CN111020667B - Method for pre-sealing hole of anodic oxide film and hole sealing agent - Google Patents
Method for pre-sealing hole of anodic oxide film and hole sealing agent Download PDFInfo
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- CN111020667B CN111020667B CN201911414463.1A CN201911414463A CN111020667B CN 111020667 B CN111020667 B CN 111020667B CN 201911414463 A CN201911414463 A CN 201911414463A CN 111020667 B CN111020667 B CN 111020667B
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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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- 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
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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Abstract
The invention discloses a method for pre-sealing holes of an anodic oxide film and a hole sealing agent, which comprises pre-sealing and spraying protection; meanwhile, a sealant scheme for pre-sealing an anodic oxide film of an aluminum alloy workpiece is disclosed, wherein the sealant comprises the following components: nickel salt: 2-10g/l, fluoride: 0.5-10g/l, complexing agent: 0.1-0.5g/l, ash inhibitor: 0.1-0.5g/l, 0.001-0.1g/l of pH regulator, graphene oxide: 0.01-0.1g/l, surfactant: 0.05-2g/l, and the solvent is pure water; and the main components of the protective agent; compared with the prior art, the method is simple, the corrosion resistance and alkali resistance of the anode oxide film of the aluminum alloy workpiece after treatment, continuous acid and alkali resistance and car washing alkali resistance can pass the test, the high-temperature thermal crack resistance is stable, and the antifouling capability is strong.
Description
Technical Field
The invention relates to the field of aluminum alloy anodic oxidation surface treatment, in particular to an alkali-resistant hole sealing process after anodic oxidation of an aluminum alloy automobile exterior trimming part.
Background
Aluminum is the most abundant metal element in the earth crust, and the content is higher than 7%. The density of pure aluminum is small (rho 2.7 g/cm)3) About 1/3 of iron, the melting point is low (660 ℃), and aluminum has a face-centered cubic structure, so that the aluminum has high plasticity (delta is 32-40%, phi is 70-90%), is easy to process, and can be made into various sections and plates. The corrosion resistance is good, but pure aluminum has a low strength and an annealed σ b value of about 8kgf/mm2, and thus it is not suitable as a structural material. The alloy formed by adding certain elements has higher strength while keeping the advantages of light weight of pure aluminum and the like, and the sigma b values can respectively reach 24-60 kgf/mm2. This makes its "specific strength" (strength to specific gravity ratio σ b/ρ) superior to many alloy steels, an ideal structural material.
The aluminum alloy is currently applied to automobiles, such as automobile exterior trimming parts, interior trimming parts, engine covers, automobile doors, wheels, cylinders, cylinder covers, radiators and the like; at present, the workpieces, especially exterior trimming parts, are treated by adopting an anodic oxidation mode commonly, and the workpieces are subjected to common anodic oxidation; however, the sealing or protecting process of the common anodic oxide film cannot meet the increasing performance requirements of people, especially the guarantee of alkali resistance, and meanwhile, the existing process is complex in process, too large in energy consumption or loses metallic feeling.
The Chinese patent CN201610455329.6 hole sealing process has complex steps and large energy consumption, and is difficult to ensure the alkali-resistant stability.
Although the sealing is improved to be a two-step method in China, the alkali resistance is stably improved, but the Chinese invention CN201610455329.6 cannot stably pass the continuous pH (1 + 13.5) acid-base test.
Disclosure of Invention
The invention aims to solve the technical problem of providing an alkali-resistant hole sealing method and a hole sealing agent applied to an anodic oxide film of an aluminum alloy workpiece, completely overcoming the defects of the prior art, changing the idea of multiple water-based sealing in the prior art, combining a pre-sealing process and a spraying process, and adopting conventional equipment, wherein a coating layer can reach a nanometer level, does not influence the appearance of metal, does not influence the texture of the metal, and is completely different from a thick paint film layer. And the alkali-resistant hole sealing or protection treatment of the anodic oxide film is greatly improved. And the process does not contain phosphorus or chromium, meets the environmental protection requirement of liquid medicine discharge, and is environment-friendly.
The invention aims to solve the technical problem of providing an alkali-resistant hole sealing process for an anodic oxide film of an aluminum alloy workpiece, wherein the pre-sealed holes are not traditional cold-sealed holes and traditional medium-temperature hole sealing, and provide a powerful combination guarantee for spraying a protective film in the second step through optimized recombination.
