CN111485240B - Pretreatment liquid and pretreatment method for aluminum profile spraying - Google Patents
Pretreatment liquid and pretreatment method for aluminum profile spraying Download PDFInfo
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- CN111485240B CN111485240B CN202010278159.5A CN202010278159A CN111485240B CN 111485240 B CN111485240 B CN 111485240B CN 202010278159 A CN202010278159 A CN 202010278159A CN 111485240 B CN111485240 B CN 111485240B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/102—Pretreatment of metallic substrates
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses an aluminum profile spraying pretreatment liquid and a spraying pretreatment method, wherein the pretreatment liquid comprises an oil removal polishing liquid and a modification liquid: the oil removal polishing solution comprises: 5-30 g/L oxalic acid, 0.5-4 g/L ammonium bifluoride, 0.001-0.01 g/L surfactant and 0.05-0.5 g/L auxiliary agent; the modifying liquid is 0.2-5 g/l polyvinyl alcohol aqueous solution. The spray coating pretreatment method of the aluminum profile comprises the steps of degreasing and polishing the aluminum profile by using the degreasing polishing solution to form a composite salt film protective layer; and forming a layer of hydrophobic modified film on the composite salt film protective layer in the modified liquid. The invention carries out pretreatment on the aluminum profile before spraying, has simple treatment method, low production cost, zero emission and zero pollution, and the treated modified film has hydrophobicity, thereby improving the binding force with the sprayed organic film.
Description
Technical Field
The invention relates to the technical field of aluminum alloy surface treatment, in particular to an aluminum profile spraying pretreatment technology.
Background
The aluminum alloy surface spraying process refers to a process of forming a coating with a certain thickness on the aluminum alloy surface by using an organic polymer material through a certain process method. The aluminum alloy spraying has three specific functions: 1. protection; 2. decoration; 3. other functions: certain special functions such as insulation, conductivity and the like are obtained through the coating properties.
The prior art pretreatment processes are roughly divided into oil removal, alkali washing, acid washing, chromizing and chromium-free passivation (fluorozirconates, organic-inorganic composite types and silanes), a large amount of water is needed between each process, and after a period of use of the treatment liquid, the treatment liquid must be replaced or renewed after being discharged due to the continuous rise of aluminum ions or the accumulation of certain substances in the treatment liquid. The pretreatment process in the prior art has the advantages that the whole production process is complex, a large amount of waste water and solid waste are generated in the production process, and the waste water and the solid waste comprise a large amount of hazardous waste, so that the production process flow is complex, the production control requirement is high, a large amount of pollutants are brought to the environment, a large amount of chemical raw materials and water are consumed, and the pretreatment is carried out, wherein each ton of Al is washed and discharged.
And the film thickness of the process treatment after the pretreatment in the prior art: chromium film 1.1-3.8mg/dm 2; chromium-free: organic type 20-160mg/m 2; inorganic 5-20g/m 2; 20-180 mg/m 2 of organic acid-titanium system; 20-180 mg/m 2 of organic-zirconium and titanium series; the film thickness of the process treatment after the pretreatment of the existing chromium-free passivation technology is less than 200mg/m 2; and the corrosion resistance is poor, the combination of the subsequent spraying treatment and the sprayed organic film is common, the adhesive force is low, and the film corrosion is easy to generate.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows: aiming at the defects existing in the prior art, the pretreatment liquid for aluminum profile spraying is provided, is used for pretreatment before aluminum profile spraying, has low production cost, zero emission and zero pollution, and the treated modified film has hydrophobicity, so that the binding force with a spraying organic film is improved.
The second technical problem to be solved by the invention is as follows: aiming at the defects existing in the prior art, the method for pre-treating the aluminum profile before spraying is provided, the method for pre-treating the aluminum profile before spraying is simple, the production cost is low, zero emission and zero pollution are realized, and the treated modified film has hydrophobicity, so that the binding force with a spraying organic film is improved.
In order to solve the first technical problem, the technical scheme of the invention is as follows:
An aluminum profile spraying pretreatment liquid comprises an oil removal polishing liquid and a modification liquid:
Wherein, the oil removal polishing solution comprises the following components: 5-30 g/L oxalic acid, 0.5-4 g/L ammonium bifluoride, 0.001-0.01 g/L surfactant and 0.05-0.5 g/L auxiliary agent;
the modifying liquid is 0.2-5 g/l polyvinyl alcohol aqueous solution.
As a preferable technical scheme, the surfactant comprises one or more of alkylphenol ethoxylates, octylphenol ethoxylates, nonylphenol ethoxylates, glycerin fatty acid esters and sorbitan fatty acid esters; the auxiliary agent comprises sodium salt: sodium nitrite, sodium oxalate, sodium fluoride, sodium carbonate, sodium bicarbonate and sodium sulfate.
As an improved technical scheme, the equilibrium concentration of Al 3+ in the oil removal polishing solution and the modified solution is less than 1g/L.
As an improved technical scheme, the oil removal polishing solution and the modifying solution are used in the sequence of firstly removing the oil and then modifying the polishing solution.
