CN110656334A - Environment-friendly aluminum material chemical polishing solution free of phosphorus element and nitrogen element - Google Patents
Environment-friendly aluminum material chemical polishing solution free of phosphorus element and nitrogen element Download PDFInfo
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- CN110656334A CN110656334A CN201911078438.0A CN201911078438A CN110656334A CN 110656334 A CN110656334 A CN 110656334A CN 201911078438 A CN201911078438 A CN 201911078438A CN 110656334 A CN110656334 A CN 110656334A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/02—Light metals
- C23F3/03—Light metals with acidic solutions
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Abstract
The invention relates to an environment-friendly aluminum material chemical polishing solution without phosphorus and nitrogen elements, which is prepared by taking sulfuric acid with the content of 500-1500g/L and sulfonic acid with the content of 50-800g/L as a basic system and matching with specific metal salt with the content of 0.01-100g/L and specific complexing agent with the content of 1-200 g/L. The invention has the beneficial effects that: the surface gloss of the aluminum product can be obviously improved, the uniformity of the polished surface of the aluminum product is improved, and a smooth and consistent surface is obtained; the chemical polishing process does not generate harmful nitrogen oxides formed by decomposing nitric acid, and realizes the real zero emission of phosphorus and nitrogen elements from the root.
Description
Technical Field
The invention relates to an aluminum chemical polishing solution, in particular to an environment-friendly aluminum chemical polishing solution free of phosphorus and nitrogen.
Background
The aluminum alloy has the advantages of light weight, good processing performance, rich and colorful anode colors and the like, and is more and more widely applied to the field of 3C shells. Phosphoric acid-based chemical polishing solutions are most widely used for aluminum alloys, and include the classic phosphoric acid-sulfuric acid-nitric acid triacid system, the phosphoric acid-sulfuric acid yellow-smoke-free diacid system, the phosphoric acid-nitric acid diacid system, and the monophosphate polishing system.
With the increasing environmental requirements, nitric acid-or nitrate-containing chemical polishing systems, which are prone to generate nitrogen oxide (NOx) fumes, have been gradually replaced by phosphoric acid-sulfuric acid-complex additives, phosphoric acid-complex additives, and other chemical polishing systems. However, the existing phosphoric acid-based chemical polishing solution adopts a large amount of phosphoric acid and uses nitrogen-containing compounds as additives to different degrees, and if the waste liquid and the waste water of the compounds containing phosphorus and nitrogen are discharged into water bodies, the problem of eutrophication of the water bodies can be caused, and the ecological balance of the water bodies is damaged. Related enterprises have to bear high sewage treatment cost in order to meet higher and higher environmental protection standards.
In recent years, attempts have been made to reduce the use of phosphorus-containing compounds from the source. Chinese patent CN104388937A discloses a chemical polishing solution prepared by compounding tartaric acid, sodium persulfate and nitrogen-containing organic brightener in a mixed solution of sulfuric acid and acrylic acid. Chinese patent CN104562019A discloses a sulfuric acid-based chemical polishing solution containing ammonium persulfate, magnesium aluminum silicate rare earth salt and a corrosion inhibitor, wherein the corrosion inhibitor relates to nitrogen-containing compounds such as hexamethylenetetramine, imidazole, triethanolamine, benzotriazole and the like. The chemical polishing solution uses sodium persulfate or ammonium persulfate which is easy to decompose quickly, and cannot be used for industrial production, and the ammonium persulfate is a nitrogen-containing compound, and other nitrogen-containing compounds are used as additives, so that the cost of sewage treatment is increased. Other chinese patents such as CN106835145A and CN104532245A also relate to nitrogen-containing compounds to varying degrees. The polishing systems also have some fatal defects, such as low light-emitting speed, high light-emitting speed attenuation, incapability of ensuring the uniformity of the surface of a workpiece, easy occurrence of spots, uneven corrosion and the like, and are not suitable for large-scale commercial use. Also, alkaline polishing solutions such as disclosed in chinese patent CN105331979A often use sodium nitrite, sodium nitrate and other nitrogen-containing compounds. At present, an alkaline chemical polishing system also has the problems of low light-emitting speed, large corrosion amount to aluminum materials in the polishing process, poor surface texture of the polished aluminum materials and the like.
Therefore, the existing chemical polishing technology for the aluminum material cannot radically use any phosphorus and nitrogen compounds, fundamentally avoids the discharge of phosphorus and nitrogen elements, and cannot achieve the unification of green environmental protection and polishing performance, thereby relieving the sewage treatment pressure of related enterprises.
