CN110777415B - Preparation method of high-temperature-resistant corrosion-resistant anodic oxide film - Google Patents
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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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- 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
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
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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
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Abstract
The invention relates to a preparation method of a high-temperature-resistant corrosion-resistant anodic oxide film, which comprises the following steps: preparing oxidation bath solution, placing a workpiece in the bath solution for anodic oxidation treatment to form an anodic oxidation film, wherein the concentration of sulfuric acid in the oxidation bath solution is 40-100g/L, the concentration of an additive is 2-10g/L, and the additive comprises the following components: 5-15% of soluble rare earth metal salt, 2-10% of organic acid, 0.5-1% of organic acid salt, 0.5-2% of lower alcohol and the balance of water; and sealing the hole of the anodic oxide film to obtain the finished product. The beneficial effects are that: the bottleneck that the high temperature resistance of the oxide film is improved through the hole sealing process in the prior art is broken through, the high temperature resistance of the oxide film is improved through the adjustment of the pore structure of the oxide film by changing the components of the oxidation bath solution, the problem of high-temperature cracking of the oxide film is solved, and the anode oxide film with excellent performances in all aspects and high temperature resistance and corrosion resistance can be obtained by combining with a proper hole sealing process.
Description
Technical Field
The invention belongs to the technical field of surface oxidation treatment of aluminum and aluminum alloy workpieces in the automobile industry, and particularly relates to a preparation method of a high-temperature-resistant corrosion-resistant anodic oxide film.
Background
The aluminum alloy anodic oxide film is widely applied to the living fields of aerospace, automobiles, electronic and electric appliances, building materials and the like. The new technical problems faced in the application are also followed. In the field of automobiles, the requirements of current host plants are generally 240h of salt spray, 240h of moisture resistance, 13.0 h of alkali resistance, 12h of CASS and 90 ℃ or 100 ℃ of high temperature resistance. Aiming at different requirements, various oxidation methods and various systems of hole sealing agents appear on the market so as to realize different performance requirements. The existing hole sealing agent system comprises a nickel salt system, a silicate system, a nickel-free and silicate-free system and the like. The nickel salt sealing can be subdivided into different categories such as a nickel fluoride system, a nickel acetate system, a nickel sulfate system and the like, and the three have very good effects on the moisture resistance of salt mist, but have a larger problem. The oxide film without sealing holes has high temperature resistance up to 200 ℃ and no cracks, but the oxide film is easy to stick to hands on one hand, and the oxide film has poor alkali resistance and corrosion resistance on all aspects and can not meet the performance requirements of various fields such as main locomotives, 3C and the like. However, once the hole is sealed, no matter what kind of hole is sealed, even after the hole is sealed by hot water or steam, the high temperature resistance of the oxide film is obviously reduced. The nickel sealing hole has the greatest influence on the high-temperature resistance of the oxide film, the high-temperature resistance of the oxide film is sharply reduced after the nickel salt sealing hole is used, most of 5-series and 6-series aluminum materials cannot pass the high-temperature resistance test requirement of the oxide film at 90 ℃ or even 100 ℃, and the oxide film is seriously cracked. And the longer the aging time is, the more serious the oxide film cracks; although the nickel-free system sealing hole has little influence on the high temperature resistance of the oxide film, the hole has no crack at 100 ℃. However, the sealing of a single fluorozirconate system or other sealing of other nickel-free systems does not have excellent alkali resistance and corrosion resistance, and the problems of semi-sealing, poor sealing and the like are easy to occur. After nickel salt sealing or nickel-free sealing (including sealing of a fluozirconate system), silicate sealing is bound to be matched as a subsequent process for improving performances of alkali resistance, weather resistance and the like, high-temperature resistance of an oxide film is also sharply reduced after matching with sealing of the silicate, and cracks are obvious after baking at 90 ℃ or even 100 ℃. Although the existing three sealing processes of cold sealing, middle sealing and heat sealing (other patents filed by the applicant) in the market have excellent performances in salt spray, moisture resistance, CASS and the like, the high-temperature resistance stability of different materials is limited, and the high-temperature film cracking of the oxidation film of partial 1-series, 5-series and 6-series aluminum materials still exists. Therefore, the problem of high-temperature cracking of the oxide film cannot be well solved through the hole sealing process, and the requirement in actual production cannot be met. The nickel-free system sealing hole can not provide good alkali resistance and weather resistance. How to balance the problems of high temperature resistance, strong alkali resistance, corrosion resistance and the like, meets the requirements of various aspects, and is a problem which needs to be solved urgently.
