CN108950645B - Aluminum and aluminum alloy anodic oxidation nickel-free sealing agent - Google Patents
Aluminum and aluminum alloy anodic oxidation nickel-free sealing agent Download PDFInfo
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- CN108950645B CN108950645B CN201811140172.3A CN201811140172A CN108950645B CN 108950645 B CN108950645 B CN 108950645B CN 201811140172 A CN201811140172 A CN 201811140172A CN 108950645 B CN108950645 B CN 108950645B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
Abstract
The aluminum and aluminum alloy anode oxidation nickel-free sealing agent at least comprises a color fixing agent, a frost ash inhibiting agent, a complexing agent, a surfactant and a pH buffering agent.
Description
Technical Field
The invention relates to metal surface treatment, in particular to a nickel-free sealing agent for aluminum and aluminum alloy anodic oxidation.
Background
In the surface treatment process of aluminum alloys, anodic oxidation treatment plays an important role. The anodic oxide film layer of the aluminum alloy can be dyed with various bright colors, so that the surface of the aluminum product is more beautiful. However, the dyed oxide film has high porosity and adsorptivity, is easily contaminated, and when used in a corrosive environment, corrosive media easily enter pores to cause corrosion; after dyeing, special treatment is not needed, and the wear resistance and the light fastness of the color are poor; therefore, the micropores of the oxide film are closed by an appropriate sealing technique, thereby reducing the adhesion property, improving the corrosion resistance and the electrical insulation property, and maintaining the beautiful color. The hole sealing method of the aluminum oxide film is various, and the hole sealing method comprises a boiling water hole sealing method and a steam hole sealing method which realize the hole sealing process based on the hydration reaction; a physical hole sealing method in a surface coating mode; the hole sealing for filling the micropores through reactions such as hydrolysis and the like comprises a dichromate method, a chromate method and a nickel acetate method; the nickel-fluorine system belongs to a normal temperature hole sealing method.
At present, the hole sealing agent is mainly used abroad as a nickel salt hole sealing agent. The sealant mainly comprises a Japanese high-temperature nickel acetate sealant and a European and American normal-temperature nickel acetate sealant. The high-temperature nickel acetate hole sealing agent has better hole sealing quality than a normal-temperature nickel acetate hole sealing agent, is widely applied, and has the principle that under certain pH, nickel ions, water, a surfactant and the like act together, and hydrolysis products are properly gathered to enter pores of an oxide film on the surface of aluminum to realize hole sealing; the pH buffering agent plays a role in stabilizing the pH value of the solution and controlling the hydrolysis degree of nickel ions; surfactant, etc. to form complex with nickel ion and to control the concentration and hydrolysis amount of simple nickel ion. Meanwhile, the hole sealing liquid has proper dispersion and wetting effects, so that the nickel ion hydrolysate is kept to be properly gathered, thereby ensuring no powder frost and minimizing the influence on dyeing dispersion, and simultaneously having higher hole sealing speed.
Due to the environmental problems caused by the sealing of nickel salt, a new nickel-free sealing agent is promoted to be developed abroad. In China, the surface treatment of the aluminum material is started late, the number of independent sealing agents is small, the aluminum material is mainly imported, and the market for surface treatment of the aluminum material in China is large, so that the independent sealing agents are needed.
Disclosure of Invention
In order to solve the problems in the prior art, the first aspect of the invention provides a nickel-free sealant for aluminum and aluminum alloy anodic oxidation, wherein the raw materials of the sealant at least comprise a color fixing agent, a frost and dust inhibitor, a complexing agent, a surfactant and a pH buffering agent.
In some embodiments, the raw materials of the blocking agent at least comprise 0.1-2g of color fixing agent, 0.8-1.5g of frost ash inhibitor, 0.1-4g of complexing agent, 0.1-5g of surfactant and 0-5g of pH buffer agent in 1L.
In some embodiments, the fixing agent is a vinyl nitrogen-containing heterocyclic polymer.
In some embodiments, the nitrogen-containing heterocycle in the vinyl nitrogen-containing heterocycle polymer is selected from at least one of pyridine, imidazole, and pyrimidine.
In some embodiments, the bloom inhibitor is selected from at least one of citric acid, tartaric acid, malic acid, ascorbic acid, gluconic acid, lactic acid, fumaric acid.
