CN111041539B - Aluminum anode oxidation dyeing pre-double-step surface conditioner and preparation and application thereof - Google Patents
Aluminum anode oxidation dyeing pre-double-step surface conditioner and preparation and application thereof Download PDFInfo
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- CN111041539B CN111041539B CN202010002549.XA CN202010002549A CN111041539B CN 111041539 B CN111041539 B CN 111041539B CN 202010002549 A CN202010002549 A CN 202010002549A CN 111041539 B CN111041539 B CN 111041539B
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- 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
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Abstract
The invention discloses a two-step surface conditioner before aluminum anodic oxidation dyeing, which comprises an alkaline surface conditioner and an acidic surface conditioner, wherein the alkaline surface conditioner is one of a sodium bicarbonate solution, a potassium bicarbonate solution and an ammonia water solution, and the concentrations of the sodium bicarbonate solution, the potassium bicarbonate solution and the ammonia water solution are 5-50 g/l; the acidic surface conditioner comprises, by 100 parts by mass, 20-70 parts of organic acid, 1-10 parts of corrosion inhibitor, 5-20 parts of inorganic salt and the balance of deionized water, and when the acidic surface conditioner is used, the acidic surface conditioner is diluted into 40-200ml/l working solution, and the pH value is adjusted to 1.2-2.5. The two-step surface adjustment can effectively prevent the aluminum and aluminum alloy materials, the aluminum-plastic composite materials and the die-casting aluminum extruded composite materials from causing undesirable phenomena of uneven dyeing, blooming, corrosion spots and the like due to residual acid introduced in the processes of pretreatment and anodic oxidation, and can improve the coloring speed and further reduce the use of dyes or shorten the dyeing time to achieve the same dyeing effect by cleaning and finishing oxide film holes.
Description
Technical Field
The invention relates to the technical field of aluminum surface treatment, in particular to a two-step surface conditioner before aluminum anodic oxidation dyeing, and preparation and application thereof.
Background
With the upgrading of electronic product industry and the deep development and application of aluminum and aluminum alloy materials, aluminum and aluminum alloy materials such as pure aluminum, aluminum magnesium silicon, aluminum magnesium zinc and the like, aluminum-plastic composite materials and die-cast aluminum extruded composite materials become a new trend of electronic product shells. The electronic product housings of these aluminum and aluminum alloy materials, aluminum-plastic composites, and die-cast aluminum extruded aluminum composite products are usually treated by an anodizing process and a dyeing process to improve the decorative and durable properties of the electronic products.
At present, electronic product shells of the aluminum and aluminum alloy materials, the aluminum-plastic composite materials and the die-casting aluminum extruded aluminum composite material products have the following problems in the process of anodic oxidation process and dyeing process treatment:
1. the joint of the aluminum and aluminum alloy material, particularly the aluminum-plastic composite material and the die-cast aluminum extruded composite material, has tiny pores and defects, and easily causes the phenomena of acid substance residue and incomplete cleaning in the anodic oxidation process, thereby causing the defects of uneven dyeing, flowering, corrosion points and the like, and causing the extremely low yield.
2. In the processes of aluminum and aluminum alloy materials, aluminum-plastic composite materials and die-cast aluminum extruded aluminum composite materials subjected to sand blasting, and the anodizing process and dyeing process of cast aluminum, due to the reasons of non-uniformity of sand subjected to mechanical sand blasting, pollution of a casting mold, non-uniformity of aluminum melt slurry in the casting process and the like, shrinkage cavities formed by thermal expansion and cold contraction, holes formed by embedded stripping oil, holes formed by sand holes in the die-casting process and other defects and holes designed in the mold easily appear on the surfaces of the aluminum materials and the cast aluminum subjected to sand blasting, residual acid can be remained in the holes in the anodizing process, the defects such as uneven dyeing, blooming, pitting corrosion and the like are directly caused, and the yield is extremely low.
3. For aluminum and aluminum alloy materials, aluminum-plastic composite materials and die-cast aluminum extruded aluminum composite materials which have dyeing requirements on the hard anodizing process, the dyeing process is difficult and uneven due to small film holes formed under the hard anodizing condition, and the dyeing process cannot be normally carried out.
