solidify to form organic coating is 7～50 μ m (being preferably 10～25 μ m) again.
In the present invention, the organic coating solidification temperature is 0-300 ℃, and the time is 15 minutes～48 hours.
The selected degreasing fluid of the present invention is mixed by sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifying agent, and the content of each component is as follows:
Sodium carbonate 10～30g/L; Tertiary sodium phosphate 20～40g/L; Sodium metasilicate 5～15g/L; OP-10 emulsifying agent 1～5g/L; All the other are water.
The selected descale liquid of the present invention is mixed by hydrofluoric acid, nitric acid, and the content of each component is as follows:
Hydrofluoric acid 2～10g/L; Nitric acid 6～30g/L; All the other are water.
The selected super anticorrosion acid and alkali-resistance ceramic coating of the present invention is evenly mixed by modified resin, ceramic powders, auxiliary agent, solvent etc., is sprayed or brushes under room temperature, cold curing 20～30h.By weight percentage, modified resin accounts for 10～30%, and ceramic powders accounts for 12～40%, and auxiliary agent accounts for 0.1～3%, and solvent accounts for 30～75%.Wherein,
Modified resin is: one or more compositions such as acrylic modified epoxy resin, acrylic acid modified polyurethane resin, organosilicon modified crylic acid resin, polyurethane modified epoxy resin;
Ceramic powder is the particles such as aluminium oxide, silicon nitride, carborundum, hexagonal boron nitride, WC, TiC, TaC, NbC or VC, and its granularity is 80～500 orders (being preferably 200～500 orders);
Auxiliary agent adopts the ceramic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.;
Solvent is: one or more compositions such as dimethylbenzene, methyl alcohol, ethanol, glycerine, ethylene glycol, propane diols, butyl glycol ether, ethylene glycol ether acetate, propylene-glycol ethyl ether acetate;
The selected nano modification organic coating of the present invention is evenly mixed by resin, nano-powder, auxiliary agent, solvent etc., spraying or brushing under room temperature, and 0-300 ℃ solidifies (being preferably room temperature to 250 ℃) 15 minutes～48 hours.By weight percentage, resin accounts for 20～50%, and nano-powder material accounts for 2～8%, auxiliary agent 0.1～3%, solvent 40～75%.
Resin is: one or more formations such as organic epoxy resin, polyurethane resin, acrylic resin, fluorocarbon resin, polyflon.
Nano-powder is: one or more compositions such as nano titanium powder, nano silicon, nano aluminium oxide, Nano-Zinc aluminium powder, nano carbon black, its granularity is 0.1-100 nanometer (being preferably the 5-50 nanometer).
Auxiliary agent adopts the organic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.;
Solvent is: one or more compositions such as dimethylbenzene, methyl alcohol, ethanol, glycerine, ethylene glycol, propane diols, butyl glycol ether, ethylene glycol ether acetate, propylene-glycol ethyl ether acetate;
The means of defence of aluminium alloy in electrolyte of vanadium redox battery of the present invention, wherein: the ceramic coating role is the adhesion improved between matrix and coating, and ceramic coating has better anti-strong acid, strong oxidation characteristic; The organic coating role is to the bottom sealing, further the anti-strong acid of strengthened coat, strong oxidation characteristic.It is good that the two synergy is issued to adhesion, the coating densification, and anti-strong acid, oxidation is effective by force.
Advantage of the present invention:
1, the present invention adopts inorganic/organic composite coating protection system, at first to aluminium alloy oil removing, descale; Then apply one deck ceramic coating in aluminum alloy surface, cold curing, form ceramic coating, apply again afterwards one deck organic coating, solidify to form organic coating, ceramic coating and organic coating composite protective system have adhesion preferably, solved the application problem of aluminium alloy under strong acid, strong oxidation environment, and provide support for the development of vanadium cell.
2, the present invention adopts ceramic coating and organic coating composite protective system, between coating, between composite coating and matrix, have adhesion preferably, obscission can not occur because of long-time the immersion.
3, the present invention adopts the nano modification organic coating well to seal ceramic coating, thereby reaches good corrosion resisting property.
