CN111188071B - High-performance hole sealing process for aluminum alloy anodic oxidation - Google Patents
High-performance hole sealing process for aluminum alloy anodic oxidation Download PDFInfo
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- CN111188071B CN111188071B CN202010114796.9A CN202010114796A CN111188071B CN 111188071 B CN111188071 B CN 111188071B CN 202010114796 A CN202010114796 A CN 202010114796A CN 111188071 B CN111188071 B CN 111188071B
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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
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Abstract
The invention belongs to the technical field of hole sealing agents, and particularly relates to a high-performance hole sealing process for aluminum alloy anodic oxidation. The medium-temperature hole sealing agent comprises the following components in parts by weight: 0.1-10 parts of metal salt, 0.01-10 parts of organic acid, 0.01-10 parts of wetting agent and 0.01-10 parts of regulator. The invention can simultaneously realize five cycle tests of CASS24H, NSS 480H, alkali resistance (PH 13.5), high humidity resistance (240 hours), acid and alkali resistance (PH1+13.5), sulfur dioxide and the like of the aluminum alloy anode oxide film only by two-step hole sealing; the effect is realized by more than three times of hole sealing in the prior art, and the process is simple to operate, convenient to maintain and very suitable for batch production; compared with transparent electrophoresis, the process has the advantages of less consumption and low cost (far lower than the cost of the transparent electrophoresis), and is suitable for large-scale popularization.
Description
Technical Field
The invention belongs to the technical field of hole sealing agents, and particularly relates to a high-performance hole sealing process for aluminum alloy anodic oxidation.
Background
With the development of the automobile industry and the aggravation of international competition, the performance requirements of customers on the aluminum alloy anodized film layer are higher and higher, and especially the appearance requirements of aluminum alloy decorating parts such as luggage racks and the like are high in brightness and high in corrosion resistance, for example: alkali resistance (ph 13.5), high humidity resistance (240 hours), 480 hours neutral salt spray test, CASS24 hours, and sulfur dioxide five-cycle test, etc., which are required by walvo, volkswagen, gallo, audi, bmu, general-purpose, etc.
Anodic oxidation hole sealing processes (including multiple hole sealing) at home and abroad can not simultaneously solve five cycle tests of oxidation films CASS24H, NSS 480H, alkali resistance (PH 13.5), high humidity resistance (240 hours), acid and alkali resistance (PH1+13.5), sulfur dioxide and the like, and some factories can only adopt a transparent electrophoresis mode to meet the requirements of customers at present.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a moderate temperature sealant, which comprises the following components in parts by weight: 0.1-10 parts of metal salt, 0.01-10 parts of organic acid, 0.01-10 parts of wetting agent and 0.01-10 parts of regulator.
As a preferable technical scheme, the metal salt is selected from one or more of nickel salt, zirconium salt and titanium salt.
As a preferable technical scheme, the nickel salt is selected from one or more of nickel sulfate, nickel fluoride, nickel acetate, nickel carbonate and nickel chloride.
As a preferred technical scheme, the zirconium salt is selected from one or more of zirconium n-propoxide, zirconium iso-octoate, potassium fluozirconate, zirconium tetraethoxide, tetrabutyl zirconate, fluozirconic acid, zirconium acetate, zirconium sulfate, zirconium acetylacetonate and tetra (dimethylamino) zirconium.
As a preferable technical scheme, the titanium salt is selected from one or more of potassium fluotitanate, titanium tetrachloride, fluotitanic acid, titanyl sulfate and tetrabutyl titanate.
As a preferable embodiment, the organic acid is selected from one or more of formic acid, acetic acid, propionic acid, succinic acid, adipic acid, oxalic acid, malic acid, citric acid, succinic acid, ascorbic acid, salicylic acid, caffeic acid, tartaric acid, phthalic acid, benzoic acid, glycine, lysine, proline, serine, arginine, glutamic acid, tryptophan, citrulline, histidine, and polyacrylic acid.