In order to solve the problems, a surface adjustment process is added between an anodic oxidation process and a dyeing process for the aluminum and aluminum alloy materials and the aluminum-plastic composite materials in the market. Since the surface conditioning solution on the market usually uses a mixture of organic acids, the mixture replaces and cleans the sulfuric acid remaining in the holes on the surface of the anodic oxide film of aluminum and aluminum alloy, and the concentration of the residual acid is diluted, so that the phenomena of uneven dyeing, blooming and pitting corrosion in the anodic oxidation process and the dyeing process are reduced to a certain extent, but the replacement and dilution of the acid still corrodes the surface of the anodic oxide film to a certain extent, so that the adverse effect of the residual acid on the surface of the anodic oxide film cannot be thoroughly removed.
Disclosure of Invention
The invention aims to provide a two-step surface conditioner before aluminum anodic oxidation dyeing, and preparation and application thereof, so as to solve the defects of the prior art.
The invention adopts the following technical scheme:
a two-step surface conditioner before aluminum anodic oxidation dyeing comprises an alkaline surface conditioner and an acidic surface conditioner, wherein the alkaline surface conditioner is one of a sodium bicarbonate solution, a potassium bicarbonate solution and an ammonia water solution, and the concentrations of the sodium bicarbonate solution, the potassium bicarbonate solution and the ammonia water solution are 5-50 g/l; the acidic surface conditioner comprises, by 100 parts by mass, 20-70 parts of organic acid, 1-10 parts of corrosion inhibitor, 5-20 parts of inorganic salt and the balance of deionized water, and when in use, the acidic surface conditioner is diluted into working solution of 40-200ml/l, and the pH is adjusted to 1.2-2.5.
Further, the organic acid is one or more of malic acid, tartaric acid, lactic acid, maleic acid, fumaric acid, succinic acid, ascorbic acid, glycine, malonic acid, gluconic acid, glutaric acid, glycolic acid and acetic acid.
Further, the corrosion inhibitor is one or more of polyacrylic acid, polyvinyl alcohol and glycerol.
Further, the inorganic salt is one or two of sodium acetate and sodium nitrate.
The preparation method of the aluminum pre-anodic oxidation dyeing two-step surface conditioner comprises the following steps:
preparation of alkaline surface conditioner: adding sodium bicarbonate, potassium bicarbonate or ammonia water into deionized water to prepare 5-50g/l sodium bicarbonate solution, potassium bicarbonate solution or ammonia water solution;
preparation of an acidic surface conditioner: adding organic acid into deionized water with the formula amount, uniformly stirring, adding the corrosion inhibitor, uniformly stirring, adding the inorganic salt, and uniformly stirring; when in use, the solution is diluted into 40-200ml/l of working solution by deionized water, and the pH is adjusted to 1.2-2.5.
The application of the two-step surface conditioner in surface conditioning before aluminum anodic oxidation dyeing is to firstly use the alkaline surface conditioner for surface conditioning and then use the acidic surface conditioner for surface conditioning.
Further, the method comprises the following steps:
step 1), placing the anodized aluminum product workpiece into an alkaline surface conditioner at normal temperature for ultrasonic alkaline surface conditioning for 5s-2min, and then washing the workpiece with water;
step 2), placing the aluminum product workpiece subjected to alkaline surface conditioning and water washing into working solution of an acidic surface conditioning agent at 20-50 ℃ for ultrasonic acidic surface conditioning for 30s-10min, and then washing the aluminum product workpiece clean; and then carrying out a subsequent dyeing process.
Further, the aluminum product workpiece comprises aluminum and aluminum alloy materials, aluminum-plastic composite materials and die-casting aluminum extruded aluminum composite materials.
Further, the ultrasonic frequency in the step 1) is 20-40 kHz.
Further, the ultrasonic frequency in the step 2) is 20-40 kHz.
The invention has the beneficial effects that:
the invention aims to solve the problem that hole residual acid on the surface of an anodic oxide film of a die-cast aluminum extruded aluminum composite material is easy to cause uneven dyeing, blooming, pitting corrosion and other adverse effects in a dyeing process, and improve the effect of surface adjustment, researches show that the two-step surface adjustment combining alkaline surface adjustment and acidic surface adjustment has a better effect, and deep researches on the composition and using conditions of the two-step surface adjustment formula are carried out to provide the two-step surface adjustment agent before aluminum anodic oxidation dyeing, and the preparation and application thereof.