In order to solve the technical problems, the invention provides a sealant for pre-sealing an anodic oxide film, which comprises the following components:
nickel salt: 2-10g/l of the total amount of the active ingredients,
fluoride: 0.5-10g/l,
complexing agent: 0.1 to 0.5g/l,
ash inhibitor: 0.1 to 0.5g/l,
pH regulator: 0.001-0.1g/l,
and (3) graphene oxide: 0.01 to 0.1g/l,
surfactant (b): 0.05-2g/l,
the solvent is pure water.
Preferably, the nickel salt is at least one of nickel fluoride, nickel acetate and nickel sulfate
Preferably, the fluoride is at least one of nickel fluoride, ammonium bifluoride, sodium fluoride and potassium fluoride.
Preferably, the complexing agent is at least one of sodium gluconate, sorbitol, polyethylene glycol and disodium EDTA.
Preferably, the ash inhibitor is at least one of lignosulfonate, methylene dinaphthalene sulfonate, alkyl sulfonate and alkylbenzene sulfonate.
Preferably, the pH regulator is at least one of formic acid, acetic acid, tartaric acid, citric acid, boric acid and alanine.
Preferably, the ash inhibitor is at least one of lignosulfonate, methylene dinaphthalene sulfonate, alkyl sulfonate and alkylbenzene sulfonate.
Preferably, the surfactant is at least one of sodium dodecyl sulfate, alkylphenol ethoxylates, lauric acid diethanolamide and fatty alcohol-polyoxyethylene ether.
The invention also discloses a method for pre-sealing an anodic oxide film by applying the sealant, which comprises the following steps:
s1, anodic oxidation: degreasing an aluminum alloy workpiece, washing, electropolishing, neutralizing and washing, and then treating in a 20% sulfuric acid solution at an oxidation tank temperature: 20 ℃; carrying out anodic oxidation treatment for 600-1440s, and then carrying out water washing to obtain an aluminum alloy workpiece with an anodic oxide film of 6-15 mu;
s2, pre-sealing holes: immersing the aluminum alloy workpiece with the 6-15 mu anodic oxide film into a pre-sealed hole groove, and taking out after 10-25 min;
s3, drying: feeding the aluminum alloy workpiece subjected to the S2 pre-hole sealing into a ventilation drying channel, and drying at the temperature of not more than 100 ℃;
s4, spray protection: and (4) conveying the aluminum alloy workpiece dried in the step (S3) into a spraying channel, and spraying to obtain a finished product, wherein the thickness of the finished product film is not more than 2 mu.
The embodiment of the invention has the following beneficial effects:
compared with the conventional anodic oxide film alkali-resistant hole sealing process, the hole sealing process disclosed by the invention has the advantages that a solution system favorable for anodic oxide film hole sealing is compounded by utilizing nickel ion salts, fluorine ions, a complexing agent, a pH regulator, an ash inhibitor, graphene oxide and surface activity, nickel salt is deposited in anodic oxide film holes of an aluminum alloy workpiece under the weak acid condition, and meanwhile, the nickel salt is gathered and combined on the surfaces of micropores to form a nano-scale net-shaped hole sealing agentThe protective film improves various performances of the surface of the workpiece, such as hydrophobicity, solvent resistance, high temperature resistance, corrosion resistance and the like, and provides favorable conditions for the treatment of the protective agent in the second step; forming 0.5-2 mu nanometer protective layer on the surface of the pre-sealed hole by spraying protective agent (50-100 parts of polysilazane as main component), further permeating into the micropores of the anodic oxide film, tightly combining with the pre-sealed layer, utilizing the special structure of polysilazane (the polysilazane is formed from- (SiR1R2-NR3) N-, wherein R1R2R3 is hydrogen, alkyl, aryl, vinyl or trialkoxysilylalkyl; N is an integer between 0-200; and converting into Si-N-H structure containing SiO atom organic substituent by polymer after spraying and curingxThe protective layer with the structure can show excellent adhesive force, super-strong hydrophobicity, solvent resistance, high temperature resistance, salt mist corrosion resistance, smoother surface and the like below the thickness of 2 microns, and achieves the purposes of strongly protecting workpieces, improving the alkali resistance of the workpieces, and continuously resisting the acid, the alkali and the stain.