As a preferable technical scheme, the wetting agent is selected from branched secondary alcohol polyoxyethylene ether, sulfonic acetaldehyde polycondensate sodium salt, tallow alkyl dihydroxyethyl amine oxide, oleyl propylene diamine, dodecyl amine oxide, glycerol polyoxyethylene ether, phosphate ester, octyl phenol polyoxyethylene ether, nonyl phenol polyoxyethylene ether, oleyl polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, sodium fatty alcohol polyoxyethylene ether sulfate, dioctyl sodium sulfosuccinate, sulfonate such as alkenyl sodium sulfonate, Tween 80, linear secondary alcohol polyoxyethylene ether, acrylic acid-acrylate-sulfonate terpolymer, maleic acid-acrylic acid copolymer, carboxylic acid-sulfonic acid-nonionic terpolymer, carboxylic acid-sulfonic acid-acrylate copolymer, dihydroxy phosphonoacetic acid, diethylene triamine pentamethylene phosphonic acid pentasodium salt, dimethyl ammonium sulfate, sodium sulfonate, sodium hydrogen ammonium sulfate, dimethyl ammonium sulfate, sodium, dimethyl ammonium sulfate, dimethyl ammonium, One or more of sodium diethylenetriamine pentamethylene phosphate and fluorine-containing surfactant.
As a preferable technical solution, the modifier is selected from one or more of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium carbonate, ammonium bicarbonate, tetrabutylammonium hydroxide, ammonia water, tetramethylammonium hydroxide, fluorosilicic acid, fluoroboric acid, hydrofluoric acid, potassium borohydride, boric acid, potassium fluoride, sodium fluoride, diethylenetriamine, polyethylene polyamine, diethanolamine, triethanolamine, cyclohexylamine, guanidine acetate, guanidine nitrate, guanidine carbonate, and acetyl urea.
The second aspect of the invention provides a high-performance hole sealing process for aluminum alloy anodic oxidation, which at least comprises a medium-temperature hole sealing step and a high-temperature hole sealing step, wherein the medium-temperature hole sealing step is to seal holes by using the medium-temperature hole sealing agent.
As a preferred technical scheme, the high-temperature hole sealing step is to seal holes by adopting a high-temperature hole sealing agent, and the high-temperature hole sealing agent comprises a silicon-containing compound, a dispersing agent, a pH regulator and a corrosion inhibitor.
Has the advantages that:
1. the invention can simultaneously realize five cycle tests of CASS24H, NSS 480H, alkali resistance (PH 13.5), high humidity resistance (240 hours), acid and alkali resistance (PH1+13.5), sulfur dioxide and the like of the aluminum alloy anode oxide film only by two-step hole sealing;
2. the effect is realized by more than three times of hole sealing in the prior art, and the process is simple to operate, convenient to maintain and very suitable for batch production;
3. compared with transparent electrophoresis, the process has the advantages of less consumption and low cost (far lower than the cost of the transparent electrophoresis), and is suitable for large-scale popularization.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
In order to solve the above problems, the first aspect of the present invention provides a moderate temperature sealant, which comprises the following components in parts by weight: 0.1-10 parts of metal salt, 0.01-10 parts of organic acid, 0.01-10 parts of wetting agent and 0.01-10 parts of regulator.
Preferably, the medium-temperature hole sealing agent comprises the following components in parts by weight: 2-8 parts of metal salt, 1-6 parts of organic acid, 1-5 parts of wetting agent and 1-3 parts of regulator.
Metal salt
Preferably, the metal salt is selected from one or more of nickel salt, zirconium salt and titanium salt.
Preferably, the nickel salt is selected from one or more of nickel sulfate, nickel fluoride, nickel acetate, nickel carbonate and nickel chloride.
Preferably, the zirconium salt is selected from one or more of zirconium n-propoxide, zirconium iso-octoate, potassium fluorozirconate, zirconium tetraethoxide, tetrabutyl zirconate, fluorozirconic acid, zirconium acetate, zirconium sulfate, zirconium acetylacetonate and tetrakis (dimethylamino) zirconium.
