CN110560344B - Aluminum alloy surface ATS composite membrane compatible with FEVE fluorocarbon powder coating and preparation method thereof - Google Patents
Aluminum alloy surface ATS composite membrane compatible with FEVE fluorocarbon powder coating and preparation method thereof Download PDFInfo
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- CN110560344B CN110560344B CN201910676652.XA CN201910676652A CN110560344B CN 110560344 B CN110560344 B CN 110560344B CN 201910676652 A CN201910676652 A CN 201910676652A CN 110560344 B CN110560344 B CN 110560344B
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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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
- B05D1/06—Applying particulate materials
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- 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
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Abstract
The invention relates to the field of surface protection of aluminum alloy, in particular to a preparation method of an ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of aluminum alloy, which comprises the following steps: spraying and cleaning the aluminum alloy for 3-15s at normal temperature by using a degreasing agent, removing oil stains on the surface of the aluminum alloy, and keeping a natural oxide film (Al) on the surface of the aluminum alloy2O30.01-0.1 μm); coating titanium dioxide passivation solution on the surface of the pretreated aluminum alloy, and naturally airing or drying to form TiO2A conversion film (0.1-0.5 μm); adding TiO into the mixture2Soaking the conversion film in silane modified solution, and drying to form a silane gel layer (SiO)20.5-2 μm) protective film. The invention utilizes the alumina protective film and TiO2Conversion film and silane gel layer protective film for realizing Al-based alloy material2O3‑TiO2‑SiO2The protective film has three protections (ATS for short), can be effectively compatible with FEVE fluorocarbon powder coated on the surface of the protective film, has all main performances of salt mist resistance, corrosion resistance, boiling water adhesion and the like reaching the standard, and provides an effective solution for reducing the VOC emission problem by using the fluorocarbon powder to replace fluorocarbon paint.
Description
Technical Field
The invention relates to the field of surface protection of aluminum alloy, in particular to an ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of aluminum alloy and a preparation method thereof.
Background
Aluminum alloys are the most widely used class of non-ferrous materials in industry and have found a number of applications in the aerospace, automotive, mechanical manufacturing and chemical industries. However, aluminum has a weak corrosion resistance, and a corrosion prevention treatment of the surface thereof is a necessary process. Currently, most domestic enterprises consider from the aspects of technical maturity, cost saving and the like, most of the enterprises select the traditional hexavalent chromium passivation process, but hexavalent chromium is a substance with extremely strong toxicity and seriously pollutes the environment. Hexavalent chromium migrates into human body through water, soil and animals and plants, and has strong carcinogenic effect. Therefore, in order to comply with the national policy and the requirement of environmental protection, chromate pretreatment films have been slowly replaced by new chromium-free pretreatment films.
For the chromium-free pretreatment film, according to the existing research hotspot and industrial application situation, the following types mainly exist: (1) organic pretreatment membrane-silanes, the pretreatment membrane mainly comprises silane hydrolysate and polymer thereof; however, the early application situation proves that the performance of the electrostatic spraying coating obtained by utilizing the chromium-free pretreatment technology is reduced and aggravated along with the time, the durability of the coating is poor, and the electrostatic spraying coating is almost not applied to the fields of buildings, industries, electronic appliances, food and medicine packaging and the like at present; (2) the inorganic pretreatment film-zirconium/titanium system, the pretreatment film is mainly composed of inorganic fluorozirconate and fluorotitanate film forming substances; the existing application conditions prove that the pure inorganic pretreatment film has poor corrosion resistance, can not reach the index required by neutral salt spray resistance of a bare film for 48h and acetic acid after electrostatic coating for 1000h, and has almost no specific application; (3) the organic matter mainly comprises acrylic resin, silane coupling agent, tannic acid and the like, the inorganic salt mainly comprises fluotitanic acid, fluozirconic acid and the like, and the composite pretreatment film has certain application in the market, but still has the problems of compatibility with powder coating, filiform corrosion resistance and the like.
In the post-treatment process of aluminum and aluminum alloy products, fluorocarbon paint is mostly adopted as a main coating mode for engineering systems with ultra-weather resistance requirements, but the solvent type fluorocarbon coating is accompanied by the emission of a large amount of Volatile Organic Compounds (VOC) in the application process, and serious air pollution is easily caused. The fluorocarbon powder coating has the characteristics of low surface tension, small friction force, hydrophobicity, non-adhesiveness and the like due to excellent weather resistance and chemical resistance, and has the advantages of very low VOC emission and the like as the powder coating, and the application prospect of the fluorocarbon powder coating is better than that of fluorocarbon paint. The existing organic-inorganic composite pretreatment film has no compatibility with super-weather-resistant fluorocarbon powder, and the adhesion force of boiling water, impact resistance, cupping resistance, salt mist resistance and the like in various indexes required by national standards can not meet the requirements, so that the industrial implementation of replacing fluorocarbon paint with fluorocarbon powder to solve the VOC (volatile organic compound) emission problem is greatly limited.