Disclosure of Invention
The invention aims to provide an environment-friendly chemical polishing solution which does not contain phosphorus element and nitrogen element, can ensure that the surface of an aluminum product can obtain sufficient luster and uniform appearance, and has no problems of flow marks, washout, pockmarks, corrosion spots and the like.
An environment-friendly aluminum material chemical polishing solution which does not contain phosphorus and nitrogen elements, wherein the chemical polishing solution comprises the following components in percentage by weight:
further, the metal salt is one or a combination of a plurality of kinds of salts of transition metal elements in IB group, IIB group, VIB group and VIII group.
Further, the metal salt may be added to the chemical polishing solution in the form of a combination of one or more of a sulfate, a carbonate, an organic acid salt, an oxysalt, an oxide, a hydroxide, and a simple metal of the corresponding metal.
Further, the sulfonic acid is one or more of alkyl sulfonic acid, benzene sulfonic acid, alkyl benzene sulfonic acid and phenol sulfonic acid.
Furthermore, the complexing agent is an organic matter containing no phosphorus element and nitrogen element.
Further, the organic matter without phosphorus and nitrogen is one or more of hydroxybenzoic acid and derivatives thereof, and hydroxyl-containing mono-or poly-acid and derivatives thereof.
The chemical polishing solution takes sulfuric acid and sulfonic acid as a basic system, and the system has excellent polishing performance, ideal light emitting speed and stable performance. The specific metal salt adopted by the invention can obviously improve the surface gloss of the aluminum material, improve the uniformity of the polished surface of the aluminum material, obtain a smooth and consistent surface and avoid uneven corrosion phenomena, such as white spots, mottling and other undesirable phenomena.
The specific complexing agent adopted by the invention can improve the solubility of metal salt and aluminum ions which are continuously dissolved out in the chemical polishing process in the chemical polishing solution, prevent the metal salt and the aluminum ions from being separated out and adsorbed on the surface of the aluminum material, and avoid influencing the polishing effect of the aluminum material, thereby stabilizing the performance of the polishing solution and continuously obtaining sufficient luster and uniform appearance on the surface of the aluminum material. More importantly, the chemical polishing solution does not use compounds containing phosphorus and nitrogen, not only does not generate harmful nitrogen oxides formed by decomposition of nitric acid in the chemical polishing process, but also fundamentally realizes real zero discharge of the phosphorus and the nitrogen, does not cause eutrophication of water, and meets the requirements of ecological environment protection.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides an environment-friendly aluminum material chemical polishing solution free of phosphorus and nitrogen, which is obtained by taking sulfuric acid and sulfonic acid as a basic system and matching with a specific metal salt and a specific complexing agent.
The chemical polishing solution of the invention adopts sulfuric acid and sulfonic acid as a basic system, and the basic system has excellent chemical polishing performance, is beneficial to continuous chemical polishing and continuously obtains a high-quality polished surface. The content of sulfuric acid in the chemical polishing solution is 500-1500g/L, and the content of sulfonic acid is 50-800 g/L. When the content of the sulfuric acid or the sulfonic acid deviates from the above range, it is difficult to maintain the continuous polishing performance of the chemical polishing bath solution, and problems such as too low light-emitting speed, insufficient metal texture on the surface of the aluminum material, and the like may occur.
The sulfonic acid adopted by the chemical polishing solution is one or a combination of more of alkyl sulfonic acid, benzene sulfonic acid, alkyl benzene sulfonic acid and phenol sulfonic acid. Examples of the alkylsulfonic acid include methanesulfonic acid, ethanesulfonic acid, propylsulfonic acid, 2-ethylhexylsulfonic acid, and dodecylsulfonic acid. Examples of the alkylbenzene sulfonic acid include p-toluene sulfonic acid, o-toluene sulfonic acid, m-ethylbenzene sulfonic acid, and dodecylbenzene sulfonic acid. Examples of the phenolsulfonic acid include phenol-4-sulfonic acid, 2-methylphenol-4-sulfonic acid, phenol-2, 4-disulfonic acid, and the like.
The chemical polishing liquid of the present invention has specific metal salt of one or several kinds of transition metal element salt in IB group, IIB group, VIB group and VIII group. Further, the metal salt is preferably selected from the group consisting of copper elements of group IB, lanthanides of group IIB, iron, cobalt and nickel elements of group VIB, and molybdenum and tungsten elements of group VIB. Further, the metal is particularly preferably selected from the group consisting of group IB copper, group VIB iron, cobalt and nickel, and group VIB molybdenum and tungsten salts.