In some embodiments, the complexing agent is selected from at least one of alcohol amines, ethylene diamine tetraacetic acid, ethylene diamine tetramethylene phosphonic acid, diethylene triamine pentamethylene methylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid, 2-phospho-1, 2, 4-tricarboxylic acid butane, sodium tripolyphosphate, sodium pyrophosphate, sodium metaphosphate, aminotrimethylene phosphonic acid, phosphonobutane tricarboxylic acid.
In some embodiments, the surfactant is a sulfonate.
In some embodiments, the sulfonate salt comprises a nitrogen heterocyclic sulfonate salt, a benzene ring sulfonate salt.
In some embodiments, the pH buffering agent is selected from at least one of ammonium acetate, ammonium benzoate, ammonium phthalate.
The second aspect of the invention provides a method for using the aluminum and aluminum alloy anodic oxidation nickel-free sealing agent, wherein the treatment temperature is 70-100 ℃, and the treatment time is 10-40 min.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
The aluminum anodic oxide film is mainly composed of anhydrous aluminum oxide, is mostly amorphous, and also contains a small amount of crystalline gamma-Al 2O 3. The anodic oxide film can effectively protect the aluminum matrix from corrosion, and the anodic oxide film has better performance than a naturally formed oxide film. The hardness of the aluminum anodic oxide film is higher than that of the aluminum substrate, the metal luster of the polished surface can be protected, and the anodic oxide film can be dyed and colored to obtain and maintain rich and colorful appearance. Anodic oxide films are a means for the aluminum surface to receive organic coatings and electroplated layers, which effectively improve the adhesion and corrosion resistance of the surface layer. Aluminum is a good conductor, and an aluminum anodized film is a high-resistance insulating film. The insulation breakdown voltage is more than 30V/mum. The higher the transparency of the anodic oxide film itself, the higher the purity of the aluminum, the higher the transparency. By using the porous type of the anodic oxide film, functional fine particles are deposited in the micropores, and various functional materials can be obtained.
Because a large number of microporous structure units exist in the oxide film after anodic oxidation, the effective area of the aluminum alloy exposed in the environment is greatly increased, and the corresponding corrosion speed is accelerated. In order to improve corrosion resistance and contamination resistance of an oxide film of aluminum or an aluminum alloy, a sealing treatment is required. The sealing method of the aluminum and aluminum alloy anodic oxide film mainly comprises hydration reaction, inorganic substance filling and organic substance filling according to the hole sealing principle. Common sealing methods include boiling water sealing, potassium dichromate sealing, cold sealing, and electrocoating.
The technology of bichromate hole sealing and nickel fluoride cold sealing belongs to a main hole sealing technology, but the technology of bichromate hole sealing and nickel fluoride cold sealing uses a solution containing heavy metal ions of chromium and nickel, so that the environment is polluted greatly, and harmful effects can be generated on human health in the using process of aluminum materials or aluminum alloy components.
The invention provides a nickel-free sealant for aluminum and aluminum alloy anodic oxidation, which at least comprises a color fixing agent, a frost ash inhibitor, a complexing agent, a surfactant and a pH buffering agent.
In some embodiments, the raw materials of the blocking agent at least comprise 0.1-2g of color fixing agent, 0.8-1.5g of frost ash inhibitor, 0.1-4g of complexing agent, 0.1-5g of surfactant and 0-5g of pH buffer agent in 1L.
In some embodiments, the fixing agent is a vinyl nitrogen-containing heterocyclic polymer.
In some embodiments, the nitrogen-containing heterocycle in the vinyl nitrogen-containing heterocycle polymer is selected from at least one of pyridine, imidazole, and pyrimidine.