Preferably, the titanium salt is selected from one or more of potassium fluotitanate, titanium tetrachloride, fluotitanic acid, titanyl sulfate and tetrabutyl titanate.
Preferably, the metal salt comprises nickel sulfate, zirconium acetate; more preferably, the metal salt is nickel sulfate and zirconium acetate according to the mass ratio of (3-5): (1-2) compounding to obtain a mixture; more preferably, the metal salt is nickel sulfate and zirconium acetate according to a mass ratio of 4: 1 compounding the obtained mixture.
The invention adopts nickel sulfate and zirconium acetate as metal salts, which can improve the corrosion resistance, and the inventor unexpectedly finds that when the content of zirconium acetate is changed, the influence on the corrosion resistance is larger, presumably because the coordination number of zirconium ions in a system is lower, a disordered solidified body structure is obtained after the reaction, so that the zirconium ions permeate into the surface of a micropore, the electropositive state of the pore wall is changed, the diffusion of the nickel ions into the pore wall is promoted, the nickel ions are hydrolyzed and deposited in the membrane, and the corrosion resistance is enhanced.
In the process of research, the sealing effect of zirconium acetate is unexpectedly better than that of zirconium sulfate, and the sealing effect of sulfate ions is slightly reduced when the concentration is the same, but the inventor speculates that the microporous oxide film is easy to physically adsorb with acetate and reacts with acetate to a certain extent to generate an aluminum soap compound, and the zirconium acetate and the hydroxide ions are combined firstly to generate hydrolysis precipitation under certain pH conditions because the stability of aluminum salt and nickel salt is higher than that of zirconium salt, and the zirconium acetate and the hydroxide ions are coordinated with nickel sulfate to ensure that the sealing effect is better.
Organic acids
Preferably, the organic acid is selected from one or more of formic acid, acetic acid, propionic acid, succinic acid, adipic acid, oxalic acid, malic acid, citric acid, succinic acid, ascorbic acid, salicylic acid, caffeic acid, tartaric acid, phthalic acid, benzoic acid, glycine, lysine, proline, serine, arginine, glutamic acid, tryptophan, citrulline, histidine, and polyacrylic acid.
Preferably, the organic acid is adipic acid.
Wetting agent
Preferably, the wetting agent is selected from branched secondary alcohol polyoxyethylene ether, sulfonic acetaldehyde polycondensate sodium salt, tallow alkyl dihydroxyethyl amine oxide, oleyl propylene diamine, dodecyl amine oxide, glycerol polyoxyethylene ether, phosphate ester, octyl phenol polyoxyethylene ether, nonyl phenol polyoxyethylene ether, oleyl polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, sodium fatty alcohol polyoxyethylene ether sulfate, dioctyl sodium sulfosuccinate, sulfonate such as alkenyl sodium sulfonate, tween 80, linear secondary alcohol polyoxyethylene ether, acrylic acid-acrylate-sulfonate terpolymer, maleic acid-acrylic acid copolymer, carboxylic acid-sulfonic acid-nonionic terpolymer, carboxylic acid-sulfonic acid-acrylate copolymer, dihydroxyphosphonoacetic acid, diethylenetriamine pentamethylene phosphonic acid pentasodium, diethylenetriamine pentamethylene sodium phosphate, tallow alkyl bishydroxyethyl amine oxide, oleyl propylene diamine, dodecyl amine oxide, glycerol polyoxyethylene ether, phosphate ester, octyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, oleyl polyoxyethylene ether, isomerol alcohol polyoxyethylene ether, sodium fatty alcohol sulfate, dioctyl sodium sulfosuccinate, linear secondary alcohol-acrylate terpolymer, maleic acid-acrylic acid-nonionic terpolymer, carboxylic acid-sulfonic acid-acrylic acid-acrylate copolymer, dihydroxyphosphonoacetic acid-phosphoric acid-penta-sodium salt, diethylenetriamine penta phosphate, sodium salt, and the like, One or more fluorosurfactants.