The metal salt may be added to the chemical polishing solution in the form of a combination of one or more of a sulfate, a carbonate, an organic acid salt, an oxysalt, an oxide, a hydroxide, and a simple metal of the corresponding metal. When the metal salt is added to the chemical polishing solution of the present invention in the form of an oxide, a hydroxide or a simple metal, the metal oxide, the metal hydroxide or the simple metal can react with the acidic component in the chemical polishing solution to convert into the metal salt.
The metal salt adopted by the invention can obviously improve the surface gloss of the aluminum material, improve the uniformity of the polished surface of the aluminum material, obtain a smooth and consistent surface and avoid uneven corrosion phenomena, such as white spots, mottling and other undesirable phenomena. The content of the metal salt in the chemical polishing solution is 0.01-100 g/L. When the content of the metal salt is lower than the range, the promotion effect on the chemical polishing solution is very limited; on the contrary, when the content of the metal salt is higher than the range, the metal salt is more than the solubility in the chemical polishing solution and is easily precipitated and precipitated on the surface of the aluminum material, thereby affecting the chemical polishing effect.
Among the salts of group IB elements of copper and group VIB elements of iron, cobalt and nickel, copper salts and iron salts are more preferable in order to improve the gloss of the aluminum material. The copper salt can obviously improve the surface gloss of the aluminum material. The ferric salt can improve the uniformity of the polished surface of the aluminum material, obtain a smooth and consistent surface and avoid uneven corrosion phenomena, such as white spots, mottling and the like. Examples of the copper salt and iron salt include salts such as copper sulfate, copper carbonate, copper acetate, ferric sulfate, and the like. Of course, as mentioned above, the metal salt can be added to the chemical polishing solution directly, or can be added in the form of copper oxide, iron oxide, copper hydroxide, iron hydroxide, copper simple substance and iron simple substance, and then converted into copper salt and iron salt by reaction in the acidic solution environment of the chemical polishing solution. The content of copper salt and iron salt is 0.01-100 g/L. If the amount of the additive is less than the above range, the effect of improving the surface gloss of the aluminum material is not achieved, and the defects of low light-emitting speed, surface pockmarks, insufficient metal texture and the like of the aluminum material are caused.
The content of the salt of the group VIB element molybdenum and tungsten is 0.01-100g/L, and preferably 0.01-50 g/L. When their content is less than this range, the surface polishing speed of the aluminum material is low and it is difficult to achieve a desired gloss effect; on the contrary, when their content is higher than this range, the solubility range of the aluminum material in the chemical polishing solution is exceeded, not only the resources are not utilized reasonably, but also the aluminum material is easy to precipitate on the surface of the aluminum material, thereby affecting the chemical polishing effect.
The specific complexing agent used in the chemical polishing solution is an organic substance which does not contain phosphorus and nitrogen, and is selected from one or more of hydroxybenzoic acid and derivatives thereof, and hydroxyl-containing monoacid or polyacid and derivatives thereof. As examples of the hydroxybenzoic acid and its derivatives, there may be mentioned o-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2, 3-dihydroxybenzoic acid, 3, 5-dihydroxybenzoic acid, 3, 4-dihydroxybenzoic acid, 2, 5-dihydroxybenzoic acid, 2, 6-dihydroxybenzoic acid, 3,4, 5-trihydroxybenzoic acid, syringic acid, vanillic acid, caffeic acid, tannic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 5-sulfosalicylic acid and the like. Examples of the hydroxyl group-containing mono-or polybasic acid and derivatives thereof include glycolic acid, hydroxypropionic acid, malic acid, lactic acid, citric acid, gluconic acid, tartaric acid, and the like.
The complexing agent used in the invention can effectively complex metal salt and aluminum ions formed by continuously dissolving the aluminum material in the chemical polishing process, improves the solubility of the metal salt and the aluminum ions in the chemical polishing solution, and prevents the metal salt and the aluminum ions from being separated out and adsorbed on the surface of the aluminum material to influence the polishing effect of the aluminum material, thereby improving the stability of the chemical polishing solution and continuously obtaining sufficient luster and uniform appearance on the surface of the aluminum material. In the chemical polishing solution, the content of the complexing agent is 1-200 g/L. If the content of the complexing agent is lower than the range, the complexing agent is not enough to complex metal salt and aluminum ions in the chemical polishing solution; on the contrary, if the content of the complexing agent is higher than the range, the problems of low light extraction speed, white spots, mottling and the like on the surface of the aluminum material are easily caused.