The prior fluorocarbon powder mainly comprises two types of PVDF and FEVE, the PVDF fluorocarbon powder coating is a thermoplastic coating, no chemical structure change occurs in the curing process, and the PVDF fluorocarbon powder has long chain length, so that when the PVDF fluorocarbon powder is coated on the surface of an aluminum alloy, the powder is easy to disperse and uneven, and the performance of the whole alloy can be influenced; the FEVE fluorocarbon powder coating is a thermosetting coating, can generate a cross-linking reaction in the curing process to form a three-dimensional network structure, has short FEVE fluorocarbon powder chain, is easy to disperse and uniform, and is more suitable for being used as a weather-resistant fluorocarbon powder coating to be coated on the surface of an alloy.
Disclosure of Invention
Aiming at the technical problems, the invention provides an aluminum alloy surface Al compatible with FEVE fluorocarbon powder coating2O3-TiO2-SiO2The preparation method of the (ATS for short) composite membrane provides a technical basis for solving the VOC emission problem by utilizing fluorocarbon powder to replace fluorocarbon paint.
The invention adopts the following technical scheme:
a preparation method of an ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of an aluminum alloy comprises the following steps: (1) spraying and cleaning the aluminum alloy for 3-15s at normal temperature by using a degreasing agent for pretreatment, removing oil stains on the surface of the aluminum alloy, and keeping an aluminum oxide film on the surface of the aluminum alloy; (2) coating the surface of the pretreated aluminum alloy with a titanium dioxide passivation solution for 45-100s, and then naturally airing or drying to form TiO2A conversion film; (3) adding TiO into the mixture2Conversion film soaking in silaneAnd (5) performing drying and curing in the aqueous solution for 3-8min to form the protective film of the silane gel layer.
Further, the oil removing agent in the step (1) is prepared by stirring and mixing 11-40 parts by weight of chelating agent, 3-230 parts by weight of corrosion inhibitor, 41-121 parts by weight of builder, 3-22 parts by weight of inorganic base, 0.05-0.35 part by weight of surfactant and 940 parts by weight of water 580-one.
Furthermore, the chelating agent is tetrasodium ethylene diamine tetraacetate and trisodium ethylene diamine tetraacetate dihydrate, the corrosion inhibitor is tetraethylenepentamine, triethanolamine and sodium metasilicate pentahydrate, the builder is potassium carbonate and sodium carbonate, and the surfactant is alkyl glycoside.
Further, the titanium dioxide passivation solution in the step (2) is prepared by mixing 1-4mmol/L titanium salt, 50-150mL hydrogen peroxide solution with the concentration of 30% and 1000mL deionized water, and the pH value is adjusted to 2-3 by adding sulfuric acid.
Further, the titanium salt is one or more of titanium sulfate, titanium tetrachloride, titanium isopropoxide and butyl titanate.
Further, the silane modified solution in the step (3) is prepared from tetraethoxysilane, ethanol, hexamethyldisiloxane and distilled water according to a molar ratio of (0.5-1.5) to (80-120) to (2-6).
Further, tetraethoxysilane, ethanol and distilled water are mixed for 10 to 12 hours at the room temperature at the rotating speed of 800-1000r/min, hexamethyldisiloxane is added and mixed evenly, and the mixture is aged for 2 to 4 hours at the temperature of 60 to 90 ℃ to obtain silane modified solution.
Further, in the step (3), the drying and curing temperature is 30-100 ℃, and the curing time is 2-3 h.
Further, FEVE fluorocarbon powder coating is electrostatically sprayed on the silane gel protective layer and is cured for 10-25min at the temperature of 210-240 ℃, and the thickness of the formed coating is 45-120 mu m.
The invention also provides an aluminum alloy surface ATS composite film compatible with FEVE fluorocarbon powder coating, which is prepared by the preparation method and comprises an aluminum oxide film (Al)2O3)，TiO2Conversion coating (TiO)2) And a protective film of a silane gel layer (SiO)2) (ii) a Oxygen gasThe aluminum oxide film is aluminum matrix natural oxide film with a thickness of 0.01-0.1 μm, and the TiO is2The thickness of the conversion film is 0.1-0.5 μm, and the thickness of the silane gel layer protective film is 1-2 μm.
The invention also provides an aluminum alloy, and the surface of the aluminum alloy comprises the ATS composite film.