In some embodiments of the invention, the nitrogen-containing heterocycle in the vinyl nitrogen-containing heterocycle polymer is pyridine, and specific examples of monomers thereof include, but are not limited to, 4-vinylpyridine, 2-vinylpyridine, 6-methyl-3-vinyl-2-pyridylamine, 4-vinyl-2-pyridinecarbonitrile, 2, 6-bis (2-phenylvinyl) pyridine, 4-vinyl-2-pyridylamine, 6-vinyl-2-pyridylamine, 2-vinyl-4-pyridylamine, 3-vinyl-2-pyridylamine, 2, 6-dimethyl-4-vinylpyridine, 4-styrylpyridinium, pyridine, 3-vinyloxypyridine, N-methyl-N-vinyl-4-pyridylamine, 3-vinylpyridine, 2-vinyl-6-methyl-pyridine, 2, 3-dimethyl-5-vinylpyridine, 6-vinyl-2-pyridinecarbonitrile, 4-vinyloxypyridine, 4- [ (E) -2-methoxyvinyl ] pyridine, 2-isopropyl-6-vinylpyridine, 1, 2-bis (4-pyridyl) ethylene, N-dimethyl-2- (2-pyridyl) vinylamine, 2, 4-divinylpyridine, 4-methyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, N-methyl-N-vinyl-4-pyridinecarbonitrile, N-methyl-N-vinyl-2-pyridinecarbonitrile, a salt thereof, and a pharmaceutically acceptable salt, 3-vinyl-1H-pyrrolo [2,3-b ] pyridine, 1- (-2-pyridyl) -2- (4-pyridyl) ethylene, 3- [2- (4-pyridyl) vinyl ] pyridine, N-dimethyl-2-vinyl-4-pyridylamine, 2- (1-styryl) pyridine, (6-vinyl-2-pyridyl) methanol, 1-isopropyl-5-vinyl-1, 2,3, 6-tetrahydropyridine, 2, 5-divinyl-pyridine, 4, 6-dimethyl-5-vinyl-2-pyridylamine, 4- (1-methyl-2-phenylvinyl) pyridine, and mixtures thereof, 4- (1-naphthylvinyl) pyridine, 2-vinylpyridin-2-yl) ethanol, 2-methyl-5-vinyl-4-pyridylamine, 2- [2- (2-furyl) vinyl ] pyridine, 5-vinylfuro [2,3-b ] pyridine, 3- (1-methylvinyl) -2-pyridylamine, 5-vinyl-2- (N, N-dimethylamino) ethylpyridine, 4- [2- (1-naphthyl) vinyl ] -pyridine hydrochloride, 2- (4-pyridyl) vinylamine, N-methyl-2-vinyl-3-pyridylamine, dimethylvinylpyridine, 2-vinyl-3-pyridylamine, 2-vinyl-3-pyridinol, 4- (2-pyridin-4-ylvinyl) aniline, 3-ethyl-2-methyl-5-vinylpyridine, 2, 3-divinylpyridine, 3-vinylimidazo [1,2-a ] pyridine, 5-ethyl-2-methyl-3-vinylpyridine, 5-ethyl-4-methyl-2-vinylpyridine, 2-methoxy-3-vinylpyridine, 2- (2- (3-pyridyl) vinyl) -1H-benzimidazole, N, 3-trimethyl-6-vinyl-2-pyridylamine, (6-vinyl-3-pyridyl) methanol, and mixtures thereof, 3-methyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine, 2- [ (2-methyl-2-propyl) oxy ] -5-vinylpyridine, 2-methyl-6- (2-styryl) pyridine, 3-vinyl-2-pyridinecarboxylic acid, 3- (2- (4-methylphenyl) vinylpyridine, (2-methyl-5-vinyl-4-pyridyl) methanol, 4-vinyl-3-pyridinol, 5-vinyl-2-pyridinecarboxylic acid, 2- [2- (p-tolyl) vinyl ] pyridine, 2- (4- (dimethylamino) styryl) pyridine, and mixtures thereof, 2- [1- (2-methylphenyl) vinyl ] -pyridine, 3- (1-styryl) pyridine, 2, 5-dimethyl-4-vinyl-3-pyridinol, 3-ethyl-6-vinyl-2-pyridylamine, 4-ethoxy-2-vinylpyridine, 4-vinyl-2-pyridinecarboxylic acid, 4- (4- (dimethylamino) styryl) pyridine.