Although the special performance of the commercially available polysilazane is applied to the aspect of the protective agent, the arrangement of the hole sealing of the pre-sealing agent guarantees that the sprayed protective agent can achieve super-strong performance; meanwhile, the process can achieve high corrosion resistance which cannot be achieved by the traditional aqueous alkali-resistant hole sealing process, is different from the traditional sprayed ultra-thick coating surface, can achieve high corrosion resistance without complex equipment, does not contain phosphorus and chromium, has no pollution to water, has no health threat to operators, and meets the requirements of environmental protection and green production.
Detailed Description
The invention discloses an alkali-resistant hole sealing process pre-sealing agent for an anodic oxide film of an aluminum alloy automobile exterior trimming part, which comprises the following components:
nickel salt: 2-10g/l of the total amount of the active ingredients,
fluoride: 0.5-10g/l,
complexing agent: 0.1 to 0.5g/l,
ash inhibitor: 0.1 to 0.5g/l,
pH regulator: 0.001-0.1g/l,
and (3) graphene oxide: 0.01 to 0.1g/l,
surfactant (b): 0.05-2g/l,
the solvent is pure water.
Specifically, the nickel salt is at least one of nickel fluoride, nickel acetate and nickel sulfate.
Specifically, the fluoride is at least one of nickel fluoride, ammonium bifluoride, sodium fluoride and potassium fluoride.
Specifically, the complexing agent is at least one of sodium gluconate, sorbitol, polyethylene glycol and EDTA disodium.
Specifically, the ash inhibitor is at least one of lignosulfonate, methylene dinaphthalene sulfonate, alkyl sulfonate and alkylbenzene sulfonate.
Specifically, the pH regulator is at least one of formic acid, acetic acid, tartaric acid, citric acid, boric acid and alanine.
Specifically, the graphene oxide is at least one of single-layer graphene oxide (one layer), few-layer graphene oxide (2-10 layers), and multilayer graphene oxide (10-20 layers).
Specifically, the ash inhibitor is at least one of lignosulfonate, methylene dinaphthalene sulfonate, alkyl sulfonate and alkylbenzene sulfonate.
Specifically, the surfactant is at least one of sodium dodecyl sulfate, alkylphenol ethoxylates, lauric acid diethanolamide and fatty alcohol-polyoxyethylene ether.
The invention also discloses a method for pre-sealing the anodic oxide film by using the sealant, which comprises the following steps:
s1, anodic oxidation: degreasing an aluminum alloy workpiece, washing, electropolishing, neutralizing and washing, and then treating in a 20% sulfuric acid solution at an oxidation tank temperature: carrying out anodic oxidation treatment at 20 ℃ for 600-1440s, and then carrying out water washing to obtain an aluminum alloy workpiece with an anodic oxide film of 6-15 mu;
s2, pre-sealing holes: immersing the aluminum alloy workpiece with the 6-15 mu anodic oxide film into a pre-sealed hole groove, and taking out after 10-25 min;
s3, drying: feeding the aluminum alloy workpiece subjected to the S2 pre-hole sealing into a ventilation drying channel, and drying at the temperature of not more than 100 ℃;
s4, spray protection: and (4) conveying the aluminum alloy workpiece dried in the step (S3) into a spraying channel, and spraying to obtain a finished product, wherein the thickness of the finished product film is not more than 2 mu.
The invention discloses an action mechanism of pre-sealing holes of an aluminum alloy workpiece anodic oxide film alkali-resistant hole sealing process, which comprises the following steps: the method is characterized in that a solution system which is beneficial to pre-sealing of an anodic oxide film is compounded by nickel ion salts, fluorine ions, a combined complexing agent, a pH regulator, an ash inhibitor, graphene oxide and surface activity, nickel salts are deposited in anodic oxide film holes of an aluminum alloy workpiece under a weak acid condition, and meanwhile, a nano-scale net-shaped protective film is assembled and combined on the surface of micropores, so that various properties of the surface of the workpiece are improved, and favorable conditions are provided for the treatment of a second-step protective agent; a 0.5-2 mu nanometer protective layer is formed on the surface of the pre-sealing hole through a sprayed protective agent (50-100 parts of polysilazane as a main component), and further permeates into micropores of an anodic oxide film to be tightly combined with the pre-sealing layer, so that the aims of strongly protecting a workpiece, improving the alkali resistance of the workpiece, and continuously resisting the acid, the alkali and the pollution are fulfilled by utilizing the special structure of the polysilazane; although the special performance of the commercially available polysilazane is applied to the aspect of the protective agent, the arrangement of the hole sealing of the pre-sealing agent guarantees that the spraying protective agent can achieve super-strong performance; meanwhile, the process can achieve high corrosion resistance which cannot be achieved by the sealing of the traditional aqueous alkali-resistant sealing process, is different from the traditional sprayed ultra-thick coating surface, can achieve high corrosion resistance without complex equipment, does not contain phosphorus and chromium, has no pollution to water, has no health threat to operators, and meets the requirement of green-color-protecting production.
