CN114133797B - Super-hydrophobic antifouling paint composition - Google Patents

Super-hydrophobic antifouling paint composition Download PDF

Info

Publication number
CN114133797B
CN114133797B CN202111650362.1A CN202111650362A CN114133797B CN 114133797 B CN114133797 B CN 114133797B CN 202111650362 A CN202111650362 A CN 202111650362A CN 114133797 B CN114133797 B CN 114133797B
Authority
CN
China
Prior art keywords
aluminum alloy
temperature
parts
treatment
super
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111650362.1A
Other languages
Chinese (zh)
Other versions
CN114133797A (en
Inventor
王永勤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Chuanyue Technology Co ltd
Original Assignee
Beijing Chuanyue Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Chuanyue Technology Co ltd filed Critical Beijing Chuanyue Technology Co ltd
Priority to CN202111650362.1A priority Critical patent/CN114133797B/en
Publication of CN114133797A publication Critical patent/CN114133797A/en
Application granted granted Critical
Publication of CN114133797B publication Critical patent/CN114133797B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C25D11/246—Chemical after-treatment for sealing layers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Plant Pathology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention provides a super-hydrophobic antifouling coating composition, which can effectively prevent the local dissolution of a copper-rich phase by carrying out secondary solid solution and secondary aging treatment on an aluminum alloy, changing the components of an electrolytic solution and controlling a power supply to be bipolar pulse, thereby alleviating the defect of hard anodic oxidation of the copper-aluminum alloy, finally obtaining high hardness, high corrosion resistance and low roughness, and finally effectively improving the overall physical and chemical properties of the aluminum alloy by spraying a super-hydrophobic coating on the surface of the aluminum alloy.

Description

Super-hydrophobic antifouling paint composition
Technical Field
The invention relates to coating treatment of an aluminum alloy material, in particular to surface treatment for 2-series and 7-series aluminum alloys.
Background
The metal material has more excellent properties, such as good process performance, higher mechanical property and the like, is one of the most widely applied engineering materials in the current economic construction, and plays an irreplaceable role particularly in the manufacture of buildings, machine tools, aerospace and parts. Aluminum is one of the important metallic materials, its density is small, 2.78g/cm3, commonly called light metal, its corresponding alloy is called light alloy, the specific gravity is about 1/3 of steel. The aluminum alloy has more advantages, such as lower price, easy molding, good heat conductivity and the like, so the aluminum alloy is widely applied to the departments of electronics, communication, light industry building materials, transportation, aerospace and the like. Of these, 2000(Al-Cu) and 7000(Al-Zn-Mg-Cu) aluminum alloys have high strength and fracture
Toughness, which is fully applied in aerospace industry (such as aircraft structural parts, wings, engines and propeller elements) and some civil products, wherein 2024 aluminum alloy is Al-Cu series heat-treatable strengthened aluminum alloy with copper as a main alloy element, and copper element plays a very important role in copper-aluminum alloy, because the addition of copper can lead the alloy to generate solid solution strengthening, the strength and hardness of the alloy can be increased, but the addition of copper element can also reduce the elongation of the alloy. When the copper element content in the aluminum-copper alloy is about 5%, the alloy can obtain better strengthening effect, so that the copper element content of most aluminum-copper alloys is about 5%. When the content of copper added into the alloy is increased, the strength and toughness of the alloy are improved, but the addition of copper also has negative influence on the welding performance and the corrosion resistance of the alloy.
The classification of aluminum anodization can be classified into architectural aluminum anodization, corrosion protection aluminum anodization, decorative aluminum anodization, engineering aluminum anodization (e.g., hard anodization), electrical insulation aluminum anodization, and the like, according to the final use of the aluminum material. Due to their different purposes of use and different performance requirements, different electrolyte compositions, power supply characteristics and process parameters should be used. The anodizing processes for aluminum and aluminum alloys are of many types and are most widely used for sulfuric acid anodizing, followed by oxalic acid anodizing and chromic acid anodizing. The hard anodizing process and the common anodizing process have no strict limit, and the hardness of two anodic oxide films has an excessively crossed range, namely the hard anodizing of aluminum and aluminum alloy is an important branch of the aluminum alloy anodic oxidation technology, and is a special anodic oxidation technology which takes the hardness and the wear resistance of the anodic oxide film as primary performance targets, and the hard anodizing is a newer method in an electrochemical oxidation treatment method. It obtains the oxide film with high hardness and thick film layer under the condition of the cooled dilute acid oxidation solution, and the process is called as hard anodic oxidation treatment or thick film anodic oxidation treatment or hard oxidation for short.
In addition, the hard anodic oxide film of the aluminum alloy has a great relationship with the alloy components of the aluminum alloy material, and even if different aluminum alloys adopt the same hard anodic oxidation process, the performance and the quality of the formed anodic oxide film can be greatly different. Hard anodizing of the 2000 series aluminum alloys is difficult due to the presence of copper rich intermetallics (e.g., CuAl) in the series2Phase) of the two phases,the dissolution speed is higher in the anodic oxidation process, so that the anode becomes a current gathering center, and the anode is easily burnt and broken down to form defects such as 'pinholes' and the like; the 2014 aluminum alloy has more and more serious defects of 'pinholes' or 'pore-trapping' along with the increase of the Fe content, and the hard anodic oxide film of the 7000 series aluminum alloy also has the problem of 'pinholes', but is not as serious as that of the 2000 series aluminum alloy.