4, coating layer thickness of the present invention is controlled, can claim according to requirement for anticorrosion.
The specific embodiment
Embodiment 1:
At first, prepare sample, aluminium alloy (150mm * 70mm * 2mm) is carried out to oil removing in alkaline degreasing liquid, cleaned with a large amount of water afterwards, then descale in acid solution, after the massive laundering drying, use alcohol the aluminum alloy surface wiped clean.
Degreasing fluid is mixed by sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifying agent, and the content of each component is as follows:
Sodium carbonate 25g/L; Tertiary sodium phosphate 30g/L; Sodium metasilicate 10g/L; OP-10 emulsifying agent 2g/L; All the other are water.
The liquid that descales is mixed by hydrofluoric acid, nitric acid, and the content of each component is as follows:
Hydrofluoric acid 7g/L; Nitric acid 25g/L; All the other are water;
Then apply one deck ceramic coating, cold curing 24h, thickness 40 μ m in aluminum alloy surface; Apply again the organic coating that one deck contains polyflon and acrylic resin, 200 ℃ of curing 15min, thickness 20 μ m; Total coating thickness 60 μ m.
In the present embodiment, ceramic coating is evenly mixed by modified resin, ceramic powders, auxiliary agent, solvent etc., under room temperature, is sprayed or brushes.By weight percentage, modified resin accounts for 20%, and ceramic powders accounts for 25%, and auxiliary agent accounts for 1%, and solvent accounts for 54%.Wherein, modified resin is acrylic modified epoxy resin; Ceramic powder is alumina particle, and its granularity is 200～300 orders; Auxiliary agent adopts the ceramic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is dimethylbenzene.
The selected nano modification organic coating of the present invention is evenly mixed by resin, nano-powder, auxiliary agent, solvent etc., spraying or brushing under room temperature.By weight percentage, resin accounts for 30%, and nano-powder material accounts for 5%, auxiliary agent 0.5%, solvent 64.5%.Wherein, resin is polyflon and acrylic resin weight ratio 1: 1; Nano-powder is nano titanium powder, and its granularity is the 20-50 nanometer; Auxiliary agent adopts the organic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is dimethylbenzene.
The duplex coating adhesion prepared by the method is good, and the coating densification is soaked 6 months without coating shedding at electrolyte of vanadium redox battery, corrosion phenomenon.
Embodiment 2:
At first, prepare sample, aluminium alloy (150mm * 70mm * 2mm) is carried out to oil removing in alkaline degreasing liquid, cleaned with a large amount of water afterwards, then descale in acid solution, after the massive laundering drying, use alcohol the aluminum alloy surface wiped clean.
Degreasing fluid is mixed by sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifying agent, and the content of each component is as follows:
Sodium carbonate 25g/L; Tertiary sodium phosphate 30g/L; Sodium metasilicate 10g/L; OP-10 emulsifying agent 2g/L; All the other are water.
The liquid that descales is mixed by hydrofluoric acid, nitric acid, and the content of each component is as follows:
Hydrofluoric acid 7g/L; Nitric acid 25g/L; All the other are water;
Then apply one deck ceramic coating, cold curing 24h, thickness 30 μ m in aluminum alloy surface; Apply again the organic coating that one deck contains epoxy resin resin and polyurethane resin, cold curing 24h, thickness 20 μ m; Total coating thickness 50 μ m.
In the present embodiment, ceramic coating is evenly mixed by modified resin, ceramic powders, auxiliary agent, solvent etc., under room temperature, is sprayed or brushes.By weight percentage, modified resin accounts for 10%, and ceramic powders accounts for 40%, and auxiliary agent accounts for 0.5%, and solvent accounts for 49.5%.Wherein, modified resin is the acrylic acid modified polyurethane resin; Ceramic powder is alumina particle, and its granularity is 100～200 orders; Auxiliary agent adopts the ceramic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is ethylene glycol ether acetate.
