CN110629267A - Alkaline anodizing solution and anodizing method for aluminum products - Google Patents
Alkaline anodizing solution and anodizing method for aluminum products Download PDFInfo
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- CN110629267A CN110629267A CN201810659854.9A CN201810659854A CN110629267A CN 110629267 A CN110629267 A CN 110629267A CN 201810659854 A CN201810659854 A CN 201810659854A CN 110629267 A CN110629267 A CN 110629267A
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- alkaline
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- aluminum product
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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
Abstract
An aluminum article alkaline anodizing solution comprising: alkaline salts, buffers, alcohols and water; the alkaline salt is carbonate and/or bicarbonate; the alcohol is water-soluble alcohol, and the boiling point of the alcohol is above 60 ℃; the pH value of the alkaline anodic oxidation liquid for the aluminum product is 8-12. According to the invention, through the mutual cooperation of the alkaline salt, the buffering agent and the alcohol in the alkaline anodic oxidation liquid, the uniform and stable growth of the aluminum product in the alkaline anodic oxidation liquid can be ensured, so that a uniform and complete anodic oxidation film layer is formed on the surface of the aluminum product, and the formed anodic oxidation film layer has high thickness and can be used for surface decoration.
Description
Technical Field
The invention relates to the field of anodic oxidation, and particularly relates to an alkaline anodic oxidation solution for an aluminum product and an anodic oxidation method.
Background
Traditional aluminum and aluminum alloy anodic oxidation is carried out under an acidic condition, and few reports show that aluminum or aluminum alloy is subjected to anodic oxidation under an alkaline condition, because an aluminum oxide film is difficult to generate under an alkaline environment, and the aluminum, the aluminum alloy and the aluminum oxide film are seriously corroded under the alkaline environment, and a complete and uniform anodic oxidation film layer is difficult to obtain by carrying out anodic oxidation treatment on an aluminum product under the alkaline environment. In the prior art, the anodic oxidation treatment of the aluminum product under the alkaline condition can not form an anodic oxide film layer or form the anodic oxide film layer with very low thickness, and the anodic oxide film layer can only be used as a coating bottom layer and can not be used for surface decoration.
Disclosure of Invention
Aiming at the technical problems that an anodic oxide film layer cannot be formed or the thickness of the anodic oxide film layer is very low and a complete and uniform anodic oxide film layer is difficult to obtain when the anodic oxidation treatment is carried out on an aluminum product under the alkaline condition in the prior art, the invention provides the alkaline anodic oxidation liquid and the anodic oxidation method.
In a first aspect of the present invention, an alkaline anodizing solution for aluminum products is provided, which includes: alkaline salts, buffers, alcohols and water; the alkaline salt is carbonate and/or bicarbonate; the alcohol is water-soluble alcohol, and the boiling point of the alcohol is above 60 ℃; the pH value of the alkaline anodic oxidation liquid for the aluminum product is 8-12.
In a second aspect of the present invention, an aluminum product is placed in the above aluminum product alkaline anodizing solution to perform anodic oxidation, so as to obtain an aluminum product with an anodic oxide film layer on the surface.
According to the invention, alcohols are added into the alkaline anodic oxidation liquid of the aluminum product, so that a film can be formed on the surface of the aluminum product subjected to anodic oxidation treatment, and further the corrosion of the anodic oxidation film generated by anodic oxidation treatment in an alkaline environment is slowed down, and the thickness of the anodic oxidation film can continuously grow; the addition of the buffering agent can adjust the pH value of the alkaline anodizing solution of the aluminum product, thereby ensuring that the aluminum product can uniformly and stably carry out the anodic oxidation reaction in the alkaline anodizing solution. The invention can ensure the uniform and stable growth of the aluminum product in the alkaline anodic oxidation liquid through the mutual matching action of the alkaline salt, the buffering agent and the alcohol in the alkaline anodic oxidation liquid, thereby forming a uniform and complete anodic oxidation film layer on the surface of the aluminum product.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In a first aspect of the present invention, an alkaline anodizing solution for aluminum products is provided, which includes: alkaline salt, buffering agent, alcohol and the balance of water; the alkaline salt is carbonate and/or bicarbonate; the alcohol is water-soluble alcohol, and the boiling point of the alcohol is above 60 ℃; the pH value of the alkaline anodic oxidation liquid for the aluminum product is 8-12.