Based on the above problems, the prior art also discloses a method for preparing an aluminum alloy hard anodic oxide film, such as CN105506705A of Jiangsu university, which comprises subjecting an aluminum alloy workpiece to a high-temperature solution treatment, and then performing a hard anodic oxidation treatment, i.e. after the aluminum alloy workpiece is subjected to the high-temperature solution treatment, an alloy compound is dissolved, and alloy elements are dissolved in a matrix to form a single solid solution, so as to eliminate the influence of the alloy compound on the reduction of the area of aluminum directly facing an anodic oxidation solution and the retardation of the alloy compound existing in the anodic oxide film on the diffusion of oxygen ions to the oxide film/matrix interface, so that the oxidation reaction can normally proceed and the anodic oxide film can normally grow, but the method disclosed in the patent has the following problems: (1) there is no maximum reduction in the concentration and size of the second phase solid solution, i.e., there is a significant direction in which the solid solution needs improvement; (2) the electrolyte is single, namely the electrolyte has a obviously improved direction; (3) the hole sealing means is simple, namely, the hole sealing has places which obviously need to be improved; (3) post-treatment means for aluminum substrates is desired to be improved, such as poor light resistance of the oxide film; the dust-proof and moisture-proof functions are not provided; the problems of color loss, white exposure, paint layer falling, matrix corrosion and the like can occur.
Disclosure of Invention
Based on the technical problems, the invention provides a super-hydrophobic antifouling paint composition, which is used for 2-series or 7-series aluminum alloy, can effectively prevent the local dissolution of a copper-rich phase by carrying out secondary solid solution and secondary aging treatment on the aluminum alloy, changing the components of an electrolytic solution and controlling a power supply to be bipolar pulse, thereby lightening the hard anodic oxidation defect of the copper-aluminum alloy, finally obtaining high hardness, high corrosion resistance and low roughness, and finally effectively improving the overall physical and chemical properties of the aluminum alloy by spraying the super-hydrophobic paint on the surface of the copper-aluminum alloy.
Specifically, the super-hydrophobic antifouling coating composition comprises the following raw materials in parts by mass:
20-35 parts of deionized water
15-30 parts of fluorocarbon emulsion
10-18 parts of water-based silicone-acrylate emulsion
0.2-15 parts of hydrophobic powder stearate
0.5 to 5.0 portions of defoaming agent
0.1-2.0 parts of film-forming assistant
0.2 to 1.0 portion of wetting dispersant
0.1-0.3 part of mildew preventive.
The hydrophobic powder stearate is one or more of sodium stearate, magnesium stearate, aluminum stearate and zinc stearate; the defoaming agent is selected from mineral oil or organic silicon defoaming agents; the film forming auxiliary agent is selected from one or more of ethylene glycol butyl ether, propylene glycol butyl ether and dodecyl alcohol ester; the wetting and dispersing agent is selected from one of digao 760W, 762W, BYK 193; the mildew preventive is isothiazolinone bactericidal mildew preventive.
A preparation method of a super-hydrophobic antifouling paint composition comprises the following steps: weighing the raw materials according to the mass parts, mixing and stirring the fluorocarbon emulsion, the water-based silicone-acrylate emulsion, the hydrophobic powder, the wetting dispersant and the deionized water uniformly, wherein the stirring speed is 500-800rpm, and the stirring time is 20-40 min; and then adding the film forming auxiliary agent, the defoaming agent and the sterilization mildew preventive, stirring and mixing at the stirring speed of 1000rpm for 30-60min, and uniformly mixing to obtain the fluorocarbon coating.
The super-hydrophobic antifouling paint composition is sprayed on the surface of aluminum alloy in a spraying mode, and the aluminum alloy is subjected to surface treatment and anodic oxidation treatment.
The aluminum alloy is a 2-series or 7-series aluminum alloy, preferably a 7-series aluminum alloy.
The aluminum alloy is treated as follows:
(1) primary solution treatment: processing the aluminum alloy to obtain the required shape, increasing the temperature to 530 ℃ and 540 ℃ at a speed of 30-50 ℃/min, carrying out constant temperature treatment for 40-60min, carrying out water quenching for 5-7min at room temperature, and carrying out quenching water temperature of 15-25 ℃;
(2) primary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace with the temperature of 160-170 ℃ for oil bath heat preservation for 6-8 h;
(3) secondary solution treatment: raising the temperature to 480-500 ℃ at a speed of 30-50 ℃/min, carrying out constant temperature treatment for 40-60min, and carrying out water quenching at room temperature for 5-7min and the quenching water temperature of 15-25 ℃;
(4) secondary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace with the temperature of 175-185 ℃ for oil bath heat preservation for 8-10 h;
(5) mechanical polishing, oil removal, alkali washing and acid washing;
(6) anodic oxidation: taking the aluminum alloy treated in the step (5) as an anode and soaking the aluminum alloy in electrolyte, wherein the electrolyte comprises sulfuric acid, oxalic acid, citric acid, tetrabutylammonium bromide and benzotriazole;
(7) sealing holes by using the super-hydrophobic antifouling paint;
(8) thermosetting and drying.
The anodic oxidation electrolyte comprises 250-280g/L sulfuric acid, 20-25 g/L oxalic acid, 30-35g/L citric acid, 10-15g/L tetrabutylammonium bromide and 5-7g/L benzotriazole.
The anodic oxidation is bipolar pulse, and the pulse condition is as follows:
forward pulse current density: 4-6A/dm2，
Forward pulse width: 2-3s of the total weight of the mixture,
forward duty cycle: 50 to 60 percent of the total weight of the mixture,
pulse number: 8-10,
negative pulse current density: 1-3 mA/cm2，
Negative pulse width: 500-800 mu.s of the sodium aluminate solution,
negative duty cycle: 20-25% of the total weight of the mixture,
pulse number: 1,
the anodic oxidation time is 20-40min,
temperature: 2 to 7 ℃ of the reaction kettle,
the stirring speed was 500-700 rpm.