Disclosure of Invention
Aiming at the problem of high-temperature cracking of an oxide film in the prior art, the invention provides a preparation method of a high-temperature-resistant corrosion-resistant anodic oxide film, aiming at ensuring that the anodic oxide film has high temperature resistance and corrosion resistance under the conditions of better neutral salt spray capacity, copper-accelerated acetate spray capacity, condensed water capacity, stain-staining capacity, acid-resistant solution capacity and alkali-resistant solution capacity by combining a unique oxidation process and a hole sealing process.
The technical scheme for solving the technical problems is as follows: a preparation method of a high temperature-resistant corrosion-resistant anodic oxide film comprises the following steps:
(1) preparing oxidation tank liquid, and placing an aluminum or aluminum alloy workpiece in the oxidation tank liquid for anodic oxidation treatment to form an anodic oxidation film, wherein the concentration of sulfuric acid in the oxidation tank liquid is 40-100g/L, the concentration of an additive is 2-10g/L, and the additive comprises the following raw materials in percentage by mass: 5-15% of soluble rare earth metal salt, 2-10% of organic acid, 0.5-1% of organic acid salt, 0.5-2% of lower alcohol and the balance of water;
(2) and sealing the hole of the anodic oxide film to obtain the high-temperature-resistant corrosion-resistant anodic oxide film.
On the basis of the above technical solutions, the present invention may further have the following further specific or preferred options.
Specifically, the soluble rare earth metal salt is one or more of soluble sulfate, nitrate and acetate corresponding to rare earth metal cations of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium and yttrium.
Preferably, the soluble rare earth metal salt comprises two rare earth metal salts with different cations, and the mass ratio of the two rare earth metal salts is 1: 1-3.
Preferably, the mass ratio of the sulfuric acid to the organic acid is 100-500: 1.
Specifically, the organic acid is one or more of oxalic acid, adipic acid, sulfamic acid, glycine, lactic acid, malic acid, tartaric acid and glycolic acid.
Preferably, the organic acid salt is sodium gluconate and/or sodium oxalate.
Preferably, the lower alcohol is glycerol and/or ethylene glycol.
Preferably, the conditions of the anodic oxidation treatment in step (1) are: the temperature is 17-22 ℃, the voltage is 20-30V, and the current density is 0.5-6A/dm2Oxidizing for 30-50min, and washing with water after oxidation.
Specifically, the hole sealing treatment in the step (2) comprises the following specific steps: placing the aluminum or aluminum alloy workpiece with the surface formed with the anodic oxide film in a 30-60g/L sealant photo seal 170, treating for 10-40min at 15-35 ℃, and then washing with water; and (3) placing the aluminum material subjected to the primary hole sealing treatment in a phoenix seal290A or a phoenix seal 290E, treating at 70-98 ℃ for 15-40min, washing with water, taking out and drying by blowing.
Compared with the prior art, the invention has the beneficial effects that:
the bottleneck that the high-temperature resistance of the oxide film is improved through the hole sealing process in the prior art is broken through, the hole sealing process cannot fundamentally solve the problem of high-temperature cracking of the oxide film, can only properly relieve the problem, and cannot be generally used for all series of aluminum or aluminum alloy materials. The high-temperature resistance of the oxide film is improved by adjusting the pore structure of the oxide film, so that the problem of high-temperature cracking of the oxide film can be fundamentally solved; the invention creatively carries out anodic oxidation treatment on an aluminum or aluminum alloy workpiece in an oxidation tank liquid containing sulfuric acid and rare earth metal salt with specific concentration, the rare earth metal salt effectively fills the microporous structure of the oxide film in the oxide film generation process, the filling of the oxide film structure by the rare earth metal salt is helpful for improving the high-temperature cracking resistance of the oxide film (when the soluble rare earth metal salt in the additive is used by soluble salts of two different rare earth metal cations according to a specific mass ratio, the additive has great enhancement effects on CASS, NSS, heat resistance and moisture resistance, and simultaneously the enhancement of organic acid salt in the additive to the performances is also very obvious), the anodic oxide film is effectively improved in acid resistance, alkali resistance, continuous acid resistance, alkali resistance, moisture resistance and the like by combining a proper hole sealing process after the oxidation treatment, particularly when the ultra-low nickel content cold seal and the silicate heat seal are used in a matching way, can achieve better effect of high moisture resistance and corrosion resistance, and simultaneously meet various standards of the automobile industry.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.