The method for preparing the chemical polishing solution of the present invention is not particularly limited. However, from the viewpoint of facilitating quick dissolution and uniform mixing, when the metal salt is added in the form of sulfate, carbonate, organic acid salt or oxysalt, it is preferable to first dissolve the complexing agent in water, then add the metal salt, add the sulfonic acid after uniform dissolution, and finally slowly add the sulfuric acid and stir uniformly; if the metal salt is added as a metal oxide, a metal hydroxide or a metal simple substance, preferably, the sulfonic acid is dissolved in water, then the sulfuric acid is slowly added and stirred uniformly, then the metal oxide, the metal hydroxide or the metal simple substance is added, heating and temperature rising can be assisted if necessary, and after complete dissolution, the complexing agent is added and stirred uniformly, so that the chemical polishing solution of the invention can be obtained. On the premise of not damaging the purpose and effect of the invention, other additives, such as surface wetting agent and defoaming agent, which do not contain phosphorus element and nitrogen element, can be further added, and are not described herein again.
The temperature and time of the polishing operation of the chemical polishing solution of the present invention are not particularly limited. However, the polishing operation temperature is preferably 100 to 140 ℃ and more preferably 110 to 120 ℃ from the viewpoint of enhancing the polishing rate and the polishing effect. If the polishing operation temperature is lower than 100 ℃, the polishing speed cannot meet the requirement, and the metal texture of the surface of the aluminum material is not strong enough; if the polishing temperature exceeds 140 ℃, the corrosion rate of the aluminum material is too high, and the probability of surface roughening or other defects is increased. The polishing time is preferably 20-300 seconds, and the polishing time and the polishing times can be properly adjusted according to different aluminum material surfaces, so that excellent polishing effect can be obtained.
In the embodiment of the invention: the preparation sequence of the chemical polishing solution is as follows: water, a complexing agent and a metal salt are sequentially added into a container or a tank body and are uniformly stirred, then sulfonic acid is added, finally sulfuric acid is slowly added, and the mixture is uniformly stirred until the sulfuric acid is completely dissolved, so that the chemical polishing solution of the embodiment of the invention is obtained, wherein the content of each component is listed in reference table 2.
The application of the chemical polishing solution of the invention is as follows: the chemical polishing solution of the embodiment of the invention is heated to a preset temperature and is kept at the constant temperature. And carrying out iron sand or zircon sand blasting treatment on aluminum materials such as the mobile phone middle frame, the notebook panel or the aluminum profile to obtain 6-20 unequal initial gloss. Firstly, cleaning dirt on the surface of the aluminum material, then immersing the aluminum material into chemical polishing solution for polishing, swinging or standing for 90-120 seconds, taking out the tank liquor, stopping for 10-20 seconds, and then performing procedures such as water washing, neutralization and the like. The specific chemical polishing process flow refers to table 1. Recently, the gloss of the surface of an aluminum material is measured by a gloss meter, and the surface of the aluminum material is evaluated visually for problems of appearance defects such as flow marks, pocks, and stains.
TABLE 1 chemical polishing process for aluminum materials
TABLE 2 chemical polishing solution composition, working conditions and evaluation of effects of examples of the present invention
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The environment-friendly aluminum material chemical polishing solution is characterized by comprising the following components in percentage by weight:
2. the environment-friendly aluminum chemical polishing solution containing no phosphorus and nitrogen as claimed in claim 1, wherein the metal salt is one or more of group IB, group IIB, group VIB and group VIII transition metal salts.
3. The environmentally friendly aluminum material chemical polishing solution of claims 1 and 2, wherein the metal salt can be added to the chemical polishing solution in the form of a combination of one or more of sulfate, carbonate, organic acid salt, oxysalt, oxide, hydroxide and simple metal of the corresponding metal.
4. The environment-friendly aluminum material chemical polishing solution containing no phosphorus element and no nitrogen element according to claim 1, wherein the sulfonic acid is one or more of alkyl sulfonic acid, benzene sulfonic acid, alkyl benzene sulfonic acid, and phenol sulfonic acid.
5. The environment-friendly aluminum material chemical polishing solution free of phosphorus and nitrogen according to claim 1, wherein the complexing agent is an organic substance free of phosphorus and nitrogen.
6. The environmentally friendly aluminum material chemical polishing solution of claim 5, wherein the organic material is one or more selected from hydroxybenzoic acid and its derivatives, hydroxyl group-containing mono-or poly-acids, and their derivatives.
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