Among them, the fluorosurfactant is preferably a perfluorinated carboxylic acid having 6 to 10 carbon atoms, such as ammonium perfluorocarboxylate, including ammonium perfluorooctanoate or ammonium perfluorooctanoate, and the like.
Preferably, the wetting agent comprises an acrylic acid-acrylate-sulfonate terpolymer, dihydroxyphosphonoacetic acid; more preferably, the wetting agent is an acrylic acid-acrylate-sulfonate terpolymer and dihydroxy phosphono acetic acid in a mass ratio of (0.5-2): (0.5-2) compounding the obtained mixture; more preferably, the wetting agent is acrylic acid-acrylate-sulfonate terpolymer and dihydroxy phosphono acetic acid in a mass ratio of 1: 1 compounding the obtained mixture. The acrylic acid-acrylate-sulfonate terpolymer is a TH-613 product and is not limited to a purchasing manufacturer.
The inventor finds that the sealing effect of the acrylic acid-acrylate-sulfonic acid terpolymer is poor when being singly added, and then in experimental research, the inventor unexpectedly finds that when a proper amount of dihydroxyphosphonoacetic acid is added, the sealing effect is improved, and the corrosion resistance is improved, when the relative metal salt mass ratio, namely when the mass ratio of the compounded wetting agent to the metal salt is 1: (1.5-2.5), the corrosion resistance is the best, and the inventors speculate that too small or too large a mass ratio may cause poor penetration of nickel sulfate, increase of viscosity of nickel sulfate, uneven deposition on the surface of pores, and formation of fine cracks during the treatment, which may result in degradation of corrosion resistance.
Regulating agent
Preferably, the modifier is selected from one or more of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium carbonate, ammonium bicarbonate, tetrabutylammonium hydroxide, ammonia, tetramethylammonium hydroxide, fluorosilicic acid, fluoroboric acid, hydrofluoric acid, potassium borohydride, boric acid, potassium fluoride, sodium fluoride, diethylenetriamine, polyethylenepolyamine, diethanolamine, triethanolamine, cyclohexylamine, guanidine acetate, guanidine nitrate, guanidine carbonate, and acetyl urea.
Preferably, the conditioning agent is a 2% sodium hydroxide solution.
The preparation method of the medium-temperature hole sealing agent comprises the following steps:
(1): two thirds of deionized water is added into a dispensing barrel, and the machine is started to stir.
(2): adding metal salt, organic acid, wetting agent and regulator in sequence according to the measured amount, supplementing deionized water to the liquid level, and stirring until the mixture is clear.
(3): and (6) subpackaging.
The second aspect of the invention provides a high-performance hole sealing process for aluminum alloy anodic oxidation, which at least comprises a medium-temperature hole sealing step and a high-temperature hole sealing step, wherein the medium-temperature hole sealing step is to seal holes by using the medium-temperature hole sealing agent.
Preferably, the high-temperature hole sealing step is to seal holes by using a high-temperature hole sealing agent, and the high-temperature hole sealing agent comprises a silicon-containing compound, a dispersing agent, a pH regulator and a corrosion inhibitor.
Preferably, the high-temperature hole sealing step is to seal holes by adopting a high-temperature hole sealing agent, and the high-temperature hole sealing agent comprises 0.1-10 parts by weight of a silicon-containing compound, 0.01-10 parts by weight of a dispersing agent, 0.01-10 parts by weight of a pH regulator and 0.01-10 parts by weight of a corrosion inhibitor.
More preferably, the high-temperature hole sealing step is to seal holes by using a high-temperature hole sealing agent, and the high-temperature hole sealing agent comprises 3-10 parts by weight of a silicon-containing compound, 1-3 parts by weight of a dispersing agent, 1-2 parts by weight of a pH regulator and 1-10 parts by weight of a corrosion inhibitor.
Silicon-containing compound
Preferably, the silicon-containing compound is selected from any one of inorganic silicates, organic silicates and organic silanes.
Examples of the inorganic silicate include, but are not limited to, sodium silicate and potassium silicate.