In some embodiments of the invention, the nitrogen-containing heterocycle in the vinyl nitrogen-containing heterocycle polymer is imidazole, and specific examples of monomers thereof include, but are not limited to, 5- (1- (2, 3-dimethylphenyl) vinyl) -1H-imidazole, 4, 5-dihydro-2-vinyl-1H-imidazole, 1-vinyl-1H-naphtho [1,2-d ] imidazole, 5, 6-dimethyl-1-vinyl-1H-benzimidazole, ethyl 4-vinyl-1H-imidazole-2-carboxylate, 1-vinyl-2-methyl-4, 5-dihydroimidazole, 1- (methoxymethyl) -5-vinyl-1H-imidazole, methyl-1-hydroxy-1, methyl-1-hydroxy-1H, 2-methyl-1-vinyl-1H-benzimidazole, 2-vinyl-1H-benzimidazole, 1, 4-divinyl-1H-imidazole, 2, 5-dimethyl-1-vinyl-1H-imidazole, 1, 5-divinyl-1H-imidazole, 1-methoxy-2-vinyl-1H-benzimidazole, 2- (vinylthio) -1H-benzimidazole, 1-ethyl-2-vinyl-4, 5-dihydro-1H-imidazole, 2-phenyl-1-vinyl-1H-imidazole, 1-vinyl-2-methyl-1H-imidazole, 1-methyl-1H-imidazole, 2-methyl-1H-imidazole, 1-methyl-1H-imidazole, 2-methyl-1H-imidazole, 1, 1-vinyl-1H-benzimidazole, 2- (2-styryl) -1H-imidazole, 2-vinyl-1H-benzimidazole-5-amine, 1- (methoxymethyl) -4-vinyl-1H-imidazole, 2-amino-1-methyl-4-vinyl-1H-imidazol-5-ol, 2-ethyl-1-vinyl-1H-benzimidazole, 2-propyl-1-vinyl-1H-benzimidazole, 3-vinylimidazo [1,2-a ] pyridine, 5-vinyl-1H-benzimidazole, 1-methyl-2-vinyl-1H-benzimidazole, 1-methoxy-1H-benzimidazole, 2- (2-styryl) -1H-imidazole, 2-methoxy-methyl-1H-benzimidazole, 2-methyl, (1-vinyl-1H-benzimidazol-2-yl) methanol, 2-vinyl-1H-imidazole, 2- (2- (3-pyridyl) vinyl) -1H-benzimidazole, 2-butyl-1-vinyl-1H-benzimidazole, 1-ethyl-5-vinyl-1H-imidazole, 1, 5-dimethyl-2-vinyl-1H-benzimidazole, 5- [ (E) -2- (2, 6-dimethylphenyl) vinyl ] -1-ethyl-1H-imidazole, 1-vinyl-1H-benzimidazol-2-amine, 3- [ (E) -2- (1-ethyl-4, 5-dihydro-1H-imidazol-2-yl) vinyl ] pyridine, 4- (4-vinylphenyl) -1H-imidazole, 2-vinyl-1H-imidazol-4-amine, 4-ethyl-1-vinyl-1H-imidazole.
In some embodiments of the invention, the nitrogen-containing heterocycle in the vinyl nitrogen-containing heterocycle polymer is a pyrimidine, specific examples of monomers thereof include, but are not limited to, 5-vinyl-2-pyrimidinamine, N-dimethyl-5-vinyl-2-pyrimidinamine, 2-vinyl-4, 6-pyrimidinediamine, 4, 6-dimethyl-2-vinylpyrimidine, 2-methoxy-5-vinylpyrimidine, 2, 4-dimethyl-6-vinylpyrimidine, N-methyl-5-vinyl-4-pyrimidinamine, 4-methyl-6-vinylpyrimidine, 4, 6-divinylpyrimidine, 4-methyl-6-vinylpyrimidine, 2, 4-dimethyl-5-vinylpyrimidine, 4-vinylpyrimidine, 2-vinyl-4-pyrimidinecarbonitrile, 2-vinylpyrimidine.
In some embodiments, the bloom inhibitor is selected from at least one of citric acid, tartaric acid, malic acid, ascorbic acid, gluconic acid, lactic acid, fumaric acid.
Citric acid is white translucent crystal or powder. Odorless, tasteless acid, citric acid crystallized from a cold solution containing 1 molecule of water, is dried in dry air or heated to 40-50 deg.C to form an anhydrate. Slightly deliquescent in humid air. Softening at 75 deg.C, melting at 100 deg.C, and dissolving in water, ethanol and diethyl ether. And is combustible. Insoluble in organic solvents such as chloroform and benzene. The aqueous solution is acidic. Citric acid is a strong organic acid, which has a strong corrosive effect on carbon steel, but has no corrosion on stainless steel. Can be oxidized to generate oxalic acid when meeting a strong oxidant (such as potassium permanganate); when melted with potassium hydroxide, it decomposes into oxalic acid and acetic acid.
