CN109487259B - Preparation method of chromium-free silane film before aluminum coil coating - Google Patents
Preparation method of chromium-free silane film before aluminum coil coating Download PDFInfo
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- CN109487259B CN109487259B CN201811626734.5A CN201811626734A CN109487259B CN 109487259 B CN109487259 B CN 109487259B CN 201811626734 A CN201811626734 A CN 201811626734A CN 109487259 B CN109487259 B CN 109487259B
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
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Abstract
The invention discloses a preparation method of a chromium-free silane film before coating of an aluminum coil. The method comprises the following steps: the method comprises the following steps: 1) cleaning; 2) rinsing with water: 3) washing with deionized water; 4) direct spraying and pure water washing: the time is 10 seconds, and the temperature is normal temperature; 5) silane treatment: processing the workpiece cleaned by the pure water in the step 4) in a roller coating, spraying or soaking mode; 6) drying: and drying by hot air at 80-120 ℃. Compared with the prior art, the preparation method of the chromium-free silane film before coating the aluminum coil material has the following beneficial effects: the conversion film has good corrosion resistance, further reduces the treatment of waste water, is free of chromium and is environment-friendly.
Description
Technical Field
The invention relates to a preparation method of a chromium-free silane film, in particular to a preparation method of a chromium-free silane film before coating of an aluminum coil.
Background
The roll coating is mainly used in the coating of aluminum coils. The specific production process of the color coating of the aluminum coiled material comprises the following steps: coating the same thickness of coating on the surface of the pretreated aluminum coil material by a precise coating machine, entering a drying oven with an exhaust device at a constant speed, curing by adopting an infrared ray or hot air circulating baking process, and crosslinking to form a film at a specific temperature to finally prepare a complete coating film with a certain thickness.
The metal coil color coating process has a history of nearly 100 years, the color coating process is formally started in the last 80 th century in China, and along with the economic development of China, the process is rapidly developed in nearly ten years, and has wide application in the aspects of buildings, automobiles, household appliances, office appliances and the like. In the aluminum product color coating production, an aluminum coil continuously goes through the steps of degreasing cleaning, chemical film conversion, painting, curing and the like. The most important link of the surface treatment is chemical conversion film treatment, and at present, chromium passivation technology is mostly adopted for treatment.
In the prior art, the following technical problems exist: the chromium passivation treatment contains chromium, and a large amount of overflow water is needed to rinse the aluminum piece after the treatment. Among them, hexavalent chromium has been proven to be a carcinogenic heavy metal, and thus its content is strictly regulated in the ROHS directive of the european union; the trivalent chromium which is relatively environment-friendly still has certain toxicity and can still be converted into hexavalent chromium in the environment.
In order to meet the increasingly strict requirements on the environment, save resources in the production treatment process, and enable people to realize the importance of adopting a phosphorus-free, chromium-free, heavy metal-free, slag-free and normal-temperature treatment process by using the least consumption of chemical substances and normal-temperature non-heating treatment in the production treatment process, the invention provides a preparation method of a chromium-free silane film before coating of an aluminum coil material, which can replace the traditional chromium passivation treatment.
Disclosure of Invention
The invention aims to provide a preparation method of a chromium-free silane film before coating of an aluminum coil, which not only has good corrosion resistance of a conversion film, but also further reduces the treatment of waste water, is chromium-free and is environment-friendly.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a chromium-free silane film before coating of an aluminum coil comprises the following steps:
1) cleaning: immersing the aluminum coil in an acid/alkaline cleaning solution at normal temperature for 30-60 seconds;
2) rinsing with water: soaking the workpiece cleaned in the step 1) in water, wherein the water is kept overflowing, the pH value is 5-92, the temperature is normal temperature, and the time is 30-60 seconds;
3) washing with deionized water: cleaning the workpiece treated in the step 2) with deionized water, wherein the dripping conductivity is less than 20us/cm, the temperature is normal temperature, and the time is 10 seconds;
4) direct spraying and pure water washing: the time is 10 seconds, and the temperature is normal temperature;
5) silane treatment: the silane treatment liquid comprises the following components in parts by mass:
2-20 parts of a silane coupling agent,
0 to 2 parts of hydroxylamine, by weight,
0.1 to 2 parts of titanium sol,
0.1 to 2 parts of zirconium sol,
1-5 parts of ethanol or methanol,
diluting the silanization treatment liquid into an aqueous solution with the mass fraction of 0.2-2%, controlling the pH value to be 4.0-7.0 by a pH regulator, and controlling the temperature to be normal temperature for the following time: treating the workpiece cleaned by the pure water in the step 4) in a roller coating, spraying or soaking mode for 1-60 seconds;
6) drying: and drying by hot air at 80-120 ℃.