1. The two-step surface conditioner before aluminum anodic oxidation dyeing comprises an alkaline surface conditioner and an acidic surface conditioner, wherein the alkaline surface conditioner is firstly used for surface conditioning, and then the acidic surface conditioner is used for surface conditioning. The two-step surface adjustment can effectively prevent the adverse phenomena of uneven dyeing, flowering, corrosion spots and the like caused by residual acid introduced in the processes of pretreatment and anodic oxidation of the aluminum and aluminum alloy materials and aluminum-plastic composite materials and die-cast extruded aluminum composite materials, and can improve the coloring speed and further reduce the use of dyes or shorten the dyeing time to achieve the same dyeing effect and improve the field processing quality level by cleaning and finishing oxide film holes.
2. The alkaline surface conditioner adopts weakly alkaline substances such as sodium bicarbonate, potassium bicarbonate, ammonia water and the like, compared with the acid surface conditioner, the alkaline surface conditioner can remove aluminum, aluminum alloy materials and aluminum-plastic composite materials more quickly and thoroughly, the die-cast aluminum extruded aluminum composite materials introduce residual acid of surface holes and defects in the processes of pretreatment and anodic oxidation, and the surface of a workpiece is not obviously corroded; in addition, aluminum sulfate crystals formed on the surface of the workpiece by oxidation when the content of aluminum ions in the oxidation tank is high and an anion adsorption layer formed on the outermost surface of the film layer in the oxidation process can be stripped; thereby preventing the substances from influencing the dyeing process to cause adverse effects such as uneven dyeing, flowering, corrosion spots and the like; usually, the acid-base reaction in the solution is carried out instantly, the auxiliary ultrasonic process can accelerate the local acid-base diffusion and reaction probability of the surface, the concentration of the residual acid on the surface can be treated lower, and the surface can be adjusted more thoroughly.
3. The working solution of the acidic surface conditioner is acidic, an alkaline film formed in the alkaline surface conditioner can be peeled off, aluminum and aluminum alloy materials and aluminum-plastic composite materials can be replaced under the action of ultrasonic waves, and residual acid in holes and defect depths of die-cast aluminum extruded aluminum composite materials can be replaced, and the opening of an anodic oxide film hole of the die-cast aluminum extruded composite materials can be adjusted and reamed, so that the small anodic oxide film hole formed by a hard anodic oxidation process can be effectively reamed, and the defects of difficulty in dyeing and unevenness in dyeing can be overcome. The acidic surface conditioner working solution contains a large amount of hydrogen ions, so that the positive charge property of the membrane pores is not damaged, the hydrogen ion concentration in the membrane pores can be maintained, and the dye adsorption capacity is improved.
Drawings
FIG. 1 is a scanning electron microscope image of the holes of the anodized film of the aluminum plate of example 1 without surface modification.
FIG. 2 is an electron microscope scanning image of the hole of the anodized film of the aluminum plate with one-step adjustment of the alkaline surface conditioning in example 1.
FIG. 3 is an electron microscope scanning image of the anodic oxide film pores of the aluminum plate adjusted by two steps of the alkaline and acidic leveling in example 1.
Fig. 4 is an external view of a sandblasted aluminum-plastic joint of example 2 without two-step surface conditioning.
Fig. 5 is an external view of a sandblasted aluminum-plastic composite part subjected to a two-step surface conditioning in example 2.
FIG. 6 is a comparison of the color differences (ODM DYE RED (R122) and ODM DYE ORANGE (OR213) staining) of the surfaces of the boards of example 3 without and with two steps of surface leveling.
FIG. 7 is a comparison of the color differences of the surfaces of the boards of example 3 without and with the two-step leveling (ODM DYE BLUE (B511) and ODM DYE BLACK (BK927) dyeings).