Tartaric acid has two asymmetric carbon atoms in its molecule, so that it has 3 optical isomers, i.e. D-tartaric acid or D-tartaric acid, L-tartaric acid or L-tartaric acid and meso-tartaric acid. Equal amount of levo-tartaric acid and dextro-tartaric acid are mixed to obtain racemic tartaric acid or DL-tartaric acid. The natural tartaric acid is dextro-tartaric acid. The largest production in industry is racemic tartaric acid. The D-tartaric acid is colorless transparent crystal or white crystal powder, and has no odor, extremely acidic taste, and relative density of 1.7598. The melting point is 168-170 ℃. Is easily soluble in water, methanol and ethanol, slightly soluble in diethyl ether, and insoluble in chloroform. DL-type tartaric acid is colorless transparent fine-grained crystal, and has no odor and relative density of 1.697. Melting point is 204-206 ℃, and decomposition is carried out at 210 ℃. Soluble in water and ethanol, slightly soluble in diethyl ether, and insoluble in toluene. Tartaric acid is stable in air. Is nontoxic.
Malic acid has 3 isomers of L-malic acid, D-malic acid and DL-malic acid. Naturally occurring malic acid is L-shaped and is present in almost all fruits, the largest of which is the pome fruits. The malic acid is colorless needle crystal or white crystal powder, has no odor, and has pungent, refreshing and sour taste. Density 1.595g/cm3Melting point 100 deg.C, decomposition point 140 deg.C, specific optical rotation of-2.3 deg. (8.5 g/100 ml water), is easily soluble in water, methanol, acetone, dioxane, and insoluble in benzene. Equal amounts of the levorotatory isomer and the dextrorotatory isomer were mixed to obtain a racemic mixture.
Ascorbic acid is relatively stable in dry air, impure and many natural products can be oxidized by air and light, the aqueous solution of ascorbic acid is unstable and is quickly oxidized into dehydroascorbic acid, especially in neutral or alkaline solution, and the oxidation is accelerated by light, heat, iron, copper and other metal ions, so that stable metal salt can be formed. Is a relatively strong reducing agent, and the color becomes dark after being stored for a long time and becomes light yellow to different degrees. Can be used as nutritional supplement and antioxidant. Ascorbic acid is useful as an antioxidant in many food products, including processed fruits, vegetables, meat, fish, dried fruits, soft drinks and beverages. Can be added into pure fruit juice to maintain flavor and enhance vitamin C for a long time; can be added into canned food and syrup to prevent color and flavor change of fructus Persicae, fructus Pruni, and fructus Pruni Pseudocerasi; can be added into beer and carbonated water to prevent oxidation and flavor deterioration. In addition, it can be used as improver for wheat flour.
Gluconic acid can be prepared by oxidizing 1-bit aldehyde group of glucose into carboxyl, is colorless to light yellow slurry liquid, is not easy to obtain crystals, is easy to dissolve in water, is slightly soluble in alcohol, and is usually used as 50% gluconic acid solution. The sour taste of the glucose acid water is refreshing, and can be used as raw material for preparing cold beverage and edible vinegar.
Lactic acid is a compound that plays a role in a variety of biochemical processes. It is a carboxylic acid of formula C3H6O3. It is a carboxylic acid containing a hydroxyl group and is therefore an alpha-hydroxy acid (AHA). Its carboxyl group in aqueous solution releases a proton, producing lactate ions.
Fumaric acid, also known as fumaric acid, corynic acid or lichenic acid, also known as fumaric acid (IUPAC name (E) -butenedioic acid), is a colorless, flammable crystal of carboxylic acid derived from butene. It has the chemical formula of C4H4O4. Burning fumaric acid releases the irritating maleic anhydride smoke. It tastes like fruit and is found in corydalis, Boletus, lichen and Iceland sea weed.
In some embodiments, the complexing agent is at least one of an alcohol amine, ethylene diamine tetraacetic acid, ethylene diamine tetramethylene phosphonic acid, diethylene triamine pentamethylene methylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid, 2-phospho-1, 2, 4-tricarboxylic acid butane, sodium tripolyphosphate, sodium pyrophosphate, sodium metaphosphate, aminotrimethylene phosphonic acid, phosphonobutane tricarboxylic acid.
The appearance quality is particularly important for aluminum alloy products having a surface decoration function. Visual inspection is generally used for the inspection of the appearance quality. The appearance quality is checked by visual inspection, and an appropriate observation distance is selected according to the final use purpose of the product, and the observation distance is generally 0.5m for a decorative anodic oxide film product and 3m for an architectural anodic oxide film product. The normal vision or corrected vision is not less than 1.2, and the defects affecting the use, such as air bubbles, pinholes, inclusions, flow marks, scratches and the like, on the decorative surface are required to be avoided when the decorative surface is observed under natural light conditions.