The mechanical grinding is realized by sequentially grinding 800# and 1000#, and the degreasing liquid is 35-40g/LNaOH and 10-15g/LNa2CO3Soaking for 1-3min at 40-50 deg.C, removing oil, and washing with deionized water; acid washing: pickling solution of 15-20vol.% HNO3Soaking at 25-30 deg.C for 20-30 s.
Sealing holes by the super-hydrophobic antifouling paint: after spraying, standing for 30-40min, and drying the surface, wherein the thermosetting drying comprises the following steps: drying at 40-45 deg.C for 8-10 h.
First, it is well known in the art that aluminum alloys differ from pure aluminum in that there are more intermetallic compounds, i.e., second phases, in the aluminum alloy structure, and these second phases behave during anodization depending on their comparison to the electrode potential of the aluminum matrix, where the aluminum matrix is anodic if the electrode potential is higher than the aluminum matrix, the compounds or single phases will enter the oxide film during anodization, as in sulfuric acid hard anodization: si, TiAl3And MnAl6Etc. are generally inert, they are more positive than the aluminum matrix in the sulfuric acid electrolyte and therefore do not preferentially oxidize or dissolve, and can be incorporated directly into the hard anodized film. Whereas if the electrode potential is more negative than the aluminum substrate, it is preferentially dissolved or oxidized relative to the aluminum substrate if it is anodic, e.g. CuAl2、Mg2Si and Mg2Intermetallic compounds such as Al3, which exhibit electronegativity to the electrode potential as compared with aluminum matrix, are directly dissolved in electrolytic solutions, like FeAl6、FeAl3And (Fe, Mn) Al6The electrode potential of the intermetallic compounds is similar to that of aluminum matrix, and they are mainly in the form of oxides (e.g., Al) after oxidation2O3And Fe2O3) The impurities enter the anodic oxide film.
For 2 series or 7 series aluminum alloy, the existence of CuAl2 phase (theta phase) in aluminum-copper alloy is the main reason of hard anodic oxidation difficulty, because each part grows unevenly, the film cell regularity and the lattice arrangement continuity are poor, therefore the hardness is lower, which is the technical problem to be solved in CN105506705A, the invention solves the technical problems that after the aluminum alloy workpiece is subjected to high-temperature solution treatment, the alloy compound is dissolved, the alloy element is dissolved in the matrix to form a single solid solution, the influence of the alloy compound on the reduction of the area of aluminum directly facing the anodic oxidation liquid and the diffusion of oxygen ions to the interface of the oxide film/matrix are eliminated, the oxidation reaction can normally proceed, the anodic oxidation film normally grows, specifically, the aluminum alloy workpiece is placed in a heat treatment furnace, heating at 530-540 ℃, keeping the temperature for 2-3 hours, taking out and immediately cooling by water, in brief, the patent dissolves a second-phase copper-aluminum alloy into an aluminum matrix through solution treatment, and then precipitates a large amount of fine and highly-dispersed copper-rich phases through aging treatment, so that the influence of CuAl2 on a hard anodic oxide film is fully reduced.
The solution treatment can make the second phase partially or completely dissolved in the matrix to form supersaturated solid solution, and the anodic oxidation after the solution treatment of the aluminum alloy can effectively eliminate the influence of the second phase alloy compound on the film thickness of the anodic oxide film, so the film thickness is increased, meanwhile, the dissolving amount of the second phase is related to the solution temperature, the higher the temperature is, the more the second phase is dissolved, namely, the less the second phase is remained, the invention adopts two times of solution treatment:
(1) primary solution treatment: processing the aluminum alloy to obtain the required shape, increasing the temperature to 530 ℃ and 540 ℃ at a speed of 30-50 ℃/min, carrying out constant temperature treatment for 40-60min, carrying out water quenching for 5-7min at room temperature, and carrying out quenching water temperature of 15-25 ℃;
(2) primary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace with the temperature of 160-170 ℃ for oil bath heat preservation for 6-8 h;
(3) secondary solution treatment: raising the temperature to 480-500 ℃ at a speed of 30-50 ℃/min, carrying out constant temperature treatment for 40-60min, and carrying out water quenching at room temperature for 5-7min and the quenching water temperature of 15-25 ℃;
(4) secondary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace with the temperature of 175-185 ℃ for oil bath heat preservation for 8-10 h;
within a certain range, the higher the solid solution temperature is, the better, but when the temperature is too high, such as 550 ℃, the alloy structure can be slightly over-burnt, the temperature is continuously increased, the grain boundary of the metallographic structure and the inside of the crystal grain can generate re-melting balls, which indicates that the structure has already generated a serious over-burning phenomenon and is not beneficial to the later anodic oxidation, therefore, the treatment temperature of the invention should be lower than the temperature, the solid solution temperature, and the solid solution time can not be excessively prolonged while ensuring that the second phase is completely dissolved to the aluminum matrix.
As shown in the attached figure 1, wherein figure 1 is a microcosmic composition diagram of the surface of the aluminum alloy after polishing, it can be seen that the second phase cannot be effectively dissolved through the primary solid solution and primary aging treatment, and a large amount of fine and highly dispersed second phase is precipitated through the secondary solid solution and secondary aging treatment, and the secondary solid solution and secondary aging treatment can almost reduce or eliminate the second phase alloy compound, so that the influence of the second phase alloy compound on the anodic oxide film forming is reduced or eliminated.
Then, hard anodizing treatment is carried out on the aluminum alloy subjected to the solution treatment, wherein the anodizing electrolyte comprises 280g/L sulfuric acid of 250-L, 20-25 g/L oxalic acid, 30-35g/L citric acid, 10-15g/L tetrabutylammonium bromide and 5-7g/L benzotriazole.