The preparation method of the aluminum alloy surface ATS composite membrane compatible with FEVE fluorocarbon powder coating of the invention comprises the step of preparing an aluminum oxide membrane Al2O3、TiO2Conversion film and silane gel layer protective film SiO2The protection of the aluminum alloy surface is realized by the triple protection; in the aluminum alloy pretreatment process, the alkaline washing, acid washing and etching steps are not needed to be carried out on the surface of the aluminum alloy, the natural oxide film on the surface of the aluminum alloy is reserved, then titanium dioxide conversion film liquid is coated, titanium dioxide nanoparticles are deposited on the surface of the aluminum alloy to form a double protection film, partial cracks still exist on the surface of the film, then the film is soaked in silane modification solution to fill the cracks, and the titanium dioxide conversion film is covered by a silane gel protection layer, so that the surface of the conversion film is smooth, and effective triple protection of the surface of the aluminum alloy is formed. The FEVE fluorocarbon powder is sprayed on the surface of the protective film, the FEVE fluorocarbon powder and the protective film can be effectively compatible, and can withstand 2000h of acid salt spray test, 1000h of filiform corrosion test and the like, an effective compatible mode is provided for the application of FEVE fluorocarbon powder paint, the prepared coating can completely meet the index requirements of Qualicoat-2017, such as salt spray resistance, corrosion resistance, boiling water adhesion and the like, and an effective solution is provided for reducing the VOC emission problem by using fluorocarbon powder to replace fluorocarbon paint.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a drawing of an aluminum alloy surface of the present invention compatible with FEVE fluorocarbon powder coatingsTiO in preparation method of ATS composite membrane2An X-ray diffraction pattern of the surface of the aluminum alloy after the conversion coating is solidified;
FIG. 2 shows TiO in the preparation method of the aluminum alloy surface ATS composite film compatible with FEVE fluorocarbon powder coating of the invention2Scanning electron microscope images of the aluminum alloy surface after the conversion coating is cured;
FIG. 3 is an X-ray diffraction pattern of the aluminum alloy surface after the curing of the protective film of the silane gel layer in the preparation method of the ATS composite film compatible with the FEVE fluorocarbon powder coating of the invention;
FIG. 4 is a scanning electron microscope image of the surface of an aluminum alloy after a protective film of a silane gel layer is cured in the preparation method of the ATS composite film compatible with FEVE fluorocarbon powder coating of the invention;
FIG. 5 shows the performance test results of the ATS composite film and inorganic zirconium-titanium system chromium-free pretreatment film prepared by the present invention, and FEVE fluorocarbon powder coating sprayed on the surface of the organic acid-titanium system chromium-free pretreatment film.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the present invention, and it is obvious 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.
A preparation method of an ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of an aluminum alloy comprises the following steps: (1) the aluminum alloy is pretreated by spraying and cleaning oil removing agent for 3-15s at normal temperature to remove oil stains on the surface of the aluminum alloy, but the natural oxide film Al on the surface of the aluminum alloy is kept2O3(ii) a (2) Coating the surface of the pretreated aluminum alloy with a titanium dioxide passivation solution for 45-100s, and then naturally airing or drying to form TiO2A conversion film; (3) adding TiO into the mixture2Soaking the conversion film in silane modified solution for 3-8min, and drying and curing to form a silane gel layer protective film SiO2。
The preparation method of the aluminum alloy surface ATS composite membrane compatible with the FEVE fluorocarbon powder coating of the invention comprises the step of passing through a natural oxidation film Al on the surface of the aluminum alloy2O3、TiO2Conversion film and silane gel layer SiO2The protection film is used for triple protection, so that the surface of the aluminum alloy is protected; the aluminum alloy surface is not required to be subjected to the steps of alkali washing, acid washing and the like, a corrosion-free neutral degreasing agent is adopted for surface pretreatment, a natural aluminum oxide protective film on the aluminum alloy surface is reserved, then titanium dioxide conversion film liquid is coated, titanium dioxide nanoparticles are deposited on the aluminum alloy surface to form a double protective film, partial cracks exist on the film surface, then the film surface is soaked in silane modification solution, the cracks are supplemented, and the titanium dioxide conversion film is covered by a silane gel protective layer, so that the conversion film surface is smooth, and effective triple protection of the aluminum alloy surface is formed.