According to the invention, alcohols are added into the alkaline anodic oxidation liquid of the aluminum product, so that a film can be formed on the surface of the aluminum product subjected to anodic oxidation treatment, and further the corrosion of the anodic oxidation film generated by anodic oxidation treatment in an alkaline environment is slowed down, and the thickness of the anodic oxidation film can continuously grow; the addition of the buffering agent can adjust the pH value of the alkaline anodizing solution of the aluminum product, thereby ensuring that the aluminum product can uniformly and stably carry out the anodic oxidation reaction in the alkaline anodizing solution. The invention can ensure the uniform and stable growth of the aluminum product in the alkaline anodic oxidation liquid through the mutual matching action of the alkaline salt, the buffering agent and the alcohol in the alkaline anodic oxidation liquid, thereby forming a uniform and complete anodic oxidation film layer on the surface of the aluminum product.
Preferably, the water-soluble alcohol has a boiling point of 80-300 ℃. The choice of an alcohol that is miscible with water and has a boiling point within the preferred ranges described above can promote the growth and maintain the integrity of the anodized film.
Preferably, the alcohol is at least one of glycerol, ethylene glycol, ethanol, 2-propanol and 1-propanol; more preferably, the alcohol is glycerol and/or ethylene glycol. The alcohol substance preferably selected by the invention can form a film on the surface of the aluminum product subjected to anodic oxidation treatment, so that the corrosion of the anodic oxide film generated by the anodic oxidation treatment in an alkaline environment is slowed down, and the thickness of the anodic oxide film can be continuously increased.
Preferably, the basic salt is at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate; further preferably, the alkaline salt is sodium carbonate and/or sodium bicarbonate. The invention preferably selects the alkaline salt, can ensure that the reaction rate of the aluminum product in an alkaline environment is moderate, and can not cause serious corrosion of the aluminum product in the alkaline anodic oxidation liquid.
Preferably, the buffer has a pH of 4 to 13. The pH value of the buffering agent is in the preferable range, and the pH value of the alkaline anodic oxidation liquid can be effectively adjusted, so that the uniform and stable reaction of the aluminum product in the alkaline anodic oxidation liquid is ensured.
Preferably, the buffer is at least one of boric acid, sodium borate, sodium citrate, sodium gluconate, sodium succinate, sodium phosphate, disodium hydrogen phosphate, sodium acetate and sodium hydrogen phosphate; preferably, the buffer is at least one of boric acid, sodium borate and sodium citrate. The boric acid is acidic, and can react with direct alkali, so that the pH value is obviously reduced; sodium borate and sodium citrate can inhibit the hydrolysis of alkaline salt to a certain extent, thereby reducing the pH value. The buffering agents such as sodium borate, boric acid, sodium citrate and the like are added into the alkaline anodic oxidation liquid, so that the pH value of the alkaline anodic oxidation liquid can be adjusted, and the uniform and stable anodic oxidation reaction is ensured.
Preferably, the content of the alkaline salt is 40-400g/L, the content of the buffering agent is 1-100g/L, and the content of the alcohol is 5-300 g/L; more preferably, the content of the alkaline salt is 40-70g/L, the content of the buffer is 5-20 g/L, and the content of the alcohol is 70-130 g/L. The components of the invention are in the preferable range, and can promote the growth of the anodic oxide film and maintain the integrity of the anodic oxide film.
Preferably, the product alkaline anodizing solution also comprises organic acid salt, wherein the solubility of the organic acid salt is 30-500g/1000g of water, and the pH value is 8-14. The solubility and pH of the organic acid salt are in the above preferable ranges, and the organic acid salt can promote the growth of an anodic oxide film and increase the stability of the solution.
Preferably, the organic acid salt is at least one of sodium oxalate, sodium tartrate, sodium benzoate, sodium malate and sodium phytate; preferably, the organic acid salt is sodium oxalate and/or sodium tartrate. The use of sodium oxalate and/or sodium tartrate can inhibit hydrogen evolution corrosion of the aluminum product under alkaline conditions, and the addition of the sodium oxalate and/or sodium tartrate increases the reaction rate of anodic oxidation, so that the growth rate of an anodic oxide film is greater than the dissolution rate of the anodic oxide film, thereby ensuring the growth rate of the anodic oxide film of the aluminum product and ensuring the uniformity and integrity of the anodic oxide film of the aluminum product.
Preferably, the content of the organic acid salt is 1-200 g/L; more preferably, the content of the organic acid salt is 20 to 50 g/L. The organic acid salt of the present invention can promote the growth of the anodic oxide film and increase the stability of the solution within the above preferable range.