Examples of organosilicates include, but are not limited to, sodium methyl silicate, potassium methyl silicate.
Examples of organosilanes include, but are not limited to, one or more of nanosilane, nanosilica sol, kH550, kH560, kH570, kH580, Z-6011, Z-6020, Z-6040, tridecafluorooctyltriethoxysilane.
Preferably, the silicon-containing compound is sodium silicate.
Dispersing agent
Preferably, the dispersant is selected from one or more of a surfactant and a high molecular polymer.
Examples of the surfactant include, but are not limited to, one or more of branched secondary alcohol polyoxyethylene ether, sulfonic acid acetaldehyde polycondensate sodium salt, tallow alkyl bis hydroxyethyl amine oxide, oleyl propylene diamine, lauryl amine oxide, glycerol polyoxyethylene ether, phosphate, octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, oleyl polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, sodium fatty alcohol polyoxyethylene ether sulfate, dioctyl sodium sulfosuccinate, sodium alkenyl sulfonate, and the like, tween 80, and linear secondary alcohol polyoxyethylene ether.
As examples of the high molecular polymer, one or more of acrylic acid-acrylate-sulfonate terpolymer, maleic acid-acrylic acid copolymer, carboxylic acid-sulfonic acid-nonionic terpolymer, and carboxylic acid-sulfonic acid-acrylate copolymer are included, but not limited thereto.
Preferably, the dispersant is dioctyl sodium sulfosuccinate.
pH regulator
The pH adjuster as the present invention may be selected from one or more of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium carbonate, ammonium bicarbonate, tetrabutylammonium hydroxide, ammonia water, borax, sodium borohydride, boric acid, formic acid, acetic acid, propionic acid, succinic acid, adipic acid, oxalic acid, malic acid, citric acid, succinic acid, ascorbic acid, salicylic acid, caffeic acid, tartaric acid, phthalic acid, benzoic acid, glycine, lysine, proline, serine, arginine, glutamic acid, tryptophan, citrulline, histidine, 2-hydroxyphosphonoacetic acid, polyaspartic acid, polyepoxysuccinic acid, and phosphonopolyacrylic acid.
Preferably, the pH adjuster is a 2% sodium hydroxide solution.
Corrosion inhibitor
The corrosion inhibitor is one or more selected from inorganic acid salt, nitrogen-containing organic matter, organic phosphine and resin.
As examples of inorganic acid salts, one or more of vanadate and molybdate are included, but not limited to.
Examples of nitrogen-containing organic compounds include, but are not limited to, one or more of benzotriazole, tolyltriazole, oleic imidazoline corrosion inhibitors.
Examples of organic phosphines include, but are not limited to, potassium hexaneditetramethylidene phosphonate, tetrasodium aminotrimethylidene phosphonate, polyol phosphate.
As examples of resins, one or more of water-soluble acrylic resins, water-soluble epoxy resins, small-soluble polyurethanes, water-soluble phenolic resins, phosphonocarboxylic acid copolymers, maleic-acrylic copolymers, polyethylene glycols are included, but not limited thereto.
Preferably, the corrosion inhibitor comprises hexanediamine tetraformic acid potassium salt, polyethylene glycol; more preferably, the corrosion inhibitor is hexanediamine tetramethylenephosphonic acid potassium salt and polyethylene glycol according to the mass ratio of 1: 1 compounding the obtained mixture.
The preparation method of the high-temperature hole sealing agent comprises the following steps:
(1): two thirds of deionized water is added into a dispensing barrel, and the machine is started to stir.
(2): adding the silicon-containing compound, the dispersing agent, the pH regulator and the corrosion inhibitor in sequence according to the measured amount, supplementing deionized water to the liquid level, and stirring uniformly.
(3): and (6) subpackaging.
The third aspect of the invention provides a hole sealing process, which specifically comprises the following steps: pretreatment → anodic oxidation → at least quadruple pure water washing → medium temperature hole sealing → at least triple pure water washing → high temperature hole sealing → quadruple pure water washing → drying → blanking inspection.