In some embodiments of the present invention, the oil removing agent in step (1) is prepared by stirring and mixing 11-40 parts by weight of chelating agent, 3-230 parts by weight of corrosion inhibitor, 41-121 parts by weight of builder, 3-22 parts by weight of inorganic base, 0.05-0.35 part by weight of surfactant, and 940 parts by weight of water 580-. Specifically, the oil removing agent in the step (1) is prepared by stirring and mixing 20-30 parts by weight of chelating agent, 230 parts by weight of corrosion inhibitor 120-. Preferably, the oil removing agent in the step (1) is prepared by stirring and mixing 25 parts by weight of chelating agent, 122 parts by weight of corrosion inhibitor, 103 parts by weight of builder, 16 parts by weight of inorganic base, 0.15 part by weight of surfactant and 750 parts by weight of water.
In some embodiments of the invention, the chelating agent is tetrasodium ethylenediaminetetraacetate and trisodium ethylenediaminetetraacetate dihydrate, the corrosion inhibitor is tetraethylenepentamine, triethanolamine and sodium metasilicate pentahydrate, the builder is potassium carbonate and sodium carbonate, and the surfactant is an alkyl glycoside.
Preferably, the oil removing agent of the present invention is diluted to a working liquid at a mass ratio of 2 to 5% in normal use.
The conventional aluminum alloy surface pretreatment process mostly comprises the steps of polishing, alkali washing, acid washing and the like, and the cleaning operations of oil removal, rust removal and the like of the aluminum alloy surface are mostly realized at the cost of removing a natural aluminum oxide protective film on the aluminum alloy surface, so that the aluminum alloy surface is damaged to a certain extent; meanwhile, in the process of removing oil on the metal surface, the traditional normal-temperature oil removing agent has the problems of long treatment time, unclean foam oil stain removal and the like. The degreasing agent is prepared by stirring and mixing the raw materials in proportion, so that oil stains on the surface of the aluminum alloy can be cleaned in 1-15s at normal temperature, the surface of the aluminum alloy is not corroded, a natural oxidation film of an aluminum alloy matrix is reserved, and corrosion protection is provided for the aluminum alloy matrix.
In some embodiments of the present invention, the passivation solution of titanium dioxide in step (2) is prepared by mixing 1-4mmol/L titanium salt, 50-150mL hydrogen peroxide solution with concentration of 30%, and 1000mL deionized water, and adjusting pH to 2-3 by adding sulfuric acid. Preferably, the concentration of sulfuric acid is 1 mol/L.
In some embodiments of the invention, the titanium salt is one or more of titanium sulfate, titanium tetrachloride, titanium isopropoxide, and butyl titanate. Preferably, the titanium salt is titanium sulfate.
When the titanium dioxide passivation solution is coated on the surface of the aluminum alloy, Al is coated in an acid environment2O3And H+Of reaction between Al and H+In between, a displacement reaction takes place, H+And O2Depolarised reduction reactions take place in between. H2O2By chemical decomposition of O2Provide to the solution and further generate more OH-Ions, promoting an increase in the pH of the solution. The specific reaction is as follows:
Al2O3+6H+→2Al3++3H2O
2Al+6H+→2Al3++3H2
O2+2H2O+4e→4OH-
OH-1the addition of ions to form Ti (OH)4And Al (OH)3Conditions are provided. Ti when the pH of the small region is more than 2.54+While inducing Ti (OH)4/TiO2Is performed. Formation of TiO under weakly alkaline conditions2Nanoparticles, TiO2The nanoparticles preferentially deposit to the aluminum alloy surface. The specific reaction is as follows:
[Ti(OH)2·(H2O)4]2++2OH-→[Ti(OH)4·(H2O)2]+2H2O
[Ti(OH)4·(H2O)2]→TiO2·4H2O
2Al3++6OH-→Al2O3·3H2O
as shown in XRD test result in FIG. 1, there is TiO on the surface of the aluminum alloy2Particles are deposited and cover the surface of the aluminum oxide to form a titanium dioxide conversion film, so that the aluminum alloy is further protected; meanwhile, as can be seen from the scanning electron microscope image in fig. 2, when the titanium dioxide conversion film is covered on the surface of the aluminum alloy, a part of cracks still exist, which may affect the performance of the aluminum alloy. Therefore, the titanium dioxide conversion film prepared by the method is soaked in the silane modification solution, and a layer of silane gel layer protective film is covered on the titanium dioxide conversion film.
In some embodiments of the invention, the silane modified solution is prepared by a sol-gel method using tetraethoxysilane as a precursor, ethanol as a solvent, and hexamethyldisiloxane as a modifying component, and tetraethoxysilane, ethanol, hexamethyldisiloxane, and distilled water are prepared in a molar ratio of (0.5-1.5): (80-120): (2-6). Preferably, the molar ratio of tetraethoxysilane, ethanol, hexamethyldisiloxane and distilled water is 1:1:96: 4.