Detailed Description
The invention is explained in more detail below with reference to exemplary embodiments and the accompanying drawings. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
A two-step surface conditioner before anodic oxidation dyeing of aluminium comprises an alkaline surface conditioner and an acidic surface conditioner. The alkaline surface conditioner is one of sodium bicarbonate solution, potassium bicarbonate solution and ammonia water (27 wt%) solution, and the concentration of the sodium bicarbonate solution, the potassium bicarbonate solution and the ammonia water solution is 5-50 g/l. The acidic surface conditioner comprises, by 100 parts by mass, 20-70 parts of organic acid, 1-10 parts of corrosion inhibitor, 5-20 parts of inorganic salt and the balance of deionized water, wherein the organic acid is one or more of malic acid, tartaric acid, lactic acid, maleic acid, fumaric acid, succinic acid, ascorbic acid, glycine, malonic acid, gluconic acid, glutaric acid, glycolic acid and acetic acid, the corrosion inhibitor is one or more of polyacrylic acid, polyvinyl alcohol and glycerol, and the inorganic salt is one or two of sodium acetate and sodium nitrate; when in use, the solution is diluted into working solution of 40-200ml/L, and the pH is adjusted to 1.2-2.5 by using 10 wt% nitric acid and 100g/L sodium hydroxide.
The preparation method of the aluminum pre-anodic oxidation dyeing two-step surface conditioner comprises the following steps:
preparation of alkaline surface conditioner: adding sodium bicarbonate, potassium bicarbonate or ammonia water into deionized water to prepare 5-50g/l sodium bicarbonate solution, potassium bicarbonate solution or ammonia water solution;
preparation of an acidic surface conditioner: adding organic acid into deionized water with the formula amount, uniformly stirring, adding the corrosion inhibitor, uniformly stirring, adding the inorganic salt, and uniformly stirring; when in use, the solution is diluted into 40-200ml/L of working solution by deionized water, and the pH is adjusted to 1.2-2.5 by using 10 wt% nitric acid and 100g/L sodium hydroxide.
The application of the two-step surface conditioner in surface conditioning before aluminum anodic oxidation dyeing firstly utilizes the alkaline surface conditioner to perform surface conditioning and then utilizes the acidic surface conditioner to perform surface conditioning, and the method specifically comprises the following steps:
step 1), placing the anodized aluminum product workpiece into an alkaline surface conditioner at normal temperature for ultrasonic alkaline surface conditioning for 5s-2min, wherein the ultrasonic frequency is 20-40 kHz, and then washing the workpiece with water;
step 2), placing the aluminum product workpiece subjected to alkaline surface conditioning and water washing into a working solution of an acidic surface conditioning agent at the temperature of 20-50 ℃ for ultrasonic and acidic surface conditioning for 30s-10min, wherein the ultrasonic frequency is 20-40 kHz, and then washing the aluminum product workpiece clean; and then carrying out a subsequent dyeing process.
The aluminum product workpiece comprises aluminum and aluminum alloy materials, aluminum-plastic composite materials and die-casting aluminum extruded composite materials.
Example 1
The basic surface conditioner used in the basic surface conditioner step in this example has the following formula: sodium bicarbonate solution 10 g/l. The operation temperature is normal temperature, the auxiliary ultrasonic equipment is used for processing, the ultrasonic frequency is 24kHz, and the operation time is 30 s.
The formula of the acidic surface conditioner used in the acidic surface conditioning step is as follows: 20 parts by mass of deionized water, 60 parts by mass of glycolic acid, 6 parts by mass of malic acid, 9 parts by mass of sodium nitrate and 5 parts by mass of polyacrylic acid. Adding deionized water into a liquid stirring tank, then adding materials according to the sequence of organic acid, corrosion inhibitor and inorganic salt, fully stirring every time one material is added, fully stirring after all materials are added, and uniformly mixing. The solution was diluted with deionized water to 100ml/L of working solution, and the pH was adjusted to 1.2 using 10 wt% nitric acid and 100g/L sodium hydroxide. The operation temperature is 30 ℃, the auxiliary ultrasonic equipment is used for processing, the ultrasonic frequency is 36kHz, and the operation time is 1 min.