In some embodiments, the surfactant is a sulfonate.
In some embodiments, the sulfonate salt comprises a nitrogen heterocyclic sulfonate salt, a benzene ring sulfonate salt.
In some embodiments, the azacyclamate is selected from at least one of a pyridine sulfonate, an imidazole sulfonate, a pyrimidine sulfonate.
In the present invention, specific examples of the pyridine sulfonate include, but are not limited to, 5-hydroxy-2-pyridine sulfonate, 3-methylpyridine-4-sulfonate, 6-amino-2-pyridine sulfonate, pyridine-2-sulfonate, 3-pyridine sulfonate, 6-amino-3-pyridine sulfonate, 6-methyl-2-pyridine sulfonate, 3 "-bipyridine-5-sulfonate, 4-methyl-2-pyridine sulfonate, 3-methyl-2-pyridine sulfonate, 2-pyridylhydroxymethane sulfonate, 4-amino-3-pyridine sulfonate.
In the present invention, specific examples of the imidazole sulfonate include, but are not limited to, 1H-benzimidazole-5-sulfonate, 2-methylimidazole-4-sulfonate, 1H-benzimidazole-1-sulfonate, 2-amino-1H-imidazole-4-sulfonate, 1-methyl-4, 5-dihydro-1H-imidazole-2-sulfonate, 2-imidazole sulfonate, 5-methylimidazole-4-sulfonate, 2-amino-4H-imidazole-4-sulfonate.
In the present invention, specific examples of the pyrimidine sulfonate include, but are not limited to, a pyrimidine trisulfonate.
In the present invention, specific examples of the benzene ring sulfonate include, but are not limited to, hexylbenzene sulfonate, octylbenzene sulfonate, decylbenzene sulfonate, dodecylbenzene sulfonate.
The sulfonate salts of the present invention can be obtained by neutralization with an acid and a base.
In some preferred embodiments, the sulfonate is a mixture of 2-imidazole sulfonate and dodecylbenzene sulfonate, the weight ratio of 2-imidazole sulfonate to dodecylbenzene sulfonate is 2: 5. the 2-imidazole sulfonate can be sodium 2-imidazole sulfonate, and 2-imidazole sulfonate and sodium hydroxide can be adopted in a molar ratio of 1: 1 are mixed to obtain the product. The dodecylbenzene sulfonate may be sodium dodecylbenzene sulfonate.
In some embodiments, the pH buffering agent is selected from at least one of ammonium acetate, ammonium benzoate, ammonium phthalate.
The sealing agent containing nickel adopted in the prior art pollutes the environment, a large amount of resources are consumed for treating the wastewater, and the substance containing nickel is harmful to human bodies. The sealing agent provided by the invention is a nickel-free sealing agent, the wastewater generated in the process is easy to treat, and the obtained aluminum and aluminum alloy anodic oxide film has better salt spray resistance. Compared with the nickel-free sealing agent in the prior art, the color difference change of the product after sealing is small, the original dyeing is not changed, and the color is not easy to fade.