Sulfuric acid: as the most main components in the electrolyte, the conductivity of the electrolyte and the capability of dissolving the oxide film can be improved, and the conductivity of the electrolyte is improved along with the increase of the content of the sulfuric acid, so that the growth speed of the film is increased more than the dissolving capability of the film on the oxide film, and the film is compact and the hardness is increased. In addition, 2A12 has high copper content, and the sigma phase (CuAl2) compound in the alloy has high dissolution speed in the oxidation process, is easily to become the center of current aggregation, and is easy to cause the film layer at the position to be overheated and dissolved, so that the part is burnt and broken down, therefore, the sulfuric acid electrolyte with high quality concentration is generally selected, for example, 80g/L sulfuric acid with low concentration can generate ablation phenomenon, when the concentration is increased within the range of 250 plus 280g/L, no ablation phenomenon can occur, and in addition, if the concentration of acid is further increased, the dissolution speed can be increased, which affects film formation.
Oxalic acid: the microhardness of the film layer is increased along with the increase of the mass concentration of oxalic acid, the concentration is preferably 20-25 g/L, the oxalic acid is a main additive in the anodic oxidation electrolyte and mainly can reduce the dissolution activity of the electrolyte on the oxide film layer, reduce the dissolution speed of the oxide film to a certain extent, reduce the porosity of the film layer, improve the growth rate of the oxide film and increase the microhardness of the oxide film, and if the concentration of the oxalic acid is too high, the dissolution action of the electrolyte on the oxide film is increased, so that the porosity of the film layer is increased, and the microhardness and the corrosion resistance of the oxide film are reduced.
And (3) citric acid: citric acid is a buffer to maintain the pH of the electrolyte as it is consumed in acid form.
Tetrabutylammonium bromide and benzotriazole: the complexing agent is used for improving the allowable temperature of the anodic oxidation bath solution, greatly improving the hardness and appearance quality of the film layer and increasing the toughness of the oxidation film.
Selecting a power supply: the power supply is selected as a reversing pulse power supply, and the generated anodic oxidation film resistor is very large, so that a large amount of heat is easily generated in the oxidation process, the density of the traditional direct current oxidation current is not too large, the voltage required by hard anodic oxidation is greatly reduced by pulse oxidation, the large pulse oxidation current can be given instantly by adjusting the duty ratio and the peak voltage value, the pulse current is discontinuous, the interface heat can be taken away by the strongly stirred electrolyte in the oxidation gap, and the pulse parameters are as follows: forward pulse current density: 4-6A/dm2The forward pulse width: 2-3s, forward duty cycle: 50-60%, pulse count: 8-10, negative pulse current density: 1-3 mA/cm2Negative pulse width: 100-: 20-25%, pulse count: 1, where the duty cycle is Ton/Ton+ToffThe duty ratio is the main heat carrying time, which is not easy to be excessively shortened, i.e. the duty ratio is too short, the oxidation interval is too long, which is not beneficial to the rapid growth of the film layer, and the time required by oxidation is increased, and under the condition of higher duty ratio, the applied voltage action time is too long, the gap is too short, the heat on the sample can not be dissipated in time, and the advantage of a pulse power supply can not be achieved, besides, in the bidirectional pulse, the reverse pulse of short time is provided, the aluminum alloy is changed from the anode to the cathode, the polarization phenomenon can be reduced in the process, the electrolyte condition near the electrode is changed, the temperature is further reduced, and the temperature is reduced along with 500-The stirring at 700rpm dissipates heat, so that the electrolyte and the surface of the anodic oxide film can fully dissipate heat.
Generally speaking, the thickness of the anodic oxide film is in direct proportion to the amount of electricity passing through the anodic oxidation process, and for hard anodic oxidation, a higher current density and a lower bath temperature are generally required, and the anodic oxidation current density is appropriately increased, so that the film forming speed of the hard anodic oxidation and the thickness of the anodic oxide film can be increased, and the hardness and the wear resistance of the film can be improved. However, when the current density is too high, a large amount of heat is generated in the electrochemical process, which causes local overheating of the workpiece, and thus local dissolution of the film occurs, resulting in non-uniformity, porosity and even burning of the hard anodic oxide film, therefore, for a general direct current power supply or a superimposed power supply, the hard anodic oxide current density is selected from the range of 2 to 5A/dm2, and usually the current density does not exceed 5A/dm2Otherwise, the heating value of the electrolyte is larger, the joule heat cannot be transferred out in time, so that the temperature in the film layer is accelerated, the dissolution of the oxide film is accelerated, the microhardness of the film layer is reduced, and no burning loss or pulverization phenomenon can occur, namely the current density in the field is selected as follows: the obtained alloy has good microhardness and corrosion resistance, and can form a compact thick film without burning loss or pulverization. In order to improve the current density, the invention adopts bipolar commutation pulse, duty ratio parameters and stirring to fully radiate the anodic oxidation film and the second phase point, and can effectively improve the anodic oxidation current density to 4-6A/dm2When the thick film with better microhardness, corrosion resistance and compactness is obtained, the burning loss or pulverization phenomenon is completely avoided.
Anodic oxidation time: the longer the anodic oxidation time is, the more the accumulated passing electricity is, the larger the thickness of the anodic oxide film is, namely the longer the anodic oxidation time is, the thickness of the hard anodic oxide film can be increased, but the film forming efficiency is reduced along with the extension of the anodic oxidation time.
Temperature: the lower temperature of the anodic oxidation bath liquid is adopted, the heat generated by anodic oxidation can be fully dissipated, and the dissolution of the anodic oxide film by the acidic electrolytic acid is weakened, so that the hardness of the aluminum anodic oxide film is improved, the thickness of the film layer is relatively increased, and the film layer also has good corrosion resistance and wear resistance.