In some embodiments of the invention, tetraethoxysilane, ethanol and distilled water are mixed for 10-12h at the room temperature at the rotating speed of 800-1000r/min, hexamethyldisiloxane is added and mixed uniformly, and the mixture is aged for 2-4h at the temperature of 60-90 ℃ to obtain the silane modified solution.
In some embodiments of the present invention, the drying curing temperature in step (3) is 30-100 ℃, and the curing time is 2-3 h.
XRD test is carried out on the cured silane gel layer protective film, and the result is shown in figure 3, and the amorphous silicon dioxide exists on the surface of the aluminum alloy, so that a new protective film is formed; it can also be seen from figure 4 that the aluminium alloy surface is relatively smooth and that the previous cracks have disappeared and have been repaired by the protective film of the silane gel layer. Specifically, the titanium dioxide conversion film is covered with a layer of silane gel, and due to the presence of hydroxyl groups on the titanium dioxide conversion film, dehydration synthesis occurs between the conversion films when the conversion films are immersed in the silane modification solution. The reaction between the titania conversion film and the silane-modified solution is as follows:
-O-Ti-OH+Si(OH)3-Si(A)3→-O-Ti-O-Si(OH)2O-Si(A)3
-O-Al-OH+Si(OH)3-Si(A)3→-O-Al-O-Si(OH)2O-Si(A)3
A:((CH3)3SiO)x(SiO)y(OH)x,y>1
in conclusion, Al is finally formed on the surface of the aluminum alloy2O3-TiO2-SiO2The composite membrane has triple protection, and all the protective films react with each other, so that the composite membrane has good compatibility and protection effects.
In some embodiments of the invention, the alumina protective film is an aluminum matrix native oxide film with a thickness of 0.01-0.1 μm, TiO2The thickness of the conversion film is 0.1-0.5 μm, and the thickness of the protective film of the silane gel layer is 1-2 μm.
In some embodiments of the invention, FEVE fluorocarbon powder coating is electrostatically sprayed on the silane gel protective layer and cured to form a coating thickness of 45-120 μm.
Preferably, in some embodiments of the present invention, the fluorocarbon powder coating has a curing temperature of 210 ℃ and 240 ℃ and a curing time of 10-25 min; preferably, the curing temperature is 240 ℃ and the curing time is 15 min.
The invention will be further described with reference to specific examples. These examples are illustrative only and are not intended to limit the invention in any way.
The metallic materials used in the following examples:
the domestic aluminum-magnesium alloy section 6063 with the thickness of 1mm comprises the following main components: 0.35%, Mg: 0.8 to 0.9%, Si: 0.65 to 0.75%, Cu: 0.85-0.95%, Mn: 0.15-0.25% and the balance of Al.
The various components used in the examples of the present invention are commercially available products.
Example 1
A preparation method of an ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of an aluminum alloy comprises the following steps:
(1) cutting a sample piece from a 6063 large-size aluminum alloy section, spraying and cleaning the aluminum alloy for 3s by using a degreasing agent at normal temperature, and then drying to remove oil stains on the surface of the aluminum alloy, but keeping an aluminum oxide protective film on the surface of the aluminum alloy;
(2) coating the surface of the pretreated aluminum alloy with a titanium dioxide passivation solution for 60s, and then naturally airing or drying to form TiO2A conversion film;
(3) adding TiO into the mixture2And soaking the conversion film in a silane modified solution for 3min, and then drying and curing at the curing temperature of 60 ℃ for 2.5h to form the silane gel layer protective film.
In this example, the degreasing agent was prepared by stirring and mixing 20 parts by weight of tetrasodium ethylenediaminetetraacetate and 5 parts by weight of trisodium ethylenediaminetetraacetate dihydrate, 1.8 parts by weight of tetraethylenepentamine, 0.2 parts by weight of triethanolamine and 120 parts by weight of sodium metasilicate pentahydrate, 97 parts by weight of potassium carbonate and 6 parts by weight of sodium carbonate, 16 parts by weight of potassium hydroxide, 0.15 parts by weight of alkylglycoside, and 750 parts by weight of water. And diluted to working liquid at a ratio of 4% when in use.
The titanium dioxide passivation solution is prepared by mixing 2.5mmol/L titanium sulfate, 60mL of 30% hydrogen peroxide solution and 940mL of deionized water, and the pH value is adjusted to 2 by adding 1mol/L sulfuric acid.
The silane modified solution is prepared from tetraethoxysilane, ethanol, hexamethyldisiloxane and distilled water according to a molar ratio of 1:1:96: 4; tetraethoxysilane, ethanol and distilled water are mixed for 12 hours at room temperature at the rotating speed of 1000r/min, hexamethyldisiloxane is added and mixed evenly, and the mixture is aged for 2 hours at the temperature of 80 ℃ to obtain silane modified solution.