The selected nano modification organic coating of the present invention is evenly mixed by resin, nano-powder, auxiliary agent, solvent etc., spraying or brushing under room temperature.By weight percentage, resin accounts for 20%, and nano-powder material accounts for 8%, auxiliary agent 1%, solvent 71%.Wherein, resin is epoxy resin resin and polyurethane resin weight ratio 1: 1; Nano-powder is nano silicon, and its granularity is the 10-30 nanometer; Auxiliary agent adopts the organic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is ethylene glycol ether acetate.
The duplex coating adhesion prepared by the method is good, and the coating densification is soaked 4 months without coating shedding at electrolyte of vanadium redox battery, corrosion phenomenon.
Embodiment 3:
At first, prepare sample, aluminium alloy (150mm * 70mm * 2mm) is carried out to oil removing in alkaline degreasing liquid, with a large amount of water, cleaned afterwards, then descale in acid solution, after the massive laundering drying, use alcohol the aluminum alloy surface wiped clean.
Degreasing fluid is mixed by sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifying agent, and the content of each component is as follows:
Sodium carbonate 25g/L; Tertiary sodium phosphate 30g/L; Sodium metasilicate 10g/L; OP-10 emulsifying agent 2g/L; All the other are water.
The liquid that descales is mixed by hydrofluoric acid, nitric acid, and the content of each component is as follows:
Hydrofluoric acid 7g/L; Nitric acid 25g/L; All the other are water;
Then apply one deck ceramic coating, cold curing 24h, thickness 35 μ m in aluminum alloy surface; Apply again the organic coating that one deck contains polyurethane resin and acrylic resin, cold curing 30h, thickness 20 μ m; Total coating thickness 55 μ m.
In the present embodiment, ceramic coating is evenly mixed by modified resin, ceramic powders, auxiliary agent, solvent etc., under room temperature, is sprayed or brushes.By weight percentage, modified resin accounts for 30%, and ceramic powders accounts for 12%, and auxiliary agent accounts for 3%, and solvent accounts for 55%.Wherein, modified resin is organosilicon modified crylic acid resin; Ceramic powder is silicon-carbide particle, and its granularity is 300～400 orders; Auxiliary agent adopts the ceramic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is propane diols.
The selected nano modification organic coating of the present invention is evenly mixed by resin, nano-powder, auxiliary agent, solvent etc., spraying or brushing under room temperature.By weight percentage, resin accounts for 50%, and nano-powder material accounts for 2%, auxiliary agent 2%, solvent 46%.Wherein, resin is polyurethane resin and acrylic resin weight ratio 1: 1; Nano-powder is nano aluminium oxide, and its granularity is the 50-80 nanometer; Auxiliary agent adopts the organic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is propane diols.
The duplex coating adhesion prepared by the method is good, and the coating densification is soaked 4 months without coating shedding at electrolyte of vanadium redox battery, corrosion phenomenon.
Embodiment 4:
At first, prepare sample, aluminium alloy (150mm * 70mm * 2mm) is carried out to oil removing in alkaline degreasing liquid, cleaned with a large amount of water afterwards, then descale in acid solution, after the massive laundering drying, use alcohol the aluminum alloy surface wiped clean.
Degreasing fluid is mixed by sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifying agent, and the content of each component is as follows:
Sodium carbonate 25g/L; Tertiary sodium phosphate 30g/L; Sodium metasilicate 10g/L; OP-10 emulsifying agent 2g/L; All the other are water.
The liquid that descales is mixed by hydrofluoric acid, nitric acid, and the content of each component is as follows:
Hydrofluoric acid 7g/L; Nitric acid 25g/L; All the other are water;
Then apply one deck ceramic coating, cold curing 24h, thickness 60 μ m in aluminum alloy surface; Apply again the organic coating that one deck contains polyflon and epoxy resin, 200 ℃ of curing 15min, thickness 25 μ m; Total coating thickness 85 μ m.
In the present embodiment, ceramic coating is evenly mixed by modified resin, ceramic powders, auxiliary agent, solvent etc., under room temperature, is sprayed or brushes.By weight percentage, modified resin accounts for 25%, and ceramic powders accounts for 15%, and auxiliary agent accounts for 1%, and solvent accounts for 59%.Wherein, modified resin is organosilicon modified crylic acid resin; Ceramic powder is hexagonal boron nitride particles, and its granularity is 400～500 orders; Auxiliary agent adopts the ceramic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is glycerine.