The existing aluminum alloy products mainly comprise 6061, 6063, 7075 and the like, and the components, the performances and the application range of various aluminum alloys are different. For example, the main alloy elements in the 6061 alloy are magnesium and silicon, and the 6061 alloy has medium strength, good corrosion resistance and weldability and good oxidation effect. The product is widely applied to various industrial structural parts which are required to have certain strength and high corrosion resistance, such as manufacturing trucks, tower buildings, ships, electric trains, railway vehicles, furniture and the like. In the 6061 alloy, 0.15-0.4 wt% of Cu, 0.4-0.8 wt% of Si, 0.7 wt% of Femax, 0.15 wt% of Mnmax, 0.8-1.2 wt% of Mg, 0.25 wt% of Znmax, 0.04-0.35 wt% of Cr, 0.15 wt% of Timax and the balance of Al are contained. The main alloying elements in the 6063 alloy are magnesium and silicon, which are typical of extrusion alloys. 6063 alloy is widely used in building section, irrigation pipe, rod and section for vehicle, rack, furniture, lifter and fence. In the 6063 alloy, 0.1 wt% Cumax, 0.2-0.6 wt% Si, 0.35 wt% Femax, 0.1 wt% Mnmax, 0.45-0.9 wt% Mg, 0.1 wt% Znmax, 0.1 wt% Crmax, 0.1 wt% Timax, and the balance Al. The 7075 alloy has high strength below 150 ℃, particularly good low-temperature strength, poor welding performance and a tendency of stress corrosion cracking. 7075 the main alloy element is zinc, which has high strength, good mechanical properties and good anodic reaction. The method is mainly used for manufacturing airplane structures and other high-stress structural parts requiring high strength and strong corrosion resistance, such as upper and lower wing surface wall plates, stringers and the like of airplanes. In the 7075 alloy, 1.2-2 wt% Cu, 0.4 wt% Simax, 0.5 wt% Femax, 0.3 wt% Mnmax, 2.1-2.9 wt% Mg, 5.1-6.1 wt% Zn, 0.4 wt% Crmax, 0.06 wt% Timax, and the balance Al. The inventor finds that 6061 contains more alloying elements than 6063, so that the strength of the material is high, and the content of Mg and Si influences the sealing effect of the surface. Particularly, the 7075 alloy has higher Mg and Si contents, so that the conditions of large color difference change and color loss are easy to occur. The invention adopts the nickel-free sealing agent with specific components and content, and can obtain better fixation and sealing effects in the alloy with higher Mg and Si contents. The inventor believes that when the vinyl nitrogen heterocyclic polymer is selected from a vinyl imidazole polymer, the vinyl imidazole polymer can play a synergistic role with imidazole sulfonate, not only can quickly fill pores and reduce porosity, but also can prevent bubbles, pinholes, flow marks and the like from being generated on the surface of the aluminum alloy. Meanwhile, the vinyl imidazole polymer and the imidazole sulfonate can have a good effect with dye, so that the dyed aluminum alloy is difficult to fade. Even in the aluminum alloy with high Mg and Si contents, the color fixing effect can be better.
In some embodiments, the aluminum and aluminum alloy anodized nickel-free sealants are used for Al6061, Al6063, Al 7075.
The second aspect of the invention provides a method for using the aluminum and aluminum alloy anodic oxidation nickel-free sealing agent, wherein the treatment temperature is 70-100 ℃, and the treatment time is 10-40 min.
The invention is further illustrated by the following specific examples.
Example 1
The aluminum and aluminum alloy anode oxidation nickel-free sealing agent comprises 1L of raw materials including 0.5g of 2- (2-styryl) -1H-imidazole, 1.1g of tartaric acid, 2g of amino trimethylene phosphonic acid, 0.8g of 2-imidazole sodium sulfonate, 2g of sodium dodecyl benzene sulfonate and 1g of ammonium acetate.
Example 2
The aluminum and aluminum alloy anode oxidation nickel-free sealing agent comprises 1L of raw materials including 0.5g of 2-vinylpyridine, 1.1g of tartaric acid, 2g of amino trimethylene phosphonic acid, 0.8g of 2-imidazole sodium sulfonate, 2g of sodium dodecyl benzene sulfonate and 1g of ammonium acetate.
Example 3
The aluminum and aluminum alloy anode oxidation nickel-free sealing agent comprises 1L of raw materials including 0.5g of 2- (2-styryl) -1H-imidazole, 1.1g of tartaric acid, 2g of amino trimethylene phosphonic acid, 0.8g of 3-pyridine sodium sulfonate, 2g of sodium dodecyl benzene sulfonate and 1g of ammonium acetate.
Example 4
The aluminum and aluminum alloy anode oxidation nickel-free sealing agent comprises 1L of raw materials including 0.5g of 2-vinylpyridine, 1.1g of tartaric acid, 2g of amino trimethylene phosphonic acid, 0.8g of 3-pyridine sodium sulfonate, 2g of sodium dodecyl benzene sulfonate and 1g of ammonium acetate.
Example 5
The aluminum and aluminum alloy anode oxidation nickel-free sealing agent comprises 1L of raw materials including 1.1g of tartaric acid, 2g of amino trimethylene phosphonic acid, 0.8g of 2-imidazole sodium sulfonate, 2g of sodium dodecyl benzene sulfonate and 1g of ammonium acetate.