Example 2
A preparation method of an ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of an aluminum alloy comprises the following steps:
(1) cutting a sample piece from a 6063 large-size aluminum alloy section, spraying and cleaning the aluminum alloy for 5s by using a degreasing agent at normal temperature, and then drying to remove oil stains on the surface of the aluminum alloy, but keeping an aluminum oxide protective film on the surface of the aluminum alloy;
(2) coating the surface of the pretreated aluminum alloy with a titanium dioxide passivation solution for 100s, and then naturally airing or drying to form TiO2A conversion film;
(3) adding TiO into the mixture2And soaking the conversion film in a silane modified solution for 6min, and then drying and curing at 100 ℃ for 2h to form the silane gel layer protective film.
In this example, the degreasing agent was prepared by stirring and mixing 10 parts by weight of tetrasodium ethylenediaminetetraacetate and 10 parts by weight of trisodium ethylenediaminetetraacetate dihydrate, 0.2 parts by weight of tetraethylenepentamine, 1.5 parts by weight of triethanolamine and 225 parts by weight of sodium metasilicate pentahydrate, 35 parts by weight of potassium carbonate and 24 parts by weight of sodium carbonate, 22 parts by weight of potassium hydroxide, 0.05 parts by weight of alkylglycoside, and 580 parts by weight of water. And diluted to working liquid by 2% proportion when in use.
The titanium dioxide passivation solution is prepared by mixing 1mmol/L titanium sulfate, 50mL of hydrogen peroxide solution with the concentration of 30% and 800mL of deionized water, and the pH value is adjusted to 3 by adding 1mol/L sulfuric acid.
The silane modified solution is prepared from tetraethoxysilane, ethanol, hexamethyldisiloxane and distilled water according to a molar ratio of 0.5:0.5:80: 2; tetraethoxysilane, ethanol and distilled water are mixed for 12 hours at room temperature at the rotating speed of 800r/min, hexamethyldisiloxane is added and mixed evenly, and aging is carried out for 4 hours at the temperature of 60 ℃ to obtain silane modified solution.
Example 3
A preparation method of an ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of an aluminum alloy comprises the following steps:
(1) cutting a sample piece from a 6063 large-size aluminum alloy section, spraying and cleaning the aluminum alloy for 15s by using a degreasing agent at normal temperature, and then drying to remove oil stains on the surface of the aluminum alloy, but keeping an aluminum oxide protective film on the surface of the aluminum alloy;
(2) coating the surface of the pretreated aluminum alloy with a titanium dioxide passivation solution for 45s, and then naturally airing or drying to form TiO2A conversion film;
(3) adding TiO into the mixture2And soaking the conversion film in a silane modified solution for 8min, and then drying and curing at the curing temperature of 30 ℃ for 3h to form the silane gel layer protective film.
In this example, the degreasing agent was prepared by stirring and mixing 30 parts by weight of tetrasodium ethylenediaminetetraacetate, 1 part by weight of trisodium ethylenediaminetetraacetate dihydrate, 3.8 parts by weight of tetraethylenepentamine, 1.9 parts by weight of triethanolamine, 3 parts by weight of sodium metasilicate pentahydrate, 64 parts by weight of potassium carbonate, 16 parts by weight of sodium carbonate, 3 parts by weight of potassium hydroxide, 0.35 part by weight of alkylglycoside, and 940 parts by weight of water. And is diluted into working liquid according to the proportion of 5% when in use.
The titanium dioxide passivation solution is prepared by mixing 4mmol/L titanium sulfate, 150mL of hydrogen peroxide solution with the concentration of 30% and 1000mL of deionized water, and the pH value is adjusted to 2 by adding 1mol/L sulfuric acid.
The silane modified solution is prepared from tetraethoxysilane, ethanol, hexamethyldisiloxane and distilled water according to a molar ratio of 1.5:1.5:120: 6; tetraethoxysilane, ethanol and distilled water are mixed for 10 hours at room temperature at the rotating speed of 900r/min, hexamethyldisiloxane is added and mixed evenly, and the mixture is aged for 3 hours at the temperature of 90 ℃ to obtain silane modified solution.
Comparative example 1
A preparation method of an aluminum alloy surface protection film comprises the following steps:
(1) cutting a sample piece from a 6063 large-size aluminum alloy section, spraying and cleaning the aluminum alloy for 60s by using a degreasing agent at normal temperature, and then drying to remove oil stains on the surface of the aluminum alloy;
(2) coating the surface of the sample piece after being cleaned with the oil stain with a titanium dioxide passivation solution for 45s, and then naturally airing or drying to form TiO2A conversion film;
(3) Adding TiO into the mixture2And soaking the conversion film in a silane modified solution for 3min, and then drying and curing at the curing temperature of 60 ℃ for 2.5h to form the silane gel layer protective film.