The invention also discloses a method for pre-sealing the anodic oxide film by using the sealant, which comprises the following steps:
s1, anodic oxidation: degreasing an aluminum alloy workpiece, washing, electropolishing, neutralizing and washing, and then treating in a 20% sulfuric acid solution at an oxidation tank temperature: carrying out anodic oxidation treatment at 20 ℃ for 600-1440s, and then carrying out water washing to obtain an aluminum alloy workpiece with an anodic oxide film of 6-15 mu;
s2, pre-sealing holes: immersing the aluminum alloy workpiece with the 6-15 mu anodic oxide film into a pre-sealed hole groove, and taking out after 10-25 min;
s3, drying: feeding the aluminum alloy workpiece subjected to the S2 pre-hole sealing into a ventilation drying channel, and drying at the temperature of not more than 100 ℃;
s4, spray protection: and (4) conveying the aluminum alloy workpiece dried in the step (S3) into a spraying channel, and spraying to obtain a finished product, wherein the thickness of the finished product film is not more than 2 mu.
Specifically, before the pre-sealing treatment in step S2, the aluminum alloy workpiece may be subjected to degreasing, water washing, electropolishing, neutralization, water washing, anodic oxidation: (20% sulfuric acid solution, oxidation tank temperature: 20 ℃, oxidation time: 600-;
in step S3, the temperature of the drying tunnel is not higher than 100 ℃, the drying tunnel is preferably ventilated, and the drying time is not longer than half an hour, so as to ensure that the workpiece can be dried by passing through the drying oven.
In step S4, it is disclosed that the main component of the protective agent is commercially available polysilazane in an amount of 50 to 100 parts (relative to the amount of the diluting solvent), and a uniform coating of not more than 2 μ is sprayed on the surface of the aluminum alloy workpiece by using a conventional liquid spraying apparatus and a passage.
The present invention will be further described with reference to specific embodiments so as to clearly understand the technical idea of the present invention.
Example 1
The embodiment discloses a sealant for pre-sealing an anodic oxide film, which comprises the following components:
nickel acetate: 2g/l of the total amount of the active ingredients,
nickel fluoride: 3g/l of the total amount of the active ingredients,
polyethylene glycol: 0.1g/l of the total amount of the components,
sodium lignosulfonate: 0.1g/l of the total amount of the components,
acetic acid: 0.05g/l of the total amount of the components,
graphene oxide (monolayer): 0.01g/l of the total amount of the active ingredients,
sodium lauryl sulfate: 0.05g/l of the total amount of the components,
the solvent is pure water.
Example 2
The embodiment discloses a sealant for pre-sealing an anodic oxide film, which comprises the following components:
nickel acetate: the concentration of the active carbon is 5g/l,
ammonium fluoride: 0.5g/l of the total amount of the components,
sorbitol: 0.1g/l of the total amount of the components,
sodium methylenedinaphthalenesulfonate: 0.15g/l of the total amount of the active ingredients,
acetic acid: 0.01g/l of the total amount of the active ingredients,
graphene oxide (monolayer): 0.03g/l of the total amount of the components,
alkylphenol ethoxylates: 0.1g/l of the total amount of the components,
the solvent is pure water.
Example 3
The embodiment discloses a sealant for pre-sealing an anodic oxide film, which comprises the following components:
nickel fluoride: 4g/l of the total amount of the active ingredients,
sodium fluoride: 0.5g/l of the total amount of the components,
polyethylene glycol: 0.3g/l of the total amount of the components,
sodium methylenedinaphthalenesulfonate: 0.2g/l of the total amount of the components,
acetic acid: 0.02g/l of the total amount of the components,
graphene oxide (monolayer): 0.1g/l of the total amount of the components,
fatty alcohol polyoxyethylene ether: 0.5g/l of the total amount of the components,
the solvent is pure water.