In this example, an aluminum plate of 6063 al-mg-si alloy material and a size of 100 × 50 × 0.5mm was used, the treatment was performed under the conditions shown in table 1, and after each step, the aluminum plate was washed with water to prevent the contamination of the next step by the chemical solution. And observing the state comparison of the aluminum plate anode oxide film holes after the processes of no surface adjustment (according to the conditions in the table 1, but no alkaline surface adjustment and no acidic surface adjustment), one-step adjustment of the alkaline surface adjustment (according to the conditions in the table 1, but no acidic surface adjustment) and two-step adjustment of the alkaline surface adjustment and the acidic surface adjustment (according to the conditions in the table 1) by scanning through an electron microscope. As shown in FIGS. 1-3, the surface of FIG. 1 is dirty, not clean, and the pore diameter of the membrane pore is small, which is likely to cause the phenomena of slow coloring speed, surface blooming and non-uniformity; FIG. 2 shows that the surface is clean, the pore diameter of a membrane pore is small, and the coloring speed is easy to slow; FIG. 3 shows that the surface is clean, the pore diameter of the membrane pores is large, the membrane pores are uniformly distributed, and the coloring speed and the dyeing uniformity of the anodic oxide membrane can be improved.
TABLE 1
Example 2
The basic surface conditioner used in the basic surface conditioner step in this example has the following formula: 5g/l potassium bicarbonate solution. The operation temperature is normal temperature, the ultrasonic treatment is assisted by ultrasonic equipment, the ultrasonic frequency is 30kHz, and the operation time is 1 min.
The formula of the acidic surface conditioner used in the acidic surface conditioning step is as follows: 20 parts by mass of deionized water, 43 parts by mass of lactic acid, 11 parts by mass of maleic acid, 9 parts by mass of glycine, 9 parts by mass of sodium acetate, 6 parts by mass of polyvinyl alcohol and 2 parts by mass of polyacrylic acid. Adding deionized water into a liquid stirring tank, then adding materials according to the sequence of organic acid, corrosion inhibitor and inorganic salt, fully stirring every time one material is added, fully stirring after all materials are added, and uniformly mixing. The solution was diluted with deionized water to 60ml/L of working solution, and the pH was adjusted to 1.8 using 10 wt% nitric acid and 100g/L sodium hydroxide. The operation temperature is 35 ℃, the auxiliary ultrasonic equipment is used for processing, the ultrasonic frequency is 40kHz, and the operation time is 5 min.
In this example, a sandblasted aluminum-plastic binder was used, and the treatment was performed under the conditions shown in Table 2, and each step was followed by water washing to avoid contamination of the next step by the chemical solution. The surface color uniformity and the appearance of the aluminum-plastic joint were observed without the two-step surface adjustment (according to the conditions in Table 2, but without the alkaline surface adjustment and the acidic surface adjustment) and after the two-step surface adjustment (according to the conditions in Table 2). As a result, as shown in FIGS. 4 and 5, respectively, FIG. 4 shows a sandblasted aluminum-plastic joint without two-step surface conditioning, having white corrosion spots and spots of blistering due to residual acid on the surface near the aluminum-plastic joint of the workpiece; FIG. 5 shows the sand-blasted plastic-aluminum combined member with two-step surface adjustment, which has uniform surface cleaning and no phenomena of blooming and corrosion.
TABLE 2
Example 3
The basic surface conditioner used in the basic surface conditioner step in this example has the following formula: 30g/l of ammonia water (27 wt.%). The operation temperature is normal temperature, the auxiliary ultrasonic equipment is used for processing, the ultrasonic frequency is 20kHz, and the operation time is 45 s.
The formula of the acidic surface conditioner used in the acidic surface conditioning step is as follows: 40 parts by mass of deionized water, 30 parts by mass of fumaric acid, 14 parts by mass of malonic acid, 6 parts by mass of gluconic acid, 8 parts by mass of sodium nitrate and 2 parts by mass of glycerol. Adding deionized water into a liquid stirring tank, then adding materials according to the sequence of organic acid, corrosion inhibitor and inorganic salt, fully stirring every time one material is added, fully stirring after all materials are added, and uniformly mixing. The solution was diluted with deionized water to 150ml/L of working solution, and the pH was adjusted to 1.5 using 10 wt% nitric acid and 100g/L sodium hydroxide. The operation temperature is 40 ℃, the ultrasonic frequency is 30kHz, and the operation time is 3 min.