The selected nano modification organic coating of the present invention is evenly mixed by resin, nano-powder, auxiliary agent, solvent etc., spraying or brushing under room temperature.By weight percentage, resin accounts for 25%, and nano-powder material accounts for 6%, auxiliary agent 1%, solvent 68%.Wherein, resin is that polyflon and weight epoxy were than 1: 1; Nano-powder is the Nano-Zinc aluminium powder, and its granularity is the 30-40 nanometer; Auxiliary agent adopts the organic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is glycerine.
The duplex coating adhesion prepared by the method is good, and the coating densification is soaked 8 months without coating shedding at electrolyte of vanadium redox battery, corrosion phenomenon.
Embodiment 5:
At first, prepare sample, aluminium alloy (150mm * 70mm * 2mm) is carried out to oil removing in alkaline degreasing liquid, cleaned with a large amount of water afterwards, then descale in acid solution, after the massive laundering drying, use alcohol the aluminum alloy surface wiped clean.
Degreasing fluid is mixed by sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifying agent, and the content of each component is as follows:
Sodium carbonate 25g/L; Tertiary sodium phosphate 30g/L; Sodium metasilicate 10g/L; OP-10 emulsifying agent 2g/L; All the other are water.
The liquid that descales is mixed by hydrofluoric acid, nitric acid, and the content of each component is as follows:
Hydrofluoric acid 7g/L; Nitric acid 25g/L; All the other are water;
Then apply one deck ceramic coating in aluminum alloy surface, after cold curing 24h, thickness 35 μ m; Apply again the organic coating that one deck contains fluorocarbon resin, cold curing 30h, thickness 25 μ m; Total coating thickness 60 μ m.
In the present embodiment, ceramic coating is evenly mixed by modified resin, ceramic powders, auxiliary agent, solvent etc., under room temperature, is sprayed or brushes.By weight percentage, modified resin accounts for 15%, and ceramic powders accounts for 35%, and auxiliary agent accounts for 2%, and solvent accounts for 48%.Wherein, modified resin is polyurethane modified epoxy resin; Ceramic powder is the TiC particle, and its granularity is 200～300 orders; Auxiliary agent adopts the ceramic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is the propylene-glycol ethyl ether acetate.
The selected nano modification organic coating of the present invention is evenly mixed by resin, nano-powder, auxiliary agent, solvent etc., spraying or brushing under room temperature.By weight percentage, resin accounts for 35%, and nano-powder material accounts for 4%, auxiliary agent 1%, solvent 60%.Wherein, resin is fluorocarbon resin; Nano-powder is nano carbon black, and its granularity is the 50-60 nanometer; Auxiliary agent adopts the organic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is the propylene-glycol ethyl ether acetate.
The duplex coating adhesion prepared by the method is good, and the coating densification is soaked 3 months without coating shedding at electrolyte of vanadium redox battery, corrosion phenomenon.
Embodiment 6:
At first, prepare sample, aluminium alloy (150mm * 70mm * 2mm) is carried out to oil removing in alkaline degreasing liquid, cleaned with a large amount of water afterwards, then descale in acid solution, after the massive laundering drying, use alcohol the aluminum alloy surface wiped clean.
Degreasing fluid is mixed by sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifying agent, and the content of each component is as follows:
Sodium carbonate 25g/L; Tertiary sodium phosphate 30g/L; Sodium metasilicate 10g/L; OP-10 emulsifying agent 2g/L; All the other are water.
The liquid that descales is mixed by hydrofluoric acid, nitric acid, and the content of each component is as follows:
Hydrofluoric acid 7g/L; Nitric acid 25g/L; All the other are water;
Then apply one deck ceramic coating, cold curing 24h, thickness 30 μ m in aluminum alloy surface; Apply again the organic coating that one deck contains acrylic resin, cold curing 24h, thickness 20 μ m; Total coating thickness 50 μ m.