In a second aspect of the present invention, an aluminum product is placed in the above aluminum product alkaline anodizing solution to perform anodic oxidation, so as to obtain an aluminum product with an anodic oxide film layer on the surface.
Preferably, the anodic oxidation voltage is 5-200V, the temperature is 12-90 ℃, and the time is 5-300 min; preferably, the voltage of the anodic oxidation is 40-80V, the temperature is 60-80 ℃, and the time is 30-90 min. The thickness of the anodic oxidation film layer of the aluminum product can be controlled by adjusting the anodic oxidation conditions (voltage, temperature, time and the like); the thickness of the anodic oxide film layer is 1-20 μm.
The aluminum product alkaline anodic oxidation liquid is adopted to carry out anodic oxidation treatment on the aluminum product, a uniform and complete anodic oxidation film layer can be formed on the surface of the aluminum product, the thickness of the formed anodic oxidation film layer is high, and the anodic oxidation film layer can be used for surface decoration.
The present invention is further illustrated by the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All the raw materials in the examples of the present invention are commercially available products unless otherwise specified.
Example 1
Preparing an alkaline anodic oxidation liquid for an aluminum product: uniformly mixing alkaline salt, a buffering agent, alcohol, organic acid salt and water required by the alkaline anodic oxidation liquid of the aluminum product, and adjusting the pH value of the alkaline anodic oxidation liquid of the aluminum product to be 10.7. Wherein the content of sodium carbonate is 40g/L, the content of boric acid is 5g/L, and the content of glycerol is 70 g/L;
anodizing the surface of the aluminum product: putting 6063 aluminum alloy serving as a base material into the alkaline anodizing solution of the aluminum product prepared in the example 1 to perform anodizing treatment, wherein the voltage of the anodizing treatment is 80V, the temperature is 80 ℃, and the time is 90 min; then surface decoration (dyeing) and hole sealing can be selectively carried out to obtain the anodic alumina product A1.
Example 2
Preparing an alkaline anodic oxidation liquid for an aluminum product: uniformly mixing alkaline salt, a buffering agent, alcohol, organic acid salt and water required by the alkaline anodic oxidation liquid of the aluminum product, and adjusting the pH value of the alkaline anodic oxidation liquid of the aluminum product to be 10.4. Wherein the content of sodium carbonate is 50g/L, the content of sodium borate is 10g/L, the content of glycerol is 100g/L, and the content of sodium tartrate is 30 g/L;
the aluminum article was subjected to anodic oxidation treatment in the same manner as in example 1 to obtain an anodized aluminum article A2.
Example 3
Preparing an alkaline anodic oxidation liquid for an aluminum product: uniformly mixing alkaline salt, a buffering agent, alcohol, organic acid salt and water required by the alkaline anodic oxidation liquid of the aluminum product, and adjusting the pH value of the alkaline anodic oxidation liquid of the aluminum product to be 10.1. Wherein the content of sodium bicarbonate is 60g/L, the content of sodium borate is 20g/L, the content of ethylene glycol is 120g/L, and the content of sodium tartrate is 40 g/L;
the aluminum article was subjected to anodic oxidation treatment in the same manner as in example 1 to obtain an anodized aluminum article A3.
Example 4
Preparing an alkaline anodic oxidation liquid for an aluminum product: uniformly mixing alkaline salt, a buffering agent, alcohol, organic acid salt and water required by the alkaline anodic oxidation liquid of the aluminum product, and adjusting the pH value of the alkaline anodic oxidation liquid of the aluminum product to 9.5. Wherein the content of the sodium bicarbonate is 70g/L, the content of the boric acid is 10g/L, the content of the ethylene glycol is 90g/L, and the content of the sodium oxalate is 50 g/L;
the aluminum article was subjected to anodic oxidation treatment in the same manner as in example 1 to obtain an anodized aluminum article A4.
Example 5
Preparing an alkaline anodic oxidation liquid for an aluminum product: uniformly mixing alkaline salt, a buffering agent, alcohol, organic acid salt and water required by the alkaline anodic oxidation liquid of the aluminum product, and adjusting the pH value of the alkaline anodic oxidation liquid of the aluminum product to be 11. Wherein the content of potassium carbonate is 40g/L, the content of sodium borate is 15g/L, the content of methanol is 80g/L, and the content of sodium oxalate is 30 g/L;
the aluminum article was subjected to anodic oxidation treatment in the same manner as in example 1 to obtain an anodized aluminum article A5.