In the comparative example, the degreasing agent is a solution consisting of sulfuric acid, hydrofluoric acid and a surfactant, has a remarkable etching effect on the surface of the aluminum alloy, and the etching amount reaches 1.0gm-2And thoroughly removing the oxide film on the surface of the aluminum alloy according to the requirement of Quolicoat-2017 to expose the aluminum matrix.
The titanium dioxide passivation solution is prepared by mixing 4mmol/L titanium sulfate, 150mL of hydrogen peroxide solution with the concentration of 30% and 1000mL of deionized water, and the pH value is adjusted to 2 by adding 1mol/L sulfuric acid.
The silane modified solution is prepared from tetraethoxysilane, ethanol, hexamethyldisiloxane and distilled water according to a molar ratio of 1:1:96: 4; tetraethoxysilane, ethanol and distilled water are mixed for 12 hours at room temperature at the rotating speed of 1000r/min, hexamethyldisiloxane is added and mixed evenly, and the mixture is aged for 2 hours at the temperature of 80 ℃ to obtain silane modified solution.
The aluminum alloy surface protective film obtained based on this comparative example was composed of TiO2-SiO2Composition, in contrast to the ATS composite membrane, is a TS membrane.
The FEVE fluorocarbon powder coating is electrostatically sprayed on the aluminum alloy materials obtained in the examples 1-3 and the comparative example 1, and then curing treatment is carried out, wherein the curing temperature is 240 ℃, and the curing time is 15 min. And then, carrying out performance test on the aluminum alloy material coated with the FEVE fluorocarbon powder coating, wherein the test standard and the requirement are shown in the table 1.
TABLE 1 aluminium alloy material Performance test Standard
The results of various tests performed on the aluminum alloy materials of examples 1 to 3 and comparative example 1 in the respective test modes are shown in tables 2 to 5.
Table 2 acid salt spray test results
TABLE 3 test results of constant temperature condensate water
TABLE 4 SO resistance2Test results
TABLE 5 filiform corrosion test results
The FEVE fluorocarbon powder has good comprehensive physical and chemical properties such as weather resistance, acid resistance, alkali resistance and the like, so the aluminum alloy protective film below the coating has good corrosion resistance and good compatibility with the coating to achieve excellent performance, and the test results in tables 2 to 5 show that the aluminum alloy surface protective film has good compatibility with the FEVE fluorocarbon powder coating, and the aluminum alloy material sprayed with the FEVE fluorocarbon powder coating has excellent salt spray resistance, and can withstand 2000h acid salt spray test, constant temperature condensate water test, 1000h filiform corrosion test and the like. On the other hand, the comparison with the comparative example 1 shows that the aluminum alloy surface of the invention realizes triple protection through a natural aluminum oxide protective film, a titanium dioxide conversion film and a silane gel layer protective film, and further improves the corrosion resistance of the aluminum alloy material. The aluminum alloy surface protective film is beneficial to improving the application of FEVE fluorocarbon powder coating, thereby realizing the industrial implementation of the technical scheme that fluorocarbon powder replaces fluorocarbon paint to reduce VOC emission.
In order to further prove the performance of the protective film prepared by the invention, an inorganic zirconium-titanium chromium-free pretreatment film and an organic acid-titanium chromium-free pretreatment film specified in YS/T1189-2017 aluminum and aluminum alloy chromium-free chemical pretreatment film standard are selected to be compared with the ATS composite film prepared in the embodiment 1 of the invention, fluorocarbon powder based on FEVE resin is electrostatically sprayed on the three films under the same working condition, and after curing, the main performance test is carried out by referring to GB5237.4(5) -2017, and the result is shown in FIG. 5. Wherein, No. 1 is an inorganic zirconium titanium system chromium-free pretreatment film, No. 2 is an organic acid-titanium system chromium-free pretreatment film, and No. 3 is the ATS composite film of the invention. The 1#, 2# and 3# are subjected to high-pressure boiling water adhesion tests according to the Qualicoat-2017 requirements, as shown in (A) (B) of FIG. 5, the results show that the 1# and 2# samples have severe coating peeling phenomena and unqualified adhesion, and the high-pressure boiling water adhesion of the 3# sample can be more than 0 grade. As shown in FIG. 5(C), the results of 80cm impact performance tests carried out on 1#, 2# and 3# according to the Qualicoat-2017 requirements show that the coating of the 1# sample is seriously peeled off, and the coating of the 2# sample has obvious cracks, which do not meet the requirements. And the No. 3 sample only has micro cracks after being impacted by 80cm, and meets the standard index requirements. Therefore, after the fluorocarbon powder based on the FEVE resin is electrostatically sprayed on the aluminum alloy surface protection film prepared by the method, the performance of the prepared coating completely meets the index requirement of Qualicoat-2017.