In the present embodiment, ceramic coating is evenly mixed by modified resin, ceramic powders, auxiliary agent, solvent etc., under room temperature, is sprayed or brushes.By weight percentage, modified resin accounts for 22%, and ceramic powders accounts for 20%, and auxiliary agent accounts for 1%, and solvent accounts for 57%.Wherein, modified resin is polyurethane modified epoxy resin; Ceramic powder is the NbC particle, and its granularity is 100～200 orders; Auxiliary agent adopts the ceramic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is propane diols.
The selected nano modification organic coating of the present invention is evenly mixed by resin, nano-powder, auxiliary agent, solvent etc., spraying or brushing under room temperature.By weight percentage, resin accounts for 45%, and nano-powder material accounts for 5%, auxiliary agent 3%, solvent 47%.Wherein, resin is acrylic resin; Nano-powder is nano aluminium oxide, and its granularity is the 10-20 nanometer; Auxiliary agent adopts the organic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is propane diols.
The duplex coating adhesion prepared by the method is good, and the coating densification is soaked 3 months without coating shedding at electrolyte of vanadium redox battery, corrosion phenomenon.
Embodiment 7:
At first, prepare sample, aluminium alloy (150mm * 70mm * 2mm) is carried out to oil removing in alkaline degreasing liquid, cleaned with a large amount of water afterwards, then descale in acid solution, after the massive laundering drying, use alcohol the aluminum alloy surface wiped clean.
Degreasing fluid is mixed by sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifying agent, and the content of each component is as follows:
Sodium carbonate 25g/L; Tertiary sodium phosphate 30g/L; Sodium metasilicate 10g/L; OP-10 emulsifying agent 2g/L; All the other are water.
The liquid that descales is mixed by hydrofluoric acid, nitric acid, and the content of each component is as follows:
Hydrofluoric acid 7g/L; Nitric acid 25g/L; All the other are water;
Then apply one deck ceramic coating, cold curing 24h, thickness 40 μ m in aluminum alloy surface; Apply again the organic coating that one deck contains polyflon, 200 ℃ of curing 15min, thickness 20 μ m; Total coating thickness 60 μ m.
In the present embodiment, ceramic coating is evenly mixed by modified resin, ceramic powders, auxiliary agent, solvent etc., under room temperature, is sprayed or brushes.By weight percentage, modified resin accounts for 18%, and ceramic powders accounts for 35%, and auxiliary agent accounts for 2%, and solvent accounts for 45%.Wherein, modified resin is acrylic modified epoxy resin; Ceramic powder is the VC particle, and its granularity is 300～400 orders; Auxiliary agent adopts the ceramic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is butyl glycol ether.
The selected nano modification organic coating of the present invention is evenly mixed by resin, nano-powder, auxiliary agent, solvent etc., spraying or brushing under room temperature.By weight percentage, resin accounts for 38%, and nano-powder material accounts for 8%, auxiliary agent 1%, solvent 53%.Wherein, resin is acrylic resin; Nano-powder is nano titanium powder, and its granularity is the 30-40 nanometer; Auxiliary agent adopts the organic coating usual auxiliaries, as: wetting agent, defoamer, levelling agent and rheological agent etc.; Solvent is butyl glycol ether.
The duplex coating adhesion prepared by the method is good, and the coating densification is soaked 4 months without coating shedding at electrolyte of vanadium redox battery, corrosion phenomenon.
The embodiment result shows, the present invention is directed to aluminum current alloy seriously corroded in electrolyte of vanadium redox battery, and some guard technologies can't meet the instructions for use in its strong acid, strong oxidation environment.Adopt inorganic/organic composite coating to be protected aluminum alloy surface, thereby solved the practical application of aluminium alloy in electrolyte of vanadium redox battery.