The pretreatment comprises the following steps: the appearance effect is achieved according to the glossiness and the roughness required by a client, and the process generally comprises the steps of removing oil from a workpiece …, washing with … water, washing with …, chemically polishing with … water, washing with … water, removing ash and washing with … water.
The anode is oxidized into: and (4) anodizing the sulfuric acid.
The at least quadruple pure water washing comprises the following steps: the workpiece is subjected to four water washes, namely … water wash … water wash … water wash … water wash.
The medium-temperature hole sealing is as follows: when the plant is used, the plant is recommended to be heated to 50-60 ℃ for use.
| Process parameters | Range | Recommending parameters |
| Concentration (volume ratio): | 5-20％ | 9-12％ |
| temperature: | 25-80℃ | 50-60℃ |
| time: | 10-20 minutes | 15 minutes or by thickness |
| pH: | 5.0-6.5 | 5.2-5.9 |
The at least triple pure water washing comprises the following steps: water washing … Water washing … Water washing
The high-temperature hole sealing is as follows: heating to 95 ℃ is recommended when the plant is in use.
| Process parameters | Range | Recommending parameters |
| Concentration: | 15-65g/L | 20-30g/L |
| temperature: | 90-100℃ | 98℃ |
| time: | 5-15 minutes | 10 minutes or as required |
| pH: | 9-11 | 9-10.5 |
| Filtration | Need to make sure that |
The quadruple pure water washing comprises the following steps: water washing … water washing … water washing … water washing,
the present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a moderate-temperature hole sealing agent, which comprises the following components in parts by weight: 2 parts of metal salt, 1 part of organic acid, 1 part of wetting agent and 1 part of regulator.
The metal salt is nickel sulfate and zirconium acetate according to a mass ratio of 3: 1 compounding the obtained mixture;
the organic acid is adipic acid;
the wetting agent is an acrylic acid-acrylate-sulfonate terpolymer and dihydroxy phosphono acetic acid in a mass ratio of 1: 1 compounding the obtained mixture; the acrylic acid-acrylate-sulfonate terpolymer is TH-613;
the regulator is 2% sodium hydroxide solution.
The preparation method of the medium-temperature hole sealing agent comprises the following steps:
(1): the nickel sulfate, zirconium acetate and deionized water are added into a 1L beaker in metered amounts and stirred to dissolve.
(2): adding wetting agent and adipic acid, and stirring.
(3): adding 2% sodium hydroxide solution to adjust the pH value of 5-6.5, supplementing deionized water to 1 liter, and stirring until the solution is clear.
Example 2
Embodiment 2 provides a moderate-temperature hole sealing agent, which comprises the following components in parts by weight: 8 parts of metal salt, 6 parts of organic acid, 5 parts of wetting agent and 3 parts of regulator.
The metal salt is nickel sulfate and zirconium acetate according to a mass ratio of 5: 2 compounding the obtained mixture;
the organic acid is adipic acid;
the wetting agent is an acrylic acid-acrylate-sulfonate terpolymer and dihydroxy phosphono acetic acid in a mass ratio of 1: 1 compounding the obtained mixture; the acrylic acid-acrylate-sulfonate terpolymer is TH-613;
the regulator is 2% sodium hydroxide solution.
The preparation steps of the medium-temperature hole sealing agent are the same as those of the example 1.
Example 3
Embodiment 3 provides a moderate-temperature hole sealing agent, which comprises the following components in parts by weight: 5 parts of metal salt, 3 parts of organic acid, 2 parts of wetting agent and 1.5 parts of regulator.
The metal salt is nickel sulfate and zirconium acetate according to a mass ratio of 4: 1 compounding the obtained mixture;
the organic acid is adipic acid;
the wetting agent is an acrylic acid-acrylate-sulfonate terpolymer and dihydroxy phosphono acetic acid in a mass ratio of 1: 1 compounding the obtained mixture; the acrylic acid-acrylate-sulfonate terpolymer is TH-613;
the regulator is 2% sodium hydroxide solution.