The existing hole sealing technology comprises inorganic hole sealing, hydrothermal hole sealing, super hydrothermal hole sealing and metal salt hole sealing, wherein the inertia of the surface is reduced by changing the chemical property of a plurality of holes, the hole sealing is similar to the process of filling or closing the holes, and the method is a means for obtaining a compact passivation effect by destroying the appearance of an anode hole, the means is irreversible, the means generally does not bring any hydrophobic and moisture-resistant effect, and the antifouling effect is poor. As shown in fig. 4.
Specifically, the paint adopted by the invention is a super-hydrophobic antifouling paint composition, and comprises the following raw materials in parts by mass:
20-35 parts of deionized water
15-30 parts of fluorocarbon emulsion
10-18 parts of water-based silicone-acrylate emulsion
0.2-15 parts of hydrophobic powder stearate
0.5 to 5.0 portions of defoaming agent
0.1-2.0 parts of film-forming assistant
0.2 to 1.0 portion of wetting dispersant
0.1-0.3 part of mildew preventive.
The hydrophobic powder stearate is one or more of sodium stearate, magnesium stearate, aluminum stearate and zinc stearate.
The defoaming agent is selected from mineral oil or organic silicon defoaming agents; the film forming assistant is one or more selected from ethylene glycol butyl ether, propylene glycol butyl ether and dodecyl alcohol ester.
The wetting and dispersing agent is selected from one of dike's height 760W and 762W, BYK 193.
The mildew preventive is an isothiazolinone bactericidal mildew preventive.
Advantageous technical effects
(1) The invention effectively refines and disperses the second phase through the secondary solution treatment, and is beneficial to the forming of the subsequent oxide film.
(2) According to the invention, through bidirectional pulse, heat is effectively dissipated, a thicker oxide film layer is obtained through high current density, and the obtained oxide film has regular and ordered pore channels.
(3) The super-hydrophobic aluminum alloy coating material has contact angle and rolling angle of 151.6 +/-1.0 degree and 4.9 +/-0.2 degree through fluorocarbon coating hole sealing.
(4) The anode oxide film has uniform pore channels and excellent binding force with the coating.
Drawings
FIG. 1 is a surface topography of an aluminum alloy at different time periods of heat treatment.
FIG. 2 shows the appearance of the anodic oxide film obtained by different treatment methods.
FIG. 3 is a sectional view and a topographic map of anodized aluminum alloy.
FIG. 4 is a morphology of an anodized aluminum alloy coating.
FIG. 5 AFM image of top coating
FIG. 6 is a graph of the morphology of the anodized aluminum alloy coating and a static water drop contact angle.
The specific implementation mode is as follows:
example 1
A super-hydrophobic antifouling paint composition is applied to the surface of an aluminum alloy and comprises the following specific steps:
(1) primary solution treatment: processing the aluminum alloy to obtain the required shape, increasing the temperature to 530 ℃ at 30 ℃/min, carrying out constant temperature treatment for 40min, and carrying out water quenching at room temperature for 5min, wherein the quenching water temperature is 15 ℃.
(2) Primary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace at 160 ℃ for oil bath holding for 6 h.
(3) Secondary solution treatment: raising the temperature to 480 ℃ at a speed of 30 ℃/min, carrying out constant temperature treatment for 40min, and carrying out water quenching at room temperature for 5min, wherein the quenching water temperature is 15 ℃.
(4) Secondary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace at 175 ℃ for oil bath holding for 8 h.
(5) Mechanical polishing, oil removal, alkali washing and acid washing: the mechanical grinding is realized by sequentially grinding 800# and 1000#, and the degreasing liquid is 35g/LNaOH and 10g/LNa2CO3Soaking for 1min at 40 deg.C, removing oil, and washing with deionized water; acid washing: pickling solution of 15vol.% HNO3Soaking at 25 deg.C for 20-30 s.
(6) Anodic oxidation: taking the aluminum alloy treated in the step (5) as an anode and soaking the aluminum alloy in electrolyte, wherein the electrolyte comprises sulfuric acid, oxalic acid, citric acid, tetrabutylammonium bromide and benzotriazole; the method specifically comprises the following steps: 250g/L sulfuric acid, 20 g/L oxalic acid, 30g/L citric acid, 10g/L tetrabutylammonium bromide and 5g/L benzotriazole.
The anodic oxidation is bipolar pulse, and the pulse condition is as follows: forward pulse current density: 4A/dm2The forward pulse width: 2s, forward duty cycle: 50%, number of pulses: 8, negative pulse current density: 1mA/cm2Negative pulse width: 500 μ s, negative duty cycle: 20%, number of pulses: anodic oxidation time of 20min, temperature: stirring speed 500rpm at 2 ℃.
(7) Sealing holes by using the super-hydrophobic antifouling paint; the super-hydrophobic antifouling paint comprises the following raw materials in parts by mass: 20 parts of deionized water; 15 parts of fluorocarbon emulsion; 10 parts of water-based silicone-acrylate emulsion; 0.2 part of hydrophobic powder stearate; 0.5 part of a defoaming agent; 0.1 part of film-forming additive; 0.2 part of wetting dispersant; 0.1 part of mildew preventive, wherein the hydrophobic powder stearate is sodium stearate; the defoaming agent is selected from organosilicon defoaming agents; the film forming assistant is selected from ethylene glycol butyl ether; the wetting and dispersing agent is selected from dyhi 760W; the mildew preventive is isothiazolinone bactericidal mildew preventive.
Weighing the raw materials according to the mass parts, mixing and stirring the fluorocarbon emulsion, the water-based silicone-acrylate emulsion, the hydrophobic powder, the wetting dispersant and the deionized water uniformly, wherein the stirring speed is 500rpm, and the stirring time is 20 min; and then adding the film forming auxiliary agent, the defoaming agent and the sterilization mildew preventive, stirring and mixing at the stirring speed of 1000rpm for 30min, and uniformly mixing to obtain the fluorocarbon coating.