Claims (8)
1. a means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery, is characterized in that: at first to aluminium alloy oil removing, descale; Then apply the super anticorrosion acid and alkali-resistance ceramic coating of one deck in aluminum alloy surface, cold curing 20-30h, form ceramic coating, and the thickness of ceramic coating is 10-70 μ m; Apply afterwards one deck nano modification organic coating, the thickness that solidify to form organic coating is 7-50 μ m again;
Selected super anticorrosion acid and alkali-resistance ceramic coating is evenly mixed by modified resin, ceramic powders, auxiliary agent, solvent, is sprayed or brushes under room temperature, cold curing 20-30h; By weight percentage, modified resin accounts for 10-30%, and ceramic powders accounts for 12-40%, and auxiliary agent accounts for 0.1-3%, and solvent accounts for 30-75%; Wherein,
Modified resin is: acrylic modified epoxy resin, acrylic acid modified polyurethane resin, organosilicon modified crylic acid resin, one or more compositions of polyurethane modified epoxy resin;
Ceramic powder is aluminium oxide, silicon nitride, carborundum, hexagonal boron nitride, WC, TiC, TaC, NbC or VC particle, and its granularity is the 80-500 order;
Solvent is: dimethylbenzene, methyl alcohol, ethanol, glycerine, ethylene glycol, propane diols, butyl glycol ether, ethylene glycol ether acetate, one or more compositions of propylene-glycol ethyl ether acetate;
Selected nano modification organic coating is evenly mixed by resin, nano-powder, auxiliary agent, solvent, spraying or brushing under room temperature, and 0-300 ℃ solidifies 15 minutes-48 hours; By weight percentage, resin accounts for 20-50%, and nano-powder material accounts for 2-8%, auxiliary agent 0.1-3%, solvent 40-75%; Wherein:
Resin is: one or more formations such as organic epoxy resin, polyurethane resin, acrylic resin, fluorocarbon resin, polyflon;
Nano-powder is: one or more compositions such as nano titanium powder, nano silicon, nano aluminium oxide, Nano-Zinc aluminium powder, nano carbon black, and its granularity is the 0.1-100 nanometer;
Solvent is: dimethylbenzene, methyl alcohol, ethanol, glycerine, ethylene glycol, propane diols, butyl glycol ether, ethylene glycol ether acetate, one or more compositions of propylene-glycol ethyl ether acetate.
2. according to the means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery claimed in claim 1, it is characterized in that, the organic coating solidification temperature is 0-300 ℃, and the time is 15 minutes-48 hours.
3. according to the means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery claimed in claim 1, it is characterized in that, selected degreasing fluid is mixed by sodium carbonate, tertiary sodium phosphate, sodium metasilicate, OP-10 emulsifying agent and water, and the content of each component is as follows:
Sodium carbonate 10-30 g/L; Tertiary sodium phosphate 20-40 g/L; Sodium metasilicate 5-15 g/L; OP-10 emulsifying agent 1-5 g/L; All the other are water.
4. according to the means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery claimed in claim 1, it is characterized in that, selected descale liquid is mixed by hydrofluoric acid, nitric acid and water, and the content of each component is as follows:
Hydrofluoric acid 2-10g/L; Nitric acid 6-30g/L; All the other are water.
5. according to the means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery claimed in claim 1, it is characterized in that, the ceramic powder granularity is the 200-500 order.
6. according to the means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery claimed in claim 1, it is characterized in that, the nano-powder granularity is the 5-50 nanometer.
7. according to the means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery claimed in claim 1, it is characterized in that, thickness of ceramic coating 30-60 μ m, the thickness of organic coating is 10-25 μ m.
8. according to the means of defence that is applied to aluminium alloy in electrolyte of vanadium redox battery claimed in claim 1, it is characterized in that, the organic coating solidification temperature is room temperature to 250 ℃.
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| JP2001020080A (en) * | 1999-07-07 | 2001-01-23 | Kobe Steel Ltd | Composite material excellent in phosphate treatability and electrolytic corrosion resistance |
| CN101550549A (en) * | 2009-03-30 | 2009-10-07 | 湖北工业大学 | Al2O3/Al-Si composite coating by spray coating on aluminium alloy surface and preparation method |
| CN101871119A (en) * | 2010-07-28 | 2010-10-27 | 哈尔滨工业大学 | Preparation method of magnesium alloy surface micro-arc oxidation/spray coating compound film |
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