For the sake of brevity, the drugs used in the following examples or comparative examples are commercially available products unless otherwise specified, and the methods used are conventional methods used by those skilled in the art unless otherwise specified.
Wherein, the phoenix Ecoseal 6, the phoenix seal147, the phoenix seal180, the phoenix seal181, the phoenix seal 184, the phoenix seal290A and the phoenix seal 290E are all products of Wuhan Sai sail electrochemical technology GmbH/Wuhan Feneck chemical GmbH, and are all products on sale.
Each of the following examples corresponds to a method for preparing a high temperature-resistant corrosion-resistant anodic oxide film, which comprises the following steps:
(1) preparing oxidation tank liquid, and placing the aluminum or aluminum alloy workpiece subjected to conventional degreasing, electro-polishing, membrane removal and ash removal treatment in the oxidation tank liquid for anodic oxidation treatment to form an anodic oxidation membrane, wherein the concentration of sulfuric acid in the oxidation tank liquid is 40-100g/L, and the concentration of an additive is 2-10 g/L;
(2) and sealing the hole of the anodic oxide film to obtain the high-temperature-resistant corrosion-resistant anodic oxide film.
Wherein, the conditions of the anodic oxidation treatment are as follows: the stainless steel plate is used as a cathode, the temperature is 17-22 ℃, the voltage is 20-30V, and the current density is 0.5-6A/dm2The oxidation duration is 30-50 min; the hole sealing treatment comprises the following specific steps: placing an aluminum or aluminum alloy workpiece with an anodic oxide film formed on the surface in a 30-60g/L sealant phoenix seal 170 (the content of nickel in the sealant is only 1/8-1/10 of conventional nickel salt sealing), treating for 10-40min at 15-35 ℃, and then washing with water; and (3) placing the aluminum material subjected to the primary hole sealing treatment in a phoenix seal290A or a phoenix seal 290E, treating at 70-98 ℃ for 15-40min, washing with water, taking out and drying by blowing to obtain the aluminum material.
The specific concentrations of sulfuric acid and additives in the oxidation bath solution of each example, and the specific compositions of the additives were as follows:
example 1
40g/L of sulfuric acid and 5g/L of additive, wherein the additive comprises the following components in percentage by mass: 6% of lanthanum sulfate, 5% of oxalic acid, 0.2% of sodium gluconate, 0.4% of sodium oxalate and 1% of glycerol.
Example 2
40g/L of sulfuric acid and 5g/L of additive, wherein the additive comprises the following components in percentage by mass: 7 percent of samarium sulfate, 2 percent of adipic acid, 0.6 percent of sodium gluconate and 0.6 percent of glycol.
Example 3
60g/L of sulfuric acid and 2g/L of additive, wherein the additive comprises the following components in percentage by mass: 5% of neodymium sulfate, 7% of sulfamic acid, 0.8% of sodium oxalate, 0.2% of glycerol and 1.2% of ethylene glycol.
Example 4
60g/L of sulfuric acid and 10g/L of additive, wherein the additive comprises the following components in percentage by mass: 10% of ytterbium sulfate, 10% of tartaric acid, 0.7% of sodium oxalate and 0.6% of glycerol.
Example 5
80g/L of sulfuric acid and 5g/L of additive, wherein the additive comprises the following components in percentage by mass: 12% of praseodymium sulfate, 3% of glycolic acid, 0.8% of sodium gluconate and 1.3% of glycerol.
Example 6
80g/L of sulfuric acid and 10g/L of additive, wherein the additive comprises the following components in percentage by mass: 15% of gadolinium sulfate, 8% of glycine, 0.5% of sodium oxalate and 1.5% of ethylene glycol.
Example 7
100g/L of sulfuric acid and 10g/L of additive, wherein the additive comprises the following components in percentage by mass: 5% of neodymium sulfate, 4% of praseodymium sulfate, 1% of oxalic acid, 6% of adipic acid, 0.9% of sodium oxalate and 1.1% of glycerol.
Example 8
100g/L of sulfuric acid and 5g/L of additive, wherein the additive comprises the following components in percentage by mass: ytterbium sulfate 3%, lanthanum cerium sulfate 4%, sulfamic acid 2%, aminoacetic acid 3%, sodium gluconate 0.9%, ethylene glycol 0.5%.