Example 4
The embodiment discloses a sealant for pre-sealing an anodic oxide film, which comprises the following components:
nickel acetate: the concentration of the mixed solution is 10g/l,
potassium fluoride: the concentration of the mixed solution is 10g/l,
disodium EDTA: 0.5g/l of the total amount of the components,
sodium dodecyl sulfate: 0.5g/l of the total amount of the components,
alanine: 0.02g/l of the total amount of the components,
graphene oxide (bilayer): 0.1g/l of the total amount of the components,
lauric acid diethanolamide: 1g/l of the total amount of the active ingredients,
the solvent is pure water.
Example 5
The embodiment discloses a sealant for pre-sealing an anodic oxide film, which comprises the following components:
nickel fluoride: 10g/l
Ammonium fluoride: the concentration of the active carbon is 5g/l,
sodium gluconate: 0.5g/l of the total amount of the components,
sodium lignosulfonate: 0.5g/l of the total amount of the components,
tartaric acid: 0.05g/l of the total amount of the components,
graphene oxide (multilayer): 0.01g/l of the total amount of the active ingredients,
fatty alcohol polyoxyethylene ether: 2.0g/l of the total amount of the active ingredients,
the solvent is pure water.
Comparative example 1
Pre-sealing holes: the composition comprises the following components in parts by mass:
nickel fluoride: 5g/l
Sodium fluoride: 1g/l
Sodium fluosilicate: 0.05g/l
Cobalt acetate: 0.05g/l
Sodium lauryl sulfate: 1.0g/l
The solvent is pure water.
Comparative example 2
The composition comprises the following components in parts by mass:
nickel acetate: 4g/l
Sodium acetate: 0.5 g/is
Acetic acid: 0.02g/l
Sodium lauryl sulfate: 0.02g/l
The solvent is pure water.
Comparative example 3
The composition comprises the following components in parts by mass:
nickel fluoride: 2.5g/l
Sodium fluoride: 0.5g/l
Sodium fluosilicate: 0.025g/l
Cobalt acetate: 0.025g/l
Nickel acetate: 2g/l
Sodium acetate: 0.25g/l
Acetic acid: 0.01g/l
Sodium lauryl sulfate: 0.01g/l
The solvent is pure water.
2. The aluminum alloy automobile exterior trimming part is made of an anodic oxidation film
Degreasing, washing, electrolytic polishing, neutralizing, washing and anodizing the aluminum alloy automobile exterior trimming part: (20% sulfuric acid solution, oxidation tank temperature: 20 ℃, voltage: 13V, oxidation time: 900 s) water washing treatment; ensuring the film thickness to be 6-15 μm.
3. Hole sealing treatment process for anodic oxide film of aluminum alloy automobile exterior trimming part
(1) Pre-sealing holes:
example 1: immersing the anodized aluminum alloy automobile exterior workpiece into the aluminum alloy automobile exterior workpiece in the sealing temperature of example 1: taking out the workpiece after 20min at 70 ℃, washing the workpiece twice by pure water, entering a ventilation flue, and drying until the temperature does not exceed 100 ℃.
Example 2: immersing the anodized aluminum alloy automobile exterior workpiece into the aluminum alloy of example 2, wherein the hole sealing temperature is as follows: taking out the workpiece after 20min at 60 ℃, washing the workpiece twice by pure water, entering a ventilation flue, and drying until the temperature does not exceed 100 ℃.
Example 3: immersing the anodized aluminum alloy automobile exterior workpiece into the aluminum alloy of example 3, wherein the hole sealing temperature is as follows: taking out the workpiece after 20min at 80 ℃, washing the workpiece twice by pure water, entering a ventilation flue, and drying until the temperature does not exceed 100 ℃.
Example 4: immersing the anodized aluminum alloy automobile exterior workpiece into the aluminum alloy of example 4, wherein the hole sealing temperature is as follows: taking out the workpiece after 20min at 55 ℃, washing the workpiece twice by pure water, entering a ventilation flue, and drying until the temperature does not exceed 100 ℃.
Example 5: the anodized aluminum alloy automotive exterior part was immersed in example 5 at a hole sealing temperature: taking out the workpiece after 20min at 50 ℃, washing the workpiece twice by pure water, entering a ventilation flue, and drying until the temperature does not exceed 100 ℃.