Example 6
The aluminum and aluminum alloy anode oxidation nickel-free sealing agent comprises 1L of raw materials including 0.5g of 2- (2-styryl) -1H-imidazole, 1.1g of tartaric acid, 2g of amino trimethylene phosphonic acid, 2.8g of sodium dodecyl benzene sulfonate and 1g of ammonium acetate.
Example 7
The aluminum and aluminum alloy anode oxidation nickel-free sealing agent comprises 1L of raw materials including 0.5g of 2- (2-styryl) -1H-imidazole, 1.1g of tartaric acid, 2g of amino trimethylene phosphonic acid, 2.8g of 2-imidazole sodium sulfonate and 1g of ammonium acetate.
Evaluation test
The sample was anodized aluminum alloy 7075, dyed with acid scarlet GR, divided into 100 grids on sample aluminum alloy 7075 with 1cm × 1cm grids, and then subjected to sealing treatment using examples 1 to 7, respectively, at a treatment temperature of 75 ℃ for 15 min.
1. Evaluation of appearance quality
The appearance quality was checked by visual inspection with an observation distance of 0.5 m. And observing whether bubbles or inclusions exist in the grids, and recording the number of the grids with the bubbles or the inclusions as appearance quality evaluation.
2. Evaluation of fixation
By usingThe reflectance at 620nm before and after the sample sealing treatment was measured by an ultraviolet-visible diffuse reflectometer. The reflectivity before the sealing treatment is R0The reflectance after the sealing treatment is R1Record R ═ R0-R1)/R0×100％。
The test results are listed in the following table.
| Appearance quality | R | |
| Example 1 | 0 | 1.2％ |
| Example 2 | 2 | 2.5％ |
| Example 3 | 3 | 3.8％ |
| Example 4 | 7 | 4.9％ |
| Example 5 | 15 | 31％ |
| Example 6 | 9 | 8.8％ |
| Example 7 | 12 | 14％ |
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (2)
1. The aluminum and aluminum alloy anodic oxidation nickel-free sealing agent is characterized in that 1L of raw materials of the sealing agent is counted, the raw materials of the sealing agent at least comprise 0.1-2g of color fixing agent, 0.8-1.5g of frost ash inhibitor, 0.1-4g of complexing agent, 0.1-5g of surfactant and 0-5g of pH buffering agent, the surfactant is sulfonate, the sulfonate is a mixture of 2-imidazole sulfonate and dodecyl benzene sulfonate, and the weight ratio of the 2-imidazole sulfonate to the dodecyl benzene sulfonate is 2: 5; the color fixing agent is a vinyl nitrogen heterocyclic ring polymer; the nitrogen-containing heterocycle in the vinyl nitrogen-containing heterocycle polymer comprises imidazole; the aluminum and aluminum alloy anodic oxidation nickel-free sealing agent is used for Al6061, Al6063 and Al 7075; the frost ash inhibitor is at least one selected from citric acid, tartaric acid, malic acid, ascorbic acid, gluconic acid, lactic acid and fumaric acid; the complexing agent is selected from at least one of alcohol amine, ethylene diamine tetraacetic acid, ethylene diamine tetramethylene phosphonic acid, diethylene triamine pentamethylene methylene phosphonic acid, hexamethylene diamine tetramethylene phosphonic acid, 2-phosphate-1, 2, 4-tricarboxylic acid butane, sodium tripolyphosphate, sodium pyrophosphate, sodium metaphosphate, amino trimethylene phosphonic acid and phosphonobutane tricarboxylic acid; the pH buffering agent is selected from at least one of ammonium acetate, ammonium benzoate and ammonium phthalate; the content of the pH buffer is not 0.
2. The method of using the aluminum and aluminum alloy anodic oxidation nickel-free sealing agent as claimed in claim 1, wherein the treatment temperature is 70-100 ℃ and the treatment time is 10-40 min.
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| CN114059129B (en) * | 2021-11-24 | 2023-04-14 | 武汉风帆电化科技股份有限公司 | Color fixing agent for aluminum and aluminum alloy after anodic oxide film dyeing and preparation method |
| CN114959829A (en) * | 2022-06-16 | 2022-08-30 | 江门市优博科技有限公司 | Normal-temperature environment-friendly sealant for dyeing aluminum and aluminum alloy anodic oxide films and preparation method and application process thereof |
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| CN107604414B (en) * | 2017-08-22 | 2020-03-24 | 珠海市奥美伦精细化工有限公司 | Aluminum and aluminum alloy anodic oxidation high-temperature nickel-free sealing agent |
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