As a further improvement, in the step 5), the silane coupling agent is any two of glycidoxypropyltrimethylsilane, 1, 2-bis (trimethoxysilyl) ethane, 1-10 parts of bis [3- (triethoxysilane) propyl ] amine and aminopropyltriethoxysilane.
As a further improvement, the pH regulator is any two of hydrofluoric acid, tannic acid, lactic acid and hydroxyethylidene diphosphonic acid.
As a further improvement, the pH regulator comprises 0.03-0.05 part of hydrofluoric acid and 0.03-0.05 part of tannic acid.
As a further improvement, the pH regulator is 0.5-1 part of lactic acid and 0.8-3 parts of hydroxyethylidene diphosphonic acid.
As a further improvement, the silane coupling agent is 1-10 parts of glycidyl ether oxypropyltrimethylsilane and 1-10 parts of 1, 2-bis (trimethoxysilyl) ethane.
As a further improvement, the silane coupling agent is 1-10 parts of aminopropylmethyldimethoxysilane and 1-10 parts of bis [3- (triethoxysilane) propyl ] amine.
The preparation method of the chromium-free silane film before coating of the aluminum coil material has the following beneficial effects:
1. after the silane treatment of the aluminum material, the water washing is not needed, the water is saved, the process treatment at normal temperature is realized, compared with the chromizing process, the process period is shortened, and the occupied area of equipment is saved
2. The silane process has short treatment time and high silane film forming efficiency, and improves the production efficiency and the productivity;
3. the silane treated aluminum material has large surface area, less chemical consumption and low use cost;
4. the use concentration of chemicals is low, the use cost is low, and the environmental pollution is low;
5. silane treatment is carried out in the bath solution, the bath solution is simple to monitor, slag removal is not needed, the use is convenient, and the labor is saved;
6. the preparation method of the chromium-free silane film before coating the aluminum coil has no reaction by-product in the treatment process, the chemical composition of the treatment liquid is stable, the treatment quality is reliable, and the silane treatment material does not contain harmful substances such as heavy metal and the like, is an environment-friendly product, is environment-friendly and does not produce pollution.
Detailed Description
In order to make the purpose, technical scheme and advantages of the invention clearer, the invention is further described with reference to embodiments 1 to 6 as follows:
1) cleaning: and immersing the aluminum coil in an acid/alkaline cleaning solution at normal temperature for 30-60 seconds.
2) Rinsing with water: immersing the workpiece cleaned in the step 1) in water, wherein the water is kept overflowing, the pH value is 5-9, the temperature is normal temperature, and the time is 30-60 seconds.
3) Washing with deionized water: and (3) cleaning the workpiece treated in the step 2) by using deionized water, wherein the dripping water conductivity is less than 20us/cm, the temperature is normal temperature, and the time is 10 seconds.
4) Direct spraying and pure water washing: time 10 seconds, temperature normal temperature.
5) Silane treatment: the silane treatment liquid comprises the following components in parts by mass:
2-20 parts of a silane coupling agent,
0 to 2 parts of hydroxylamine, by weight,
0.1 to 2 parts of titanium sol,
0.1 to 2 parts of zirconium sol,
1-5 parts of ethanol or methanol,
diluting the silanization treatment liquid into an aqueous solution with the mass fraction of 0.2-2%, controlling the pH value to be 4.0-7.0 by a pH regulator, and controlling the temperature to be normal temperature for the following time: and (3) treating the workpiece cleaned by the pure water in the step 4) in a roller coating, spraying or soaking mode for 1-60 seconds.