Comparative example 1: immersing the anodized aluminum alloy automobile exterior trimming workpiece into the comparative example 1, wherein the hole sealing temperature is as follows: taking out the workpiece after 20min at 35 ℃, washing the workpiece twice by pure water, taking out the workpiece, entering an air duct, and drying until the temperature does not exceed 100 ℃.
Comparative example 2: immersing the anodized aluminum alloy automobile exterior trimming workpiece into the comparative example 2, wherein the hole sealing temperature is as follows: taking out the workpiece after 20min at 90 ℃, washing the workpiece twice by pure water, taking out the workpiece, entering an air duct, and drying until the temperature does not exceed 100 ℃.
Comparative example 3: immersing the anodized aluminum alloy automobile exterior trimming workpiece into the comparative example 3, wherein the hole sealing temperature is as follows: and (3) taking out the workpiece after 20min at the temperature of 85 ℃, washing the workpiece twice by using pure water, taking out the workpiece, introducing the workpiece into a ventilation flue, and drying until the temperature does not exceed 100 ℃.
(2) Spraying:
the main component is the commercial polysilazane, the content is 50-100 parts, and the surface of the aluminum alloy workpiece is sprayed with a uniform coating layer of less than 2 mu by using the traditional liquid spraying equipment and a channel. (the product can be completely dried after being placed at normal temperature for 5-10 min or enter a drying channel at the temperature of 150-
(3) Reference technology
And (3) high-temperature hole sealing: chinese patent is referred to and reproduced: example 7, in which the performance test results are the best in case of CN201610455330.9, (sealing agent a: sealing agent B ═ 40:80), where sealing agent a: aqueous silicate (50-200g/l)
The sealant B comprises the following components:
sodium hexafluorosilicate: 200g/l
Citric acid: 5g/l
Disodium hydrogen phosphate: 5/l
r-aminopropyltriethoxysilane: 0.1g/l
Coconut oil ammonium polyoxyethylene ether: 0.1g/l
Ethanol 0.1g/l
4. Performance testing
(1) Stain testing
According to GB/T8753.4-2005: evaluation method of hole sealing quality of anodic oxide films of aluminum and aluminum alloys part 4: stain spots after acid treatment
Wherein: acid solution A: 25ml sulfuric acid (. rho.1.84 g/ml) was removed, 10g potassium fluoride was weighed into a 1000ml volumetric flask and diluted to the mark by slow addition of water.
Acid solution B: 25ml of fluosilicic acid (rho 1.29g/ml) is transferred into a 1000ml volumetric flask and is slowly diluted to the scale mark by adding water.
Dyeing solution A: 5g of aluminum blue (2LW) was transferred into a 1000ml volumetric flask and the pH of the solution was adjusted to 5.0. + -. 0.5 (about 23 ℃ C.) with dilute sulfuric acid or dilute sodium hydroxide solution and slowly diluted with water to the desired volume.
(2) Alkali resistance test (13.0/13.5)
The preparation method of the alkaline test solution with pH value of 13.0 comprises the following steps:
sodium hydroxide: 4g/l
Sodium phosphate: 4.64g/l
Sodium chloride: 0.33g/l
Method for alkaline test solutions with pH 13.5:
sodium hydroxide: 12.7g/l
Sodium phosphate: 4.64g/l
Sodium chloride: 0.33 g/is
The test method comprises the following steps: soaking the workpiece in a solution with the pH value of 13.0 or 13.5 of an alkaline test solution, washing the workpiece at 25 ℃ after 10min, observing the workpiece surface without any changes such as extinction, discoloration and corrosion, if no change exists, marking that the test is passed, otherwise, not passing the test.
(3) Continuous acid and alkali resistance test (pH1+ pH13.5)
The preparation method of the acidic test solution with pH value of 1 comprises the following steps:
HCL: 0.1ml/l (commercially available HCL: 36.5% AR grade, 10ml/l required)
The test method comprises the following steps: soaking the workpiece in a solution with pH of 1.0 of an acidic test solution at 25 deg.C for 10min, and washing; placing the workpiece into an oven preheated to 40 +/-2 ℃, ventilating and baking for 30min, then soaking the workpiece into a solution with an alkaline test solution of which the pH is 13.0 or 13.5, washing the workpiece cleanly after 10min at the temperature of 25 ℃, and observing whether the surface of the workpiece has any changes such as extinction, color change, corrosion and the like, if the surface has no changes, indicating that the test is passed, otherwise, indicating that the test is not passed.