The paint is sprayed and then is placed for 30min and then dried.
(8) Thermosetting and drying: drying at 40 deg.C for 8 h.
Example 2
A super-hydrophobic antifouling paint composition is applied to the surface of an aluminum alloy and comprises the following specific steps:
(1) primary solution treatment: processing aluminum alloy to obtain required shape, raising the temperature to 535 deg.C at 40 deg.C/min, treating at constant temperature for 50min, and water quenching at room temperature for 6min and 20 deg.C.
(2) Primary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace at 165 ℃ for oil bath holding for 7 h.
(3) Secondary solution treatment: raising the temperature to 490 ℃ at 40 ℃/min, carrying out constant temperature treatment for 50min, and carrying out water quenching at room temperature for 6min, wherein the quenching water temperature is 20 ℃.
(4) Secondary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace at 180 ℃ for oil bath holding for 9 h.
(5) Mechanical polishing, oil removal, alkali washing and acid washing: the mechanical grinding is realized by sequentially grinding 800# and 1000#, and the degreasing liquid is 37.5g/LNaOH and 12.5g/LNa2CO3Soaking for 2min at 45 deg.C, removing oil, and washing with deionized water; acid washing: pickling solution of 17.5vol.% HNO3Soaking at 27.5 deg.C for 25 s.
(6) Anodic oxidation: taking the aluminum alloy treated in the step (5) as an anode and soaking the aluminum alloy in electrolyte, wherein the electrolyte comprises sulfuric acid, oxalic acid, citric acid, tetrabutylammonium bromide and benzotriazole; the method specifically comprises the following steps: 265g/L sulfuric acid, 22.5g/L oxalic acid, 32.5g/L citric acid, 12.5g/L tetrabutylammonium bromide and 6g/L benzotriazole.
The anodic oxidation is bipolar pulse, and the pulse condition is as follows: forward pulse current density: 5A/dm2The forward pulse width: 2.5s, forward duty cycle: 55%, number of pulses: 9, negative pulse current density: 2mA/cm2And negative pulse width: 650 μ s, negative duty cycle: 23%, number of pulses: anodizing for 30min at high temperatureDegree: 4 ℃ and a stirring speed of 600 rpm.
(7) Sealing holes by using the super-hydrophobic antifouling paint; the super-hydrophobic antifouling paint comprises the following raw materials in parts by mass: 27.5 parts of deionized water; 22.5 parts of fluorocarbon emulsion; 14 parts of water-based silicone-acrylate emulsion; 7 parts of hydrophobic powder stearate; 2.5 parts of a defoaming agent; 1 part of a film-forming assistant; 0.5 part of wetting dispersant; 0.2 part of mildew preventive, wherein the hydrophobic powder stearate is aluminum stearate; the defoaming agent is selected from organosilicon defoaming agents; the film forming aid is selected from dodecyl alcohol ester; the wetting and dispersing agent is selected from 762W; the mildew preventive is isothiazolinone bactericidal mildew preventive.
Weighing the raw materials according to the mass parts, mixing and stirring the fluorocarbon emulsion, the water-based silicone-acrylic emulsion, the hydrophobic powder, the wetting dispersant and the deionized water uniformly, wherein the stirring speed is 650rpm, and the stirring time is 30 min; and then adding the film-forming assistant, the defoamer and the sterilization mildew preventive, stirring and mixing at the stirring speed of 1000rpm for 45min, and uniformly mixing to obtain the fluorocarbon coating.
And after the coating is sprayed, the surface is dried after the coating is placed for 35 min.
(8) Thermosetting and drying: drying was carried out at 43 ℃ for 9 h.
Example 3
A super-hydrophobic antifouling paint composition is applied to the surface of an aluminum alloy and comprises the following specific steps:
(1) primary solution treatment: processing aluminum alloy to obtain required shape, increasing to 540 deg.C at a rate of 50 deg.C/min, treating at constant temperature for 60min, and water quenching at room temperature for 7min and 25 deg.C.
(2) Primary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace at 170 ℃ for oil bath holding for 8 h.
(3) Secondary solution treatment: raising the temperature to 500 ℃ at a speed of 50 ℃/min, treating the mixture at constant temperature for 60min, and performing water quenching at room temperature for 7min and the quenching water temperature of 25 ℃.
(4) Secondary aging treatment: transferring the aluminum alloy into a 185 ℃ constant temperature holding furnace, and carrying out oil bath heat preservation for 10 h.
(5) Mechanical polishing, oil removal, alkali washing and acid washing: the mechanical grinding is sequentially grinding by using 800# and 1000#, and the deoiling liquid is 40g/LNaOH and 15 g/or greater than or equal to the standardLNa2CO3Soaking for 3min at 40-50 deg.C, removing oil, and washing with deionized water; acid washing: pickling solution of 20vol.% HNO3Soaking at 30 deg.C for 30 s.
(6) Anodic oxidation: taking the aluminum alloy treated in the step (5) as an anode to be soaked in electrolyte, wherein the electrolyte comprises sulfuric acid, oxalic acid, citric acid, tetrabutylammonium bromide and benzotriazole; the method specifically comprises the following steps: 280g/L sulfuric acid, 25 g/L oxalic acid, 35g/L citric acid, 15g/L tetrabutylammonium bromide and 7g/L benzotriazole.
The anodic oxidation is bipolar pulse, and the pulse condition is as follows: forward pulse current density: 6A/dm2The forward pulse width: 3s, forward duty cycle: 60%, pulse count: 10, negative pulse current density: 3 mA/cm2Negative pulse width: 800 μ s, negative duty cycle: 25%, number of pulses: anodic oxidation time of 40min, temperature: at 7 ℃ the stirring speed was 700 rpm.