In the oil removal polishing treatment process of the aluminum profile, grease enters treatment liquid, under the combined action of oxalic acid, fluoride ions, ammonia ion surfactant, oxidation auxiliary agent and the like, a transparent fiber with the specific gravity of less than 1 is generated, the main component is polyamide, and the updating and replacement caused by the increase of the concentration of the grease in the fiber removal tank liquid are avoided by periodic filtration. The sediment (the quantity is very small) caused by the foreign impurities is removed every year, and the inverted groove is removed. The invention has no pollution when no discharge is carried out, and the invention has the difference with the prior art that the tank liquor does not need to be replaced and updated, and flocculent fibers polymerized by grease can be removed by periodic filtration, thereby ensuring the clear and sustainable reuse of the tank liquor and solving the environmental protection problem.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
the spraying pretreatment method of the aluminum profile uses the pretreatment liquid and comprises the following steps:
(1) And (3) oil removal and polishing: placing the aluminum profile to be treated in oil removal polishing solution, reacting until bubbles emerge in the treatment solution, and then continuing the soaking reaction for 1-10 min, wherein the surface of the aluminum profile and the low-lying part of the profile are covered with a uniform composite salt film protective layer;
(2) Film modification: and dripping the aluminum profile subjected to oil removal and polishing, then placing the aluminum profile into the modifying solution, and soaking for 1-5 min to form a layer of hydrophobic modified film on the composite salt film protective layer.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
The aluminum profile spraying pretreatment liquid comprises oil removal polishing liquid and modification liquid: the oil removal polishing solution comprises the following components: 5-30 g/L oxalic acid, 0.5-4 g/L ammonium bifluoride, 0.001-0.01 g/L surfactant and 0.05-0.5 g/L auxiliary agent; the modifying liquid is 0.2-5 g/l polyvinyl alcohol aqueous solution. According to the pretreatment liquid, oil stains and natural oxidation on the surface of the aluminum profile can be removed by carrying out oil removal and polishing on the aluminum profile, fluoride ions, aluminum oxide on the surface of the aluminum profile and aluminum ions generated by aluminum are captured and deposited at the low-lying position on the surface of the profile by oxalic acid, so that mechanical lines of the profile are filled, a layer of composite salt film protective layer of aluminum oxalate, aluminum oxide and aluminum fluoride is formed on the surface of the profile, then a layer of modified film is formed on the surface of the composite salt film protective layer by modifying liquid, esterification reaction is generated in the curing process by utilizing-OH of polyvinyl alcohol in the modified liquid and free C=O-OH groups in the composite salt film, the hydrophobicity of the film is improved, the boiling resistance adhesion of an organic film and the composite salt film is improved, and the binding force with a sprayed organic film is improved.
The oil removal and polishing are completed in one step, the steps are simplified, the water washing step between each step in the prior art is saved, the oil removal and polishing are directly modified by dripping, the modified drying can be directly sprayed and cured, compared with the prior art, the waste water is reduced by 80%, the solid waste is reduced by 90%, the heavy metal emission is avoided, the pretreatment weight of the product is not reduced, and instead, the pretreatment weight is increased by about 1 kg per ton of section bar; the oil removal polishing solution and the modified solution do not need to be replaced regularly, only the oil removal polishing solution and the modified solution need to be increased according to consumption conditions, no waste water is discharged, no hazardous waste is generated, chemical raw materials and water resources are saved, and the production cost is reduced.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is a graph of the surface topography of a composite film formed after degreasing, polishing and modification in accordance with the present invention.
Detailed Description
The application is further illustrated in the following, in conjunction with the accompanying drawings and examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The attached drawing is a morphology diagram of the composite film formed by degreasing, polishing and modifying the aluminum profile, which is amplified by five million times.
Example 1
An aluminum profile spraying pretreatment liquid comprises an oil removal polishing liquid and a modification liquid:
the oil removal polishing solution comprises the following components: oxalic acid 10g/L, ammonium bifluoride 2.0g/L, surfactant octyl phenol polyoxyethylene ether 0.004g/L and auxiliary sodium nitrite 0.18g/L;
The modifying liquid is 2.5g/l polyvinyl alcohol aqueous solution;
The equilibrium concentration of Al 3+ in the oil removal polishing solution and the modification solution is 0.16g/L.
Example 2
An aluminum profile spraying pretreatment liquid comprises an oil removal polishing liquid and a modification liquid:
the oil removal polishing solution comprises the following components: 20g/L oxalic acid, 3.0g/L ammonium bifluoride, 0.003g/L surfactant glycerin fatty acid ester and 0.15g/L auxiliary sodium oxalate;
the modifying liquid is a polyvinyl alcohol aqueous solution with the concentration of 3.3 g/l;
the equilibrium concentration of Al 3+ in the oil removal polishing solution and the modification solution is 2.5g/L.
Example 3
An aluminum profile spraying pretreatment liquid comprises an oil removal polishing liquid and a modification liquid:
The oil removal polishing solution comprises the following components: oxalic acid 22g/L, ammonium bifluoride 1.2g/L, surfactant sorbitan fatty acid ester 0.01g/L and auxiliary sodium fluoride 0.35g/L;
The modifying liquid is 4.0g/l polyvinyl alcohol aqueous solution;
the equilibrium concentration of Al 3+ in the oil removal polishing solution and the modification solution is 4.0g/L.