The preparation steps of the medium-temperature hole sealing agent are the same as those of the example 1.
Example 4
Embodiment 4 provides a medium-temperature hole sealing agent, which comprises the following components in parts by weight: 5 parts of metal salt, 3 parts of organic acid, 2 parts of wetting agent and 1.5 parts of regulator.
The metal salt is nickel sulfate;
the organic acid is adipic acid;
the wetting agent is an acrylic acid-acrylate-sulfonate terpolymer and dihydroxy phosphono acetic acid in a mass ratio of 1: 1 compounding the obtained mixture; the acrylic acid-acrylate-sulfonate terpolymer is TH-613;
the regulator is 2% sodium hydroxide solution.
The preparation steps of the medium-temperature hole sealing agent are the same as those of the example 1.
Example 5
Embodiment 5 provides a moderate temperature hole sealing agent, which comprises the following components in parts by weight: 5 parts of metal salt, 3 parts of organic acid, 2 parts of wetting agent and 1.5 parts of regulator.
The metal salt is zirconium acetate;
the organic acid is adipic acid;
the wetting agent is an acrylic acid-acrylate-sulfonate terpolymer and dihydroxy phosphono acetic acid in a mass ratio of 1: 1 compounding the obtained mixture; the acrylic acid-acrylate-sulfonate terpolymer is TH-613;
the regulator is 2% sodium hydroxide solution.
The preparation steps of the medium-temperature hole sealing agent are the same as those of the example 1.
Example 6
Embodiment 6 provides a moderate temperature hole sealing agent, which comprises the following components in parts by weight: 5 parts of metal salt, 3 parts of organic acid, 2 parts of wetting agent and 1.5 parts of regulator.
The metal salt is zirconium sulfate;
the organic acid is adipic acid;
the wetting agent is an acrylic acid-acrylate-sulfonate terpolymer and dihydroxy phosphono acetic acid in a mass ratio of 1: 1 compounding the obtained mixture; the acrylic acid-acrylate-sulfonate terpolymer is TH-613;
the regulator is 2% sodium hydroxide solution.
The preparation steps of the medium-temperature hole sealing agent are the same as those of the example 1.
Example 7
Embodiment 7 provides a moderate temperature hole sealing agent, which comprises the following components in parts by weight: 5 parts of metal salt, 3 parts of organic acid, 2 parts of wetting agent and 1.5 parts of regulator.
The metal salt is nickel sulfate and zirconium sulfate according to a mass ratio of 4: 1 compounding the obtained mixture;
the organic acid is adipic acid;
the wetting agent is an acrylic acid-acrylate-sulfonate terpolymer and dihydroxy phosphono acetic acid in a mass ratio of 1: 1 compounding the obtained mixture; the acrylic acid-acrylate-sulfonate terpolymer is TH-613;
the regulator is 2% sodium hydroxide solution.
The preparation steps of the medium-temperature hole sealing agent are the same as those of the example 1.
Example 8
Embodiment 8 provides a moderate temperature hole sealing agent, which comprises the following components in parts by weight: 5 parts of metal salt, 3 parts of organic acid, 2 parts of wetting agent and 1.5 parts of regulator.
The metal salt is nickel sulfate and zirconium acetate according to a mass ratio of 4: 1 compounding the obtained mixture;
the organic acid is adipic acid;
the wetting agent is an acrylic acid-acrylate-sulfonate terpolymer; the acrylic acid-acrylate-sulfonate terpolymer is TH-613;
the regulator is 2% sodium hydroxide solution.
The preparation steps of the medium-temperature hole sealing agent are the same as those of the example 1.
Example 9
Embodiment 9 provides a medium-temperature hole sealing agent, which comprises the following components in parts by weight: 5 parts of metal salt, 3 parts of organic acid, 2 parts of wetting agent and 1.5 parts of regulator.
The metal salt is nickel sulfate and zirconium acetate according to a mass ratio of 4: 1 compounding the obtained mixture;
the organic acid is adipic acid;
the wetting agent is propylene dihydroxy phosphono acetic acid;
the regulator is 2% sodium hydroxide solution.