(4) Alkali resistance test after car washing (pH13.5)
And rubbing the surface of the workpiece back and forth 100 times by using a grinding tester with the force of 1KG, soaking the workpiece in a solution with the pH value of 13.5 in an alkaline test solution at the temperature of 25 ℃, washing the workpiece completely after 10min, observing the surface of the workpiece without any changes such as extinction, color change, corrosion and the like, and marking that the test is passed if no change exists, otherwise, not passing the test.
(5) Copper accelerated acetate salt spray test (CASS)
According to GB/T12967.3-2008, the aluminum and aluminum alloy anode oxygen film detection method part 3: standard execution of copper accelerated acetate spray test (CASS)
(6) Neutral salt spray test (NSS)
The method is carried out according to the standard of GB/T10125-2012, Artificial atmosphere Corrosion test (salt fog test).
(7) High temperature cracking resistance test
The test method comprises the following steps: soaking the workpiece in an acetone solvent for 30s, taking out, air-drying, putting into an oven with a preheating temperature of 110 ℃, keeping the temperature constant for 1H, taking out, observing whether cracks exist, marking that the test is passed if no change exists, and otherwise, not passing the test.
The results of the tests for each of the embodiments are shown in the following table, wherein (PASS means test passed; NG means test failed)
From the above results of the performance tests, the components and contents of the examples 1-5 of the present invention are within the range required by the first-step pre-sealing agent disclosed in the present invention, and after the aluminum alloy automobile exterior trimming parts are treated, we have individually tested the relevant performances: in the stain spot test, example 3, example 5, rated spots appeared on a 1-grade scale, but still within a 2-grade scale; the single alkali resistance of 13.0 can pass through, but the single alkali resistance of 13.5 cannot pass through continuous acid and alkali resistance (pH1+ pH13.5), and the alkali resistance of car washing (pH13.5) cannot pass through the continuous acid and alkali resistance; the three items are not the same as those of comparative examples 1-3 (+ high temperature sealing), (the technology of example 7 with the best performance test result in Chinese patent CN201610455330.9 case is adopted, and the technology is combined and applied), and the patent technologies of comparative examples 1-3 really realize the improvement of performances in the aspects of single alkali resistance (pH13.0/pH13.5), continuous acid and alkali resistance (pH1+ pH13.5) and car washing alkali resistance (13.5); of course, the car washing alkali resistance (13.5) is not passed, but the corrosion strength can be seen to be weaker than the test corrosion strength of only the pre-sealing hole examples 1-5, the car washing alkali resistance (13.0) of the patent technology is passed, and the test is repeated; but examples 1-5, after pretreatment, excellent performance was achieved by spraying our preferred polysilazane coating (material not documented for use in aluminum alloy automotive exterior trim) to a thickness of only 2 μ: the single alkali resistance (pH13.0/pH13.5), the continuous acid and alkali resistance (pH1+ pH13.5) and the car washing alkali resistance (pH13.5) can stably pass the test, and the passing rate reaches 100%;
in the aspect of the weather resistance test of the workpiece, a neutral salt spray test (NSS), a copper salt acidity accelerated salt spray test (CASS), and pre-sealing hole examples 1 to 5 cannot pass industry default set values: the NSS test (480H), the CASS test (12H), and comparative examples 1 to 3(+ high temperature blocking), all showed excellent performance: even in comparative example 2, the basic hole sealing scheme is adopted, but the high-temperature hole sealing by the patent technology also shows better corrosion resistance; however, after the pre-sealing examples 1 to 5 and the second spraying step, the aluminum alloy exterior trimming parts of the automobile still have no any foreign body and have excellent performance after the NSS test (1000H) and the CASS test (96H) far exceeding the set values of the industry standard.