Example 6
Preparing an alkaline anodic oxidation liquid for an aluminum product: uniformly mixing alkaline salt, a buffering agent, alcohol, organic acid salt and water required by the alkaline anodic oxidation liquid of the aluminum product, and adjusting the pH value of the alkaline anodic oxidation liquid of the aluminum product to 9.5. Wherein the content of sodium carbonate is 10g/L, the content of boric acid is 8g/L, the content of glycol is 90g/L, and the content of sodium oxalate is 50 g/L;
the aluminum article was subjected to anodic oxidation treatment in the same manner as in example 1 to obtain an anodized aluminum article A6.
Example 7
Preparing an alkaline anodic oxidation liquid for an aluminum product: uniformly mixing alkaline salt, a buffering agent, alcohol, organic acid salt and water required by the alkaline anodic oxidation liquid of the aluminum product, and adjusting the pH value of the alkaline anodic oxidation liquid of the aluminum product to be 10.7. Wherein the content of sodium carbonate is 50g/L, the content of boric acid is 10g/L, the content of ethylene glycol is 30g/L, and the content of sodium oxalate is 30 g/L;
the aluminum article was subjected to anodic oxidation treatment in the same manner as in example 1 to obtain an anodized aluminum article A7.
Example 8
Preparing an alkaline anodic oxidation liquid for an aluminum product: uniformly mixing alkaline salt, a buffering agent, alcohol, organic acid salt and water required by the alkaline anodic oxidation liquid of the aluminum product, and adjusting the pH value of the alkaline anodic oxidation liquid of the aluminum product to be 10.5. Wherein the content of sodium carbonate is 50g/L, the content of boric acid is 10g/L, the content of glycol is 200g/L, and the content of sodium oxalate is 30 g/L;
the aluminum article was subjected to anodic oxidation treatment in the same manner as in example 1 to obtain an anodized aluminum article A8.
Comparative example 1
An anodized aluminum product B1 was prepared in the same manner as in example 2, except that the solution contained no alcohol and had a pH of 11.
Comparative example 2
An anodized aluminum product B2 was prepared in the same manner as in example 2, except that the composition contained no buffer and no organic acid salt and the pH of the basic anodizing solution was 11.1.
Comparative example 3
Sodium borate, ethylene glycol and sodium tartrate are dissolved in water to form an anodic oxidation solution with the pH of 8.5. Wherein the content of the sodium borate is 20g/L, the content of the ethylene glycol is 120g/L, and the content of the sodium tartrate is 40 g/L;
the aluminum article was anodized in the same manner as in example 1 to obtain an anodized aluminum article B3.
Comparative example 4
Dissolving sodium borate, ethylene glycol, sodium tartrate and sodium hydroxide in water to form an anodic oxidation solution with the pH value of 14. Wherein the content of the sodium borate is 20g/L, the content of the ethylene glycol is 120g/L, the content of the sodium tartrate is 40g/L, and the content of the sodium hydroxide is 45 g/L;
the aluminum article was anodized in the same manner as in example 1 to obtain an anodized aluminum article B4.