The preparation steps of the medium-temperature hole sealing agent are the same as those of the example 1.
Evaluation of Performance
The process flow comprises the following steps: pretreatment → anodic oxidation → at least quadruple pure water washing → medium temperature hole sealing → at least triple pure water washing → high temperature hole sealing → quadruple pure water washing → drying → blanking inspection.
Aluminum material: 5-series aluminum
The medium-temperature hole sealing is as follows:
| process parameters | Range | Recommending parameters |
| Concentration (volume ratio): | 5-20％ | 9-12％ |
| temperature: | 25-80℃ | 50-60℃ |
| time: | 10-20 minutes | 15 minutes or by thickness |
| pH: | 5.0-6.5 | 5.2-5.9 |
The high-temperature hole sealing is as follows:
high-temperature sealant (6 parts of sodium silicate, 2 parts of dioctyl sodium sulfosuccinate, 1.5 parts of 2% sodium hydroxide solution, 5 parts of a mixture of hexamethylene diamine tetramethy phosphonic acid potassium salt and polyethylene glycol in a mass ratio of 1: 1.)
1. And (3) corrosion resistance test: according to the process, the obtained samples are respectively soaked in HCl with the pH value of 1, NaOH with the pH value of 13.5 for 10 minutes and 10-percent NaCl corrosive medium for 10 days by adopting the medium-temperature hole sealing agents of different embodiments, and the appearance surface color change of the samples is observed.
Evaluation results were as follows: the darker the surface color of the coupon indicates the more severe the coupon is corroded, the color scale is indicated by x, and the more x the surface color is darker.
TABLE 1
2. And (3) evaluating comprehensive performance: the product of example 3 was subjected to the tests as given in the table below, and the results were all in accordance with the standards.
TABLE 2
Claims (2)
1. The medium-temperature hole sealing agent is characterized by comprising the following components in parts by weight: 5 parts of metal salt, 3 parts of organic acid, 2 parts of wetting agent and 1.5 parts of regulator;
the metal salt is nickel sulfate and zirconium acetate according to a mass ratio of 4: 1 compounding the obtained mixture;
the wetting agent is an acrylic acid-acrylate-sulfonate terpolymer and dihydroxy phosphono acetic acid in a mass ratio of 1: 1 compounding the obtained mixture; the acrylic acid-acrylate-sulfonate terpolymer is TH-613;
the organic acid is adipic acid;
the regulator is 2% sodium hydroxide solution.
2. A high-performance hole sealing process for anodic oxidation of aluminum alloy is characterized by at least comprising a medium-temperature hole sealing step and a high-temperature hole sealing step, wherein the medium-temperature hole sealing step is to seal holes by using the medium-temperature hole sealing agent in claim 1; the high-temperature hole sealing step is to seal holes by adopting a high-temperature hole sealing agent, and the high-temperature hole sealing agent comprises sodium silicate, a dispersing agent, a pH regulator and a corrosion inhibitor.
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| CN113279035A (en) * | 2021-05-15 | 2021-08-20 | 江门市优博科技有限公司 | Novel sealing agent for aluminum and aluminum alloy anodic oxide film and preparation method thereof |
| JP2023144470A (en) * | 2022-03-28 | 2023-10-11 | アイシン軽金属株式会社 | Exterior member and manufacturing method thereof |
| CN115029755B (en) * | 2022-07-08 | 2023-05-16 | 重庆理工大学 | Lithium salt grading hole sealing treatment method for aluminum alloy anodic oxide film |
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| US20050155162A1 (en) * | 2002-02-06 | 2005-07-21 | Hans-Thomas Schacht | Process for the coloration of aluminium |
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| JPH03277797A (en) * | 1990-03-27 | 1991-12-09 | Okuno Seiyaku Kogyo Kk | Sealing treatment of aluminum anodically oxidized film |
| JP2005097707A (en) * | 2003-09-26 | 2005-04-14 | Techno Kogyo Kk | Sealing treatment method for aluminum anodized coating |
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