And comparative examples 1-3 (+ spraying) also failed the car wash alkali resistance (ph13.5) test; although the normal-temperature hole sealing of the conventional nickel fluoride system which belongs to the foundation in the proportion 1 is also protected by spraying a new material in the second step, the continuous acid-base test (pH1+ pH13.5) can not be passed even when the film thickness is about 2 mu, and the corrosion resistance is excellent even when the film thickness exceeds 10 mu, so that the deep explanation is not made, and the hand feeling and the texture are lost in the aspect of aluminum alloy automobile exterior trimming parts because the thick-film workpiece is not deeply explained; and the comparative example 3 belongs to the fusion of the traditional basic nickel fluoride and nickel acetate system, the quality of the pre-sealing hole is greatly improved, and the pre-sealing hole can not pass the aspect of high-temperature film cracking at 110 ℃ after the new material spraying in the second step is combined.
Comparative examples 1 to 3(+ high temperature sealing) are techniques for reference fusion, and are also common hole sealing techniques in the aspect of anodic oxidation post-treatment processes of aluminum alloy automobile exterior parts by host plants and supporting manufacturers at the present international stage, and it can be known from experimental comparison results that the comparative examples 1 to 3 are matched with the patent technical example 7, all performances are still wrong, but the alkali resistance (13.5) for car washing cannot pass through; the prior standard of alkali resistance (13.0) for washing vehicles is changed into alkali resistance (PH13.5) for washing vehicles in most of the current host factories of the vehicle enterprises.
In conclusion, the pre-hole sealing technology and the spraying of the optimized new material ultra-thin film layer form an alkali-resistant hole sealing process technology for the anode film of the automobile exterior trimming part; the technology is simple, the equipment cost is low, but the technology is far beyond the automobile accessory industry standard, and a new direction is provided for improving the performance, especially the alkali resistance, of high-performance aluminum alloy automobile exterior trimming parts.
The above description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes that can be made by the present invention as described in the specification or directly or indirectly applied to other related technical fields are also included in the scope of the present invention.
Claims (7)
1. A method for pre-sealing an anodic oxide film is characterized by comprising the following steps: the method comprises the following steps:
s1, anodic oxidation: degreasing an aluminum alloy workpiece, washing, electropolishing, neutralizing and washing, and then treating in a 20% sulfuric acid solution at an oxidation tank temperature: carrying out anodic oxidation treatment at 20 ℃ for 600-1440s, and then carrying out water washing to obtain an aluminum alloy workpiece with an anodic oxide film of 6-15 mu;
s2, pre-sealing holes: immersing the aluminum alloy workpiece with the 6-15 mu anodic oxide film into a pre-sealing hole groove, taking out after 10-25min, wherein the sealing agent comprises the following components:
nickel salt: 2-10g/l of the total amount of the active ingredients,
fluoride: 0.5-10g/l,
complexing agent: 0.1 to 0.5g/l,
ash inhibitor: 0.1 to 0.5g/l,
pH regulator: 0.001-0.1g/l,
and (3) graphene oxide: 0.01 to 0.1g/l,
surfactant (b): 0.05-2g/l,
the solvent is pure water;
s3, drying: feeding the aluminum alloy workpiece subjected to the S2 pre-hole sealing into a ventilation drying channel, and drying at the temperature of not more than 100 ℃;
s4, spray protection: and (4) conveying the dried aluminum alloy workpiece of S3 into a spraying channel, and spraying to obtain a finished product, wherein the thickness of the finished product film is not more than 2 mu.
2. The method for pre-sealing an anodic oxide film according to claim 1, wherein the nickel salt is at least one of nickel fluoride, nickel acetate and nickel sulfate.
3. The method for pre-sealing the anodic oxide film according to claim 1, wherein the fluoride is at least one of nickel fluoride, ammonium bifluoride, sodium fluoride and potassium fluoride.
4. The method for pre-sealing an anodic oxide film according to claim 1, wherein the complexing agent is at least one of sodium gluconate, sorbitol, polyethylene glycol and disodium EDTA.
5. The method for pre-sealing an anodic oxide film according to claim 1, wherein the ash inhibitor is at least one of lignosulfonate, methylenedinaphthalene sulfonate, alkyl sulfonate and alkylbenzene sulfonate.
6. The method for pre-sealing an anodic oxide film according to claim 1, wherein the pH regulator is at least one of formic acid, acetic acid, tartaric acid, citric acid, boric acid and alanine.
7. The method for pre-sealing an anodic oxide film according to claim 1, wherein: the surfactant is at least one of sodium dodecyl sulfate, alkylphenol ethoxylates, lauric acid diethanolamide and fatty alcohol-polyoxyethylene ether.
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