Example 9
100g/L of sulfuric acid and 2g/L of additive, wherein the additive comprises the following components in percentage by mass: samarium sulfate 4%, gadolinium sulfate 8%, tartaric acid 4%, glycolic acid 5%, and sodium gluconate 1.0%.
Example 10
100g/L of sulfuric acid and 10g/L of additive, wherein the additive comprises the following components in percentage by mass: 2% of neodymium sulfate, 5% of samarium sulfate, 5% of oxalic acid, 4% of aminoacetic acid, 1% of glycolic acid, 0.3% of sodium gluconate, 0.3% of sodium oxalate, 0.3% of glycerol and 0.4% of ethylene glycol.
Comparative example 1
Ordinary oxidation + nickel-containing cold sealing: the common oxidation process treatment uses H with the concentration of 160-200g/L2SO4Using lead plate as cathode and aluminum material as anode, oxidizing for 20-40min with current density of 0.5-2A/dm2Washing after oxidation; placing the aluminum material after oxidation treatment in 4.5-5.5g/L cold sealing agents photo six seal180 and photo six seal147, treating for 10-40min at 15-35 ℃, and then washing with water.
Comparative example 2
Ordinary oxidation + conventional nickel containing cold seal + silicate heat seal: the common oxidation process treatment uses H with the concentration of 160-200g/L2SO4Using lead plate as cathode and aluminum material as anode, oxidizing for 20-40min with current density of 0.5-2A/dm2Washing after oxidation; placing the aluminum material after oxidation treatment in 4.5-5.5g/L cold sealing agents photo six seal180 and photo six seal147, treating for 10-40min at 15-35 ℃, and then washing with water; and (3) placing the aluminum material subjected to the primary hole sealing treatment in 290A/290E, treating at 70-98 ℃ for 15-40min, and washing with water.
Comparative example 3
Ordinary oxidation + nickel-free and silicate-free hole sealing: the common oxidation process treatment uses H with the concentration of 160-200g/L2SO4Using lead plate as cathode and aluminum material as anode, oxidizing for 20-40min with current density of 0.5-2A/dm2Washing after oxidation; and (3) placing the oxidized aluminum material in 20-50g/L sealant phoenix Ecoseal 6, treating for 10-40min at 15-35 ℃, and washing with water.
Comparative example 4
Ordinary oxidation + nickel-free and silicate-free sealing + silicate sealing: the common oxidation process treatment uses H with the concentration of 160-200g/L2SO4Using lead plate as cathode and aluminum material as anode, oxidizing for 20-40min with current density of 0.5-2A/dm2Washing after oxidation; placing the oxidized aluminum material in 20-50g/L sealant phoenix Ecoseal 6, treating for 10-40min at 15-35 ℃, and washing with water; and (3) placing the aluminum material subjected to the primary hole sealing treatment in 290A/290E, treating at 70-98 ℃ for 15-40min, and washing with water.
Comparative example 5
Ordinary oxidation + nickel-containing cold sealing + nickel-free and silicate-free sealing + silicate heat sealing: the common oxidation process treatment uses H with the concentration of 160-200g/L2SO4Using lead plate as cathode and aluminum material as anode, oxidizing for 20-40min with current density of 0.5-2A/dm2Washing after oxidation; placing the aluminum material after oxidation treatment in 4.5-5.5g/L cold sealing agent photo enix seal180, photo enix seal147, photo enix seal181 or photo enix seal 182, treating for 10-40min at 15-35 ℃, and then washing with water; placing the washed aluminum material subjected to the primary hole sealing treatment in 20-50g/L hole sealing agent phoenix Ecoseal 6, treating for 10-40min at 15-35 ℃, and then washing; and (3) placing the aluminum material subjected to the two hole sealing treatments in a phoenix seal 290A/290E, treating at 70-98 ℃ for 15-40min, and washing with water.
Comparative example 6
The same procedure as in example 1 was repeated except that the sulfuric acid concentration in the oxidation bath was 25 g/L.
Comparative example 7
The same procedure as in example 7 was repeated, except that the sulfuric acid concentration in the oxidation bath was 120 g/L.
Comparative example 8
The same procedure as in example 1 was followed, except that lanthanum sulfate was not contained in the additive.