(7) Sealing holes by using the super-hydrophobic antifouling paint; the super-hydrophobic antifouling paint comprises the following raw materials in parts by mass: 35 parts of deionized water; 30 parts of fluorocarbon emulsion; 18 parts of water-based silicone-acrylate emulsion; 15 parts of hydrophobic powder stearate; 5.0 parts of a defoaming agent; 0.1-2.0 parts of a film-forming assistant; 0.2-1.0 part of wetting dispersant; 0.1-0.3 part of mildew preventive, wherein the hydrophobic powder stearate is one or more of zinc stearate; the defoaming agent is selected from mineral oil defoaming agents; the film forming assistant is selected from propylene glycol butyl ether dialkyl carbonate; the wetting dispersant is selected from Digao BYK 193; the mildew preventive is isothiazolinone bactericidal mildew preventive.
Weighing the raw materials according to the mass parts, mixing and stirring the fluorocarbon emulsion, the water-based silicone-acrylate emulsion, the hydrophobic powder, the wetting dispersant and the deionized water uniformly, wherein the stirring speed is 800rpm, and the stirring time is 40 min; and then adding the film forming auxiliary agent, the defoaming agent and the sterilization mildew preventive, stirring and mixing at the stirring speed of 1000rpm for 60min, and uniformly mixing to obtain the fluorocarbon coating.
The paint is sprayed and then is placed for 40min and then dried.
(8) Thermosetting and drying: drying at 45 deg.C for 10 h.
Comparative example 1
A super-hydrophobic antifouling paint composition is applied to the surface of an aluminum alloy and comprises the following specific steps:
(1) mechanical polishing, oil removal, alkali washing and acid washing: the mechanical grinding is realized by sequentially grinding 800# and 1000#, and the degreasing liquid is 37.5g/LNaOH and 12.5g/LNa2CO3Soaking for 2min at 45 deg.C, removing oil, and washing with deionized water; acid washing: pickling solution of 17.5vol.% HNO3Soaking at 27.5 deg.C for 25 s.
(2) Anodic oxidation: taking the aluminum alloy treated in the step (5) as an anode and soaking the aluminum alloy in electrolyte, wherein the electrolyte comprises sulfuric acid, oxalic acid, citric acid, tetrabutylammonium bromide and benzotriazole; the method comprises the following specific steps: 265g/L sulfuric acid, 22.5g/L oxalic acid, 32.5g/L citric acid, 12.5g/L tetrabutylammonium bromide and 6g/L benzotriazole.
The anodic oxidation is bipolar pulse, and the pulse condition is as follows: forward pulse current density: 5A/dm2The forward pulse width: 2.5s, forward duty cycle: 55%, number of pulses: 9, negative pulse current density: 2mA/cm2Negative pulse width: 650 μ s, negative duty cycle: 23%, number of pulses: anodic oxidation time of 30min, temperature: 4 ℃ and a stirring speed of 600 rpm.
(3) Sealing holes by using the super-hydrophobic antifouling paint; the super-hydrophobic antifouling paint comprises the following raw materials in parts by mass: 27.5 parts of deionized water; 22.5 parts of fluorocarbon emulsion; 14 parts of water-based silicone-acrylate emulsion; 7 parts of hydrophobic powder stearate; 2.5 parts of a defoaming agent; 1 part of a film-forming assistant; 0.5 part of wetting dispersant; 0.2 part of mildew preventive, wherein the hydrophobic powder stearate is aluminum stearate; the defoaming agent is selected from organosilicon defoaming agents; the film forming aid is selected from dodecyl alcohol ester; the wetting and dispersing agent is selected from 762W; the mildew preventive is isothiazolinone bactericidal mildew preventive.
Weighing the raw materials according to the mass parts, mixing and stirring the fluorocarbon emulsion, the water-based silicone-acrylate emulsion, the hydrophobic powder, the wetting dispersant and the deionized water uniformly, wherein the stirring speed is 650rpm, and the stirring time is 30 min; and then adding the film-forming assistant, the defoamer and the sterilization mildew preventive, stirring and mixing at the stirring speed of 1000rpm for 45min, and uniformly mixing to obtain the fluorocarbon coating.
And after the coating is sprayed, the surface is dried after the coating is placed for 35 min.
(4) Thermosetting and drying: drying was carried out at 43 ℃ for 9 h.
Comparative example 2
A super-hydrophobic antifouling paint composition is applied to the surface of an aluminum alloy and comprises the following specific steps:
(1) primary solution treatment: processing aluminum alloy to obtain required shape, raising the temperature to 535 deg.C at 40 deg.C/min, treating at constant temperature for 50min, and water quenching at room temperature for 6min and 20 deg.C.
(2) Primary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace at 165 ℃ for oil bath holding for 7 h.
(3) Secondary solution treatment: raising the temperature to 490 ℃ at 40 ℃/min, carrying out constant temperature treatment for 50min, and carrying out water quenching at room temperature for 6min, wherein the quenching water temperature is 20 ℃.
(4) Secondary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace at 180 ℃ for oil bath holding for 9 h.
(5) Mechanical polishing, oil removal, alkali washing and acid washing: the mechanical grinding is realized by sequentially grinding 800# and 1000#, and the degreasing liquid is 37.5g/LNaOH and 12.5g/LNa2CO3Soaking for 2min at 45 deg.C, removing oil, and washing with deionized water; acid washing: pickling solution of 17.5vol.% HNO3Soaking at 27.5 deg.C for 25 s.