Example 4
A spray pretreatment method of aluminum profiles uses the pretreatment liquid described in the embodiment 1, and comprises the following steps:
(1) And (3) oil removal and polishing: placing the aluminum profile to be treated in oil removal polishing solution, reacting until bubbles begin to emerge in the treatment solution, and then continuing to soak the aluminum profile for 5.5min, wherein the surface of the aluminum profile and the low-lying part of the profile are covered with a uniform composite salt film protective layer;
(2) Film modification: and dripping the aluminum profile subjected to oil removal and polishing, then placing the aluminum profile into the modifying solution, and soaking for 3min to form a layer of hydrophobic modified film on the composite salt film protective layer.
Example 5
The pretreatment method for spraying the aluminum profile uses the pretreatment liquid in the embodiment 2, and comprises the following steps:
(1) And (3) oil removal and polishing: placing the aluminum profile to be treated in oil removal polishing solution, reacting until bubbles emerge in the treatment solution, then continuing to soak the aluminum profile for 3min, and covering the surface of the aluminum profile and the low-lying part of the profile with a uniform composite salt film protective layer;
(2) Film modification: and dripping the aluminum profile subjected to oil removal and polishing, then placing the aluminum profile into the modifying solution, soaking for 4min, and forming a layer of hydrophobic modified film on the composite salt film protective layer.
Comparative example 1
Comparative example 1 differs from example 5 in that the film modification of step (2) was not performed and only degreasing and polishing were performed to form a composite salt film protective layer.
Salt spray resistance test and comparison are carried out on the aluminum alloy sections modified in the examples 1-5 and the aluminum alloy section not modified by the film in the comparative example 1 according to GB/T5237.4, after the soaking test is carried out for 48 hours, the aluminum alloy sections modified in the examples 1-5 have no defects of foaming, delamination, wrinkling and the like, and after the aluminum alloy sections are boiled in water for 2 hours under 0.1MP, the film adhesion is 0 grade and the impact resistance is qualified. The protective film of comparative example 1 was not modified, but had a film adhesion of 0 grade in the dry state, and was prone to foaming, delamination, and wrinkling after the water boiling test.
Claims (2)
1. A spray coating pretreatment method of an aluminum profile is characterized by using pretreatment liquid, and comprises the following steps of;
the pretreatment liquid comprises oil removal polishing liquid and modifying liquid:
(1) And (3) oil removal and polishing: placing the aluminum profile to be treated in oil removal polishing solution, reacting until bubbles emerge in the treatment solution, and then continuing the soaking reaction for 1-10 min, wherein the surface of the aluminum profile and the low-lying part of the profile are covered with a uniform composite salt film protective layer; the oil removal polishing solution comprises the following components: 5-30 g/L oxalic acid, 0.5-4 g/L ammonium bifluoride, 0.001-0.01 g/L surfactant and 0.05-0.5 g/L auxiliary agent; the surfactant comprises one or more of alkylphenol ethoxylates, octylphenol ethoxylates, nonylphenol ethoxylates, glycerin fatty acid esters and sorbitan fatty acid esters; the auxiliary agent comprises sodium salt: one or more of sodium nitrite, sodium oxalate, sodium fluoride, sodium carbonate, sodium bicarbonate and sodium sulfate;
(2) Film modification: dripping the degreased and polished aluminum profile into the modifying liquid, soaking for 1-5 min, and forming a layer of hydrophobic modified film on the composite salt film protective layer; the modifying liquid is 0.2-5 g/l polyvinyl alcohol aqueous solution.
2. The pretreatment method for spraying of aluminum profiles as claimed in claim 1, wherein: the equilibrium concentration of Al 3+ in the oil removal polishing solution and the modifying solution is less than 1g/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102666716A (en) * | 2009-12-28 | 2012-09-12 | 阿克佐诺贝尔化学国际公司 | Functionalized polyvinyl alcohol films |
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| JP3766707B2 (en) * | 1995-10-25 | 2006-04-19 | ディップソール株式会社 | Water-soluble composition for water-repellent treatment of zinc and zinc alloy and water-repellent treatment method |
| JP2002086059A (en) * | 2000-09-13 | 2002-03-26 | Unitika Ltd | Coated metal material and manufacture of the same |
| US9085664B2 (en) * | 2004-12-28 | 2015-07-21 | The Nippon Synthetic Chemical Industry Co., Ltd. | Polyvinyl alcohol film, and polarizing film and polarizing plate using the same |
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| CN109749666B (en) * | 2018-12-17 | 2021-06-25 | 恒美光电股份有限公司 | Adhesive for high-water-resistance and high-weather-resistance polarizing plate, polarizing plate and preparation method |
| CN109852978B (en) * | 2019-03-26 | 2021-04-06 | 高瑞安 | Aluminum alloy oil-removing and polishing two-in-one treatment solution and method for performing oil-removing and polishing treatment on aluminum alloy |
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