In this example, a plate made of 7075 al-mg-zn alloy and having a size of 50 × 25 × 0.5mm was treated under the conditions shown in table 3 (hard anodizing), and the plate was washed with water after each step to prevent the liquid from contaminating the next step. The color difference of the surface of the plate without the two-step leveling (according to the conditions in Table 3, but without the alkaline leveling and the acidic leveling) and with the two-step leveling (according to the conditions in Table 3) was compared. Reference standard GB/T12967.6-2008 aluminum and aluminum alloy anode oxide film detection method part 6: the color difference and appearance quality of the colored anodic oxide film were examined by visual observation, wherein the value L in the color difference represents lightness, the value a represents red-green value, and the value b represents yellow-blue value. As shown in fig. 6 and 7, fig. 6 and 7 are graphs comparing the hard anodizing condition without the two-step tone and with the two-step tone, and it can be seen from the graphs that the workpiece with the two-step tone has a smaller L value, a darker representative color and a faster coloring speed, and a larger absolute value of a and b, a brighter representative color and a more saturated representative color, and a faster coloring speed is also illustrated.
TABLE 3
Claims (4)
1. The application of the aluminum pre-anodic oxidation dyeing two-step surface conditioner in the surface conditioning of the aluminum pre-anodic oxidation dyeing is characterized in that the aluminum pre-anodic oxidation dyeing two-step surface conditioner comprises an alkaline surface conditioner and an acidic surface conditioner;
the alkaline surface conditioner is one of sodium bicarbonate solution, potassium bicarbonate solution and ammonia water solution, and the concentration of the sodium bicarbonate solution, the potassium bicarbonate solution and the ammonia water solution is 5-50 g/l; the preparation method specifically comprises the following steps: adding sodium bicarbonate, potassium bicarbonate or ammonia water into deionized water to prepare 5-50g/l sodium bicarbonate solution, potassium bicarbonate solution or ammonia water solution;
the acidic surface conditioner comprises, by 100 parts by mass, 20-70 parts of organic acid, 1-10 parts of corrosion inhibitor, 5-20 parts of sodium acetate or/and sodium nitrate and the balance of deionized water, and when in use, the acidic surface conditioner is diluted into working solution of 40-200ml/l, and the pH is adjusted to 1.2-2.5; wherein the organic acid is one or more of malic acid, tartaric acid, lactic acid, maleic acid, fumaric acid, succinic acid, ascorbic acid, glycine, malonic acid, gluconic acid, glutaric acid, glycolic acid and acetic acid; the corrosion inhibitor is one or more of polyacrylic acid, polyvinyl alcohol and glycerol; the preparation method specifically comprises the following steps: adding organic acid into deionized water with the formula amount, uniformly stirring, adding the corrosion inhibitor, uniformly stirring, adding sodium acetate or/and sodium nitrate, and uniformly stirring; when in use, deionized water is used for diluting the solution into working solution of 40-200ml/l, and the pH value is adjusted to 1.2-2.5;
when in use, firstly, the alkaline surface conditioner is used for surface conditioning, and then the acidic surface conditioner is used for surface conditioning, and the method comprises the following steps:
step 1), placing the anodized aluminum product workpiece into an alkaline surface conditioner at normal temperature for ultrasonic alkaline surface conditioning for 5s-2min, and then washing the workpiece with water;
step 2), placing the aluminum product workpiece subjected to alkaline surface conditioning and water washing into working solution of an acidic surface conditioning agent at 20-50 ℃ for ultrasonic acidic surface conditioning for 30s-10min, and then washing the aluminum product workpiece clean; and then carrying out a subsequent dyeing process.
2. The use of the pre-anodic oxidation dyeing two-step conditioner for aluminum surface conditioning according to claim 1, wherein the aluminum product workpiece comprises aluminum and aluminum alloy material, aluminum-plastic composite material.
3. The application of the aluminum pre-anodic oxidation dyeing two-step surface conditioner in the aluminum pre-anodic oxidation dyeing surface conditioning is characterized in that the ultrasonic frequency in the step 1) is 20-40 kHz.
4. The application of the aluminum pre-anodic oxidation dyeing two-step surface conditioner in the aluminum pre-anodic oxidation dyeing surface conditioning is characterized in that the ultrasonic frequency in the step 2) is 20-40 kHz.
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| CN111809211B (en) * | 2020-07-22 | 2022-02-15 | 中山市三美高新材料技术有限公司 | Anodic oxidation processing method for cast aluminum surface |
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