Performance testing and results
1. And (3) testing the film thickness: testing the thickness of the anodic oxide film layer of the sample wafer by adopting a crystal image slicing method, wherein the model of the adopted testing instrument is an Axio Scope A1 crystal image microscope;
2. and (3) appearance inspection: visually observing whether appearance defects such as heterochromatic spots exist on the surface of the sample;
the test results are shown in table 1:
TABLE 1
| PH | Film thickness/. mu.m | Appearance of the product | |
| Example 1 | 10.7 | 12 | Good and uniform |
| Example 2 | 10.4 | 13 | Good and uniform |
| Example 3 | 10.1 | 14 | Good and uniform |
| Example 4 | 9.5 | 14 | Good and uniform |
| Example 5 | 11 | 5 | The film formation is more uniform |
| Example 6 | 9.5 | 5 | The film formation is more uniform |
| Example 7 | 10.7 | 5 | Uniform film formationUniform mixing |
| Example 8 | 10.5 | 5 | The film formation is more uniform |
| Comparative example 1 | 11 | 3 | The surface has different color spots |
| Comparative example 2 | 11.1 | 3 | Rough surface with different color spots |
| Comparative example 3 | 11.5 | 2 | The surface has different color spots |
| Comparative example 4 | 14 | 2 | Rough surface with different color spots |
From the above test results, it can be seen that: the formulations adopted in examples 1-4 are the preferred formulations of the present invention, and the anodized aluminum articles prepared therefrom have high thickness and uniform and complete appearance; the alcohol used in example 5 was methanol, the amount of sodium carbonate added in example 6 was small, the amount of alcohol added in example 7 was small, the amount of alcohol added in example 8 was large, and the thickness and appearance of the anodized aluminum products prepared in examples 5 to 8 were slightly inferior, but the effect was still better than those of comparative examples 1 to 4. That is, the invention can ensure the uniform and stable growth of the aluminum product in the alkaline anodic oxidation liquid through the mutual coordination of the alkaline salt, the buffering agent and the alcohol in the alkaline anodic oxidation liquid, thereby forming a uniform and complete anodic oxidation film layer on the surface of the aluminum product. Of course, the invention can also control the thickness of the aluminum alloy oxidation film layer by controlling the condition of anodic oxidation, namely, by adjusting the voltage, temperature, time and the like of anodic oxidation, thereby preparing the aluminum alloy with anodic oxidation film layers with different thicknesses.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. It is not necessary or necessary to exhaustively enumerate all embodiments herein, and obvious variations or modifications can be introduced thereby while remaining within the scope of the invention as claimed.
Claims (14)
1. An aluminum product alkaline anodizing solution, comprising: alkaline salts, buffers, alcohols and water; the alkaline salt is carbonate and/or bicarbonate; the alcohol is water-soluble alcohol, and the boiling point of the alcohol is above 60 ℃; the pH value of the alkaline anodic oxidation liquid for the aluminum product is 8-12.
2. The aluminum product alkaline anodizing solution of claim 1, wherein the water-soluble alcohol has a boiling point of 80-300 ℃.
3. The aluminum product alkaline anodizing solution of claim 1, wherein said alcohol is at least one of glycerol, ethylene glycol, ethanol, 2-propanol, and 1-propanol; more preferably, the alcohol is glycerol and/or ethylene glycol.
4. The aluminum product alkaline anodizing solution of claim 1, wherein the alkaline salt is at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, and ammonium bicarbonate; more preferably, the alkaline salt is sodium carbonate and/or sodium bicarbonate.
5. The aluminum product alkaline anodizing solution of claim 1, wherein the buffer has a pH of 4-13.
6. The aluminum product alkaline anodizing solution of claim 1, wherein the buffering agent is at least one of boric acid, sodium borate, sodium citrate, sodium gluconate, sodium succinate, sodium phosphate, disodium hydrogen phosphate, sodium acetate, and sodium hydrogen phosphate; preferably, the buffer is at least one of boric acid, sodium borate and sodium citrate.
7. The aluminum product alkaline anodizing solution of claim 1, wherein the alkaline salt content is 40-400g/L, the buffer content is 1-100g/L, and the alcohol content is 5-300 g/L.
8. The aluminum product alkaline anodizing solution of claim 1, wherein the alkaline salt content is 40-70g/L, the buffer content is 5-20 g/L, and the alcohol content is 70-130 g/L.
9. The alkaline anodizing solution for aluminum products as claimed in claim 1, further comprising an organic acid salt, wherein the solubility of the organic acid salt is 30-500g/1000g water, and the pH value is 8-14.
10. The alkaline anodizing solution for aluminum products of claim 9, wherein the organic acid salt is at least one of sodium oxalate, sodium tartrate, sodium benzoate, sodium malate and sodium phytate; preferably, the organic acid salt is sodium oxalate and/or sodium tartrate.
11. The aluminum product alkaline anodizing solution of claim 9, wherein the content of the organic acid salt is 1-200 g/L; preferably, the content of the organic acid salt is 20-50 g/L.
12. An aluminum product alkaline anodizing method is characterized in that an aluminum product is placed into the aluminum product alkaline anodizing solution of any one of claims 1-11 to be anodized, and an aluminum product with an anodized film layer on the surface is prepared.
13. The aluminum product alkaline anodizing method of claim 12, wherein the anodizing voltage is 5-200V, the temperature is 12-90 ℃, and the time is 5-300 min; preferably, the voltage of the anodic oxidation is 40-80V, the temperature is 60-80 ℃, and the time is 30-90 min.
14. The aluminum product alkaline anodization method of claim 12, wherein the thickness of the anodic oxide film layer is 1-20 μ ι η.
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