The raw material components in step 5) in examples 1 to 3 are shown in Table 1
TABLE 1 examples 1-3 raw material components in step 5)
The raw material components in step 5) in examples 4 to 6 are shown in Table 2
TABLE 2 compositions of the raw materials in examples 4 to 6, step 5)
TABLE 3 test results of chromium-free conversion films of examples 1 to 6
As shown in Table 3, in the salt spray resistance test, the results of the tests on the chromium-free silane films before coating of the aluminum coil materials prepared in examples 1-6 are all 1, and the standard requirements are met. Test results show that the preparation method of the chromium-free silane film before coating the aluminum coil can form a compact protective film layer on the surface of the aluminum coil before coating, so that the protective performance of the aluminum coil is enhanced, and the salt spray resistance is good. The coating has good flexibility and impact resistance, the impact resistance of example 2 is as high as 60 kg-cm, and the high-temperature boiling test and the high-temperature acid resistance test are both qualified.
Moreover, the pH regulator selected by the invention not only can regulate the pH value, but also can form a complex with a zirconium or titanium compound or dehydrate with a metal hydroxylate to form a polymer, carry out doping modification on a silane film, and simultaneously can form a combined film with an aluminum substrate.
In conclusion, the chromium-free silane film prepared by the method of the invention before coating of the aluminum coil has excellent adhesive force and impact resistance, and can fully meet the adhesive force requirement of the aluminum coil. The chrome-free silane film prepared in the embodiment 1-6 before coating is excellent in comprehensive performance; in addition, the preparation process of the invention completely uses environment-friendly nontoxic components, and a large amount of overflow water is not needed to rinse the aluminum piece after treatment, thereby not only avoiding the pollution to the environment and the harm to human bodies, but also saving water resources.
The above description is only for the preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention are within the scope of the present invention.
Claims (1)
1. The preparation method of the chromium-free silane film before coating the aluminum coil is characterized by comprising the following steps of:
1) cleaning: immersing the aluminum coil in an acid/alkaline cleaning solution at normal temperature for 30-60 seconds;
2) rinsing with water: soaking the workpiece cleaned in the step 1) in water, wherein the water is kept overflowing, the pH value is 5-9, the temperature is normal temperature, and the time is 30-60 seconds;
3) washing with deionized water: cleaning the workpiece treated in the step 2) with deionized water, wherein the dripping conductivity is less than 20us/cm, the temperature is normal temperature, and the time is 10 seconds;
4) direct spraying and pure water washing: the time is 10 seconds, and the temperature is normal temperature;
5) silane treatment: the silane treatment liquid comprises the following components in parts by mass:
in the step 5), the silane coupling agent is 1-10 parts of glycidoxypropyltrimethylsilane and 1-10 parts of 1, 2-bis (trimethoxysilyl) ethane or 1-10 parts of aminopropylmethyldimethoxysilane and 1-10 parts of bis [3- (triethoxysilane) propyl ] amine;
1-2 parts of hydroxylamine, namely,
0.1 to 2 parts of titanium sol,
0.1 to 2 parts of zirconium sol,
1-5 parts of ethanol or methanol,
diluting the silanization treatment liquid into an aqueous solution with the mass fraction of 0.2-2%, controlling the pH value to be 4.0-7.0 by a pH regulator, and controlling the temperature to be normal temperature for the following time: treating the workpiece cleaned by the pure water in the step 4) in a roller coating, spraying or soaking mode for 1-60 seconds;
6) drying: drying with hot air at 80-120 ℃;
the pH regulator comprises 0.03-0.05 part of hydrofluoric acid and 0.03-0.05 part of tannic acid;
or the pH regulator comprises 0.5-1 part of lactic acid and 0.8-3 parts of hydroxyethylidene diphosphonic acid.
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| CN201811626734.5A CN109487259B (en) | 2018-12-28 | 2018-12-28 | Preparation method of chromium-free silane film before aluminum coil coating |
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| CN109487259B true CN109487259B (en) | 2021-05-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102747355B (en) * | 2012-07-27 | 2015-01-14 | 重庆长宇金属表面处理技术有限公司 | Metal surface vitrification agent and application method thereof |
| JP6318248B2 (en) * | 2013-08-06 | 2018-04-25 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ | Coating composition for the preparation of metal surfaces, its production and its use |
| CN103469192A (en) * | 2013-09-04 | 2013-12-25 | 余庆县兴达家具制造有限公司 | Metal surface treatment agent |
| CN104233273A (en) * | 2014-09-26 | 2014-12-24 | 山东大学 | Chromium-free silicon passivation solution for passivating aluminum or aluminum alloy surface as well as preparation and using methods |
| CN105088218B (en) * | 2015-09-12 | 2018-04-10 | 杭州萧山金润表面活性材料厂 | A kind of metal surface coating process |
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