The present invention has been further described with reference to specific embodiments, but it should be understood that the detailed description should not be construed as limiting the spirit and scope of the present invention, and various modifications made to the above-described embodiments by those of ordinary skill in the art after reading this specification are within the scope of the present invention.
Claims (8)
1. A preparation method of an ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of an aluminum alloy is characterized by comprising the following steps:
(1) spraying and cleaning the aluminum alloy for 3-15s at normal temperature by using a degreasing agent for pretreatment, removing oil stains on the surface of the aluminum alloy, and keeping a natural oxide film on the surface of the aluminum alloy;
(2) coating the surface of the pretreated aluminum alloy with a titanium dioxide passivation solution for 45-100s, and then naturally airing or drying to form TiO2A conversion film;
(3) adding TiO into the mixture2Soaking the conversion film in a silane modified solution for 3-8min, and then drying and curing to form a silane gel layer protective film;
in the step (2), the titanium dioxide passivation solution is prepared by mixing 1-4mmol/L titanium salt, 50-150mL hydrogen peroxide solution with the concentration of 30% and 1000mL deionized water, and the pH value is adjusted to 2-3 by adding sulfuric acid;
the silane modified solution in the step (3) is prepared from tetraethoxysilane, ethanol, hexamethyldisiloxane and distilled water according to the molar ratio of (0.5-1.5) to (80-120) to (2-6).
2. The method for preparing the ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of the aluminum alloy as set forth in claim 1, wherein the oil removing agent in the step (1) is prepared by stirring and mixing 11-40 parts by weight of chelating agent, 3-230 parts by weight of corrosion inhibitor, 41-121 parts by weight of builder, 3-22 parts by weight of inorganic base, 0.05-0.35 part by weight of surfactant and 940 parts by weight of water 580-.
3. The method of claim 2, wherein the chelating agent is tetrasodium ethylenediaminetetraacetate and trisodium ethylenediaminetetraacetate dihydrate, the corrosion inhibitor is tetraethylenepentamine, triethanolamine, and sodium metasilicate pentahydrate, the builder is potassium carbonate and sodium carbonate, and the surfactant is an alkyl glycoside.
4. The method for preparing an ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of aluminum alloy according to claim 1, wherein the titanium salt is one or more of titanium sulfate, titanium tetrachloride, titanium isopropoxide and butyl titanate.
5. The method for preparing the ATS composite film compatible with FEVE fluorocarbon powder coating as claimed in claim 1, wherein the silane modified solution is prepared by mixing tetraethoxysilane, ethanol and distilled water at room temperature at the rotation speed of 800-1000r/min for 10-12h, adding hexamethyldisiloxane, mixing uniformly, and aging at 60-90 ℃ for 2-4 h.
6. The method for preparing the ATS composite film compatible with the FEVE fluorocarbon powder coating on the surface of the aluminum alloy according to claim 1, wherein the drying curing temperature in the step (3) is 30-100 ℃, and the curing time is 2-3 h.
7. The preparation method of the ATS composite film compatible with FEVE fluorocarbon powder coating on the surface of the aluminum alloy as claimed in any one of claims 1 to 6, wherein FEVE resin-based fluorocarbon powder coating is electrostatically sprayed on the protective film of the silane gel layer, and the coating thickness is 45-120 μm after curing for 10-25min at 210-240 ℃.
8. An ATS composite film compatible with FEVE fluorocarbon powder coating on aluminum alloy surface, wherein the composite film is obtained by the preparation method of any one of claims 1 to 7, and comprises an aluminum oxide film and TiO2A conversion film and a protective film of a silane gel layer, wherein the aluminum oxide film is an aluminum matrix natural oxide film with the thickness of 0.01-0.1 mu m, and the TiO film2The thickness of the conversion film is 0.1-0.5 μm, and the thickness of the silane gel layer protective film is 1-2 μm.
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| CN114481112A (en) * | 2021-12-27 | 2022-05-13 | 湖北安登环保科技有限公司 | Preparation method and application process of fluoride-free zirconium-free aluminum alloy passivator |
| CN115613022A (en) * | 2022-09-28 | 2023-01-17 | 湖南金裕环保科技有限公司 | Chromium-free natural color passivating agent for aluminum and aluminum alloy and preparation method thereof |
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