Comparative example 9
The procedure of example 1 was followed except that the additive contained no sodium gluconate or sodium oxalate.
Comparative example 10
The procedure of example 7 was followed except that the additive contained no sodium oxalate.
Comparative example 11
The same procedure as in example 7 was repeated, except that the additive contained neodymium sulfate in an amount of 5% by mass and praseodymium sulfate in an amount of 1% by mass.
Performance testing
The performance test was performed on the anodized films formed on the surfaces of the aluminum or aluminum alloy workpieces obtained in the above examples and comparative examples:
(1) acid resistance test
Preparing an acid solution (HCl:0.1mol/L) with the pH value of 1, soaking a workpiece in the acid solution for 10min, taking out the workpiece, washing the workpiece with running water, drying the workpiece by blowing, observing whether the surface appearance of the workpiece has obvious change, and if the surface appearance of the workpiece has no obvious change, testing the acid-resistant pH value of the workpiece to be 1.0 to pass, otherwise, testing the workpiece to not pass.
(2) Alkali resistance test
Preparing an alkaline solution with the pH value of 13.5(NaOH:12.7g/L, sodium phosphate: 2g/L and NaCl: 0.33g/L), soaking the workpiece in the alkaline solution for 10min, taking out, washing with running water, drying, observing whether the surface appearance of the workpiece has obvious change or not, if not, testing that the alkali-resistant pH value of the workpiece is 13.5 or not, and otherwise, testing that the workpiece does not pass.
(3) Continuous acid and alkali resistance test
The workpiece is soaked in an acid solution with the pH value of 1(HCl:0.1mol/L) for 10min, washed clean, then soaked in a solution with the pH value of 13.5(NaOH:12.7g/L, sodium phosphate: 2g/L, NaCl: 0.33g/L) for 10min, and washed clean, and then the surface is observed to have no change.
(4) 13.5 performance test for car washing
The test adopts a test for simulating the car washing process in the automobile industry: rubbing the surface of the workpiece back and forth by using fiber cloth with the force of 1kg for 100 times, then soaking the workpiece in the following alkaline 13.5 solution for 10min, taking out the workpiece, and observing whether the surface of the workpiece has change after the workpiece is washed clean, wherein the change is represented by passing a car washing 13.5 test.
pH13.5 alkaline solution preparation: 4g/L of NaOH, sodium phosphate: 4.64g/L, NaCl: 0.33g/L to 1000mL volumetric flask and diluted with water to the mark.
(5) Copper accelerated acetate salt spray test (CASS)
The method implements the national standard: GB/T12967.3-2008: a method for detecting anodic oxide films of aluminum and aluminum alloys in section 3 includes a copper accelerated acetic acid salt spray test (CASS test).
The method is carried out by adopting a special CASS salt spray box, atomizing an acidic solution with the pH value of 3.05 +/-0.05 by using compressed air under the condition of the temperature of 50 DEG C2, and continuously spraying. The acid mist is deposited on the surface of the sample, so that the sample generates certain change. The preparation method of the acid solution comprises the following steps: preparing 50 +/-5 g/L sodium chloride solution, adding (0.26 +/-0.02) g/L copper chloride, and adding a proper amount of glacial acetic acid to adjust the pH value to be about 3.05 +/-0.05.
(6) Neutral salt spray test (NSS)
The detection method comprises the following steps: GB/T10125-: artificial atmosphere corrosion test (salt spray test).
Specifically, the method comprises the following steps: the method is carried out in a special salt fog box, a neutral sodium chloride solution (the concentration of which is 50g/L and 5g/L) is atomized by compressed air under the condition of (35 DEG 2) DEG C, and then the neutral sodium chloride solution is settled on the surface of a sample.
(7) Thermal cracking resistance test
The workpiece is firstly put into an acetone solvent for 30s, oil stain is washed off, the workpiece is air-dried, then the workpiece is vertically put into a preheated oven at 70-110 ℃, test points are arranged at every 10 ℃ from 70 ℃, the temperature of each test point is kept constant for 1h, then the workpiece is taken out, whether cracks are visible on the surface is observed, if not, the passing of the thermal cracking resistance of the test point is indicated, if so, the failing of the thermal cracking resistance of the test point is indicated, and the thermal cracking resistance is indicated by the highest temperature capable of passing and is recorded in the following table.
(8) Moisture resistance test
The experiment is carried out in a special moisture-proof box, and the sample is placed in a condensed water experimental box with the temperature of 40 +/-2 ℃ and the relative humidity of 98% +/-2%. The test specimens should be arranged at an angle of 60 ° or more in the test chamber, and in this case they should not abut against each other in order to sufficiently release heat.
The results of the performance tests for each example are shown in the following table (where OK represents passing and NO is failing): in the examples, the ultralow nickel + silicate hole sealing process is adopted, and the thickness of the oxide film in all the examples and comparative examples is 6-8 um.
From the test results in the table above, the anodic oxide film prepared by the preparation method of the anodic oxide film with high temperature resistance and corrosion resistance provided by the invention has excellent acid resistance, alkali resistance, stain resistance, moisture resistance and the like, and can simultaneously meet various standards of the automobile industry. Particularly, the high temperature resistance of aluminum materials with different grades is obviously improved, and the comparative example shows that when the preparation method provided by the invention is not adopted, the heat cracking performance of the anodic oxide film of the aluminum and aluminum alloy anode workpiece is reduced or all performance requirements cannot be met (particularly, at least one performance of stain, CASS, NSS and the like is adversely affected when the preparation method is changed as follows, for example, common oxidation + hole sealing is adopted, the concentration of sulfuric acid in oxidation tank liquid is not in the specified range of the invention, or the additive in the oxidation tank liquid does not contain rare earth metal salt). In addition, by comparing the examples with the comparative examples, the present inventors have found that when the soluble rare earth metal salt in the additive is used in a specific mass ratio using salts of two different cations, the present invention has a great effect of enhancing CASS, NSS, heat and humidity resistance, and at the same time, organic acid salts (sodium gluconate and sodium oxalate) in the additive have a great effect of enhancing the above properties.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A preparation method of a high temperature-resistant corrosion-resistant anodic oxide film is characterized by comprising the following steps:
(1) preparing oxidation tank liquid, and placing an aluminum or aluminum alloy workpiece in the oxidation tank liquid for anodic oxidation treatment to form an anodic oxidation film, wherein the concentration of sulfuric acid in the oxidation tank liquid is 40-100g/L, the concentration of an additive is 2-10g/L, and the additive comprises the following raw materials in percentage by mass: 5-15% of soluble rare earth metal salt, 2-10% of organic acid, 0.5-1% of organic acid salt, 0.5-2% of lower alcohol and the balance of water; the organic acid salt is sodium gluconate and/or sodium oxalate;
(2) and sealing the hole of the anodic oxide film to obtain the high-temperature-resistant corrosion-resistant anodic oxide film.
2. The method according to claim 1, wherein the soluble rare earth metal salt is one or more of soluble sulfate, nitrate and acetate corresponding to rare earth metal cations of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium and yttrium.
3. The method for preparing the anodic oxide film with high temperature resistance and corrosion resistance according to claim 2, wherein the soluble rare earth metal salt comprises two rare earth metal salts with different cations, and the mass ratio of the two rare earth metal salts is 1: 1-3.
4. The method for preparing the anodic oxide film with high temperature resistance and corrosion resistance according to claim 1, wherein the mass ratio of the sulfuric acid to the organic acid is 100-500: 1.
5. The method for preparing the anodic oxide film with high temperature resistance and corrosion resistance according to claim 1, wherein the organic acid is one or more of oxalic acid, adipic acid, sulfamic acid, glycine, lactic acid, malic acid, tartaric acid and glycolic acid.
6. The method according to claim 1, wherein the lower alcohol is glycerol and/or ethylene glycol.
7. The method for preparing the anodic oxide film with high temperature resistance and corrosion resistance according to claim 1, wherein the conditions of the anodic oxidation treatment in the step (1) are as follows: the temperature is 17-22 ℃, the voltage is 20-30V, and the oxidation duration is 30-50 min.
8. The method for preparing the anodic oxide film with high temperature resistance and corrosion resistance according to any one of claims 1 to 7, wherein the hole sealing treatment in the step (2) comprises the following specific steps: placing the aluminum or aluminum alloy workpiece with the surface formed with the anodic oxide film in a 30-60g/L sealant photo seal 170, treating for 10-40min at 15-35 ℃, and then washing with water; and (3) placing the aluminum material subjected to the primary hole sealing treatment in a phoenix seal290A or a phoenix seal 290E, treating at 70-98 ℃ for 15-40min, washing with water, taking out and drying.
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