(6) Anodic oxidation: taking the aluminum alloy treated in the step (5) as an anode and soaking the aluminum alloy in electrolyte, wherein the electrolyte comprises sulfuric acid, oxalic acid, citric acid, tetrabutylammonium bromide and benzotriazole; the method specifically comprises the following steps: 265g/L sulfuric acid, 22.5g/L oxalic acid, 32.5g/L citric acid, 12.5g/L tetrabutylammonium bromide and 6g/L benzotriazole.
The anode is oxidized into direct current with the current density of 4A/dm2Anodizing time is 30min, temperature: 4 ℃ and a stirring speed of 600 rpm.
(7) Sealing holes by using the super-hydrophobic antifouling paint; the super-hydrophobic antifouling paint comprises the following raw materials in parts by mass: 27.5 parts of deionized water; 22.5 parts of fluorocarbon emulsion; 14 parts of water-based silicone-acrylic emulsion; 7 parts of hydrophobic powder stearate; 2.5 parts of a defoaming agent; 1 part of a film-forming assistant; 0.5 part of wetting dispersant; 0.2 part of mildew preventive, wherein the hydrophobic powder stearate is aluminum stearate; the defoaming agent is selected from organosilicon defoaming agents; the film forming aid is selected from dodecyl alcohol ester; the wetting and dispersing agent is selected from 762W; the mildew preventive is isothiazolinone bactericidal mildew preventive.
Weighing the raw materials according to the mass parts, mixing and stirring the fluorocarbon emulsion, the water-based silicone-acrylate emulsion, the hydrophobic powder, the wetting dispersant and the deionized water uniformly, wherein the stirring speed is 650rpm, and the stirring time is 30 min; and then adding the film forming auxiliary agent, the defoaming agent and the sterilization mildew preventive, stirring and mixing at the stirring speed of 1000rpm for 45min, and uniformly mixing to obtain the fluorocarbon coating.
And after the coating is sprayed, the surface is dried after the coating is placed for 35 min.
(8) Thermosetting and drying: drying was carried out at 43 ℃ for 9 h.
As shown in the attached figure 2, for the 2 series aluminum alloy, due to the existence of the copper phase second alloy, the anodic oxidation is difficult, the effective and regular anodic oxide film can not be formed, the surface roughness is higher than 1.73 μm (comparative example 1, when organic matter is not coated), after the secondary solution treatment, the bidirectional pulse is changed into the direct current power supply, the surface oxide film tends to be effective, the surface roughness is 1.08 μm (comparative example 2, when organic matter is not coated), after the secondary solution treatment and the bidirectional pulse treatment are carried out on the embodiment 2 of the invention, the surface roughness is 0.29 μm, the surface roughness is obviously reduced, and the extremely high surface regular nano array oxide film is inevitably obtained, as shown in the attached figure 3, the polarization curve test is carried out on the aluminum alloy coating material obtained in the embodiment 2, and the self-corrosion potential E is testedcorris-0.448V and corrosion current IcorrIs 1.192 x 10-8A/cm2FIG. 6 shows the coating topography and static contact angle of 151.6 + -1.0 deg., and FIG. 5 shows the AMF results of the coating surface.
The invention is in no way limited to the above-described embodiments, and further embodiments may be combined according to the solutions described in the present invention in combination with the means known in the art, all falling within the scope of the invention as claimed.

Claims (6)

1. The method for treating the aluminum alloy is characterized by comprising the following steps of: (1) primary solution treatment: processing the aluminum alloy to obtain the required shape, increasing the temperature to 530 ℃ and 540 ℃ at a speed of 30-50 ℃/min, carrying out constant temperature treatment for 40-60min, carrying out water quenching for 5-7min at room temperature, and carrying out quenching water temperature of 15-25 ℃;
(2) primary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace with the temperature of 160-170 ℃ for oil bath holding for 6-8 h;
(3) secondary solution treatment: raising the temperature to 480-500 ℃ at a speed of 30-50 ℃/min, carrying out constant temperature treatment for 40-60min, and carrying out water quenching at room temperature for 5-7min and the quenching water temperature of 15-25 ℃;
(4) secondary aging treatment: transferring the aluminum alloy into a constant temperature holding furnace at 185 ℃ of 175-plus-material temperature, and carrying out oil bath heat preservation for 8-10 h;
(5) mechanical polishing, oil removal, alkali washing and acid washing;
(6) anodic oxidation: taking the aluminum alloy treated in the step (5) as an anode, and soaking the aluminum alloy in electrolyte, wherein the electrolyte comprises sulfuric acid, oxalic acid, citric acid, tetrabutylammonium bromide and benzotriazole;
the anodic oxidation adopts bipolar pulse, and the pulse conditions are as follows:
forward pulse current density: 4-6A/dm2，
Forward pulse width: 2-3s of the reaction solution for the first time,
forward duty cycle: 50 to 60 percent of the total weight of the mixture,
number of forward pulses: 8-10,
negative pulse current density: 1-3 mA/cm2，
Negative pulse width: 500-800 mu.s of the reaction solution,
negative duty cycle: 20 to 25 percent of the total weight of the mixture,
negative pulse number: 1,
anodizing time is 20-40min, temperature: 2-7 ℃, the stirring speed is 500-700 rpm;
(7) sealing holes by using the super-hydrophobic antifouling paint composition: spraying the super-hydrophobic antifouling paint composition on the surface of the aluminum alloy obtained by anodic oxidation treatment; after spraying, standing for 30-40min and drying the surface;
the super-hydrophobic antifouling paint composition is prepared from the following raw materials in parts by mass:
20-35 parts of deionized water;
15-30 parts of fluorocarbon emulsion;
10-18 parts of water-based silicone-acrylate emulsion;
0.2-15 parts of hydrophobic powder stearate;
0.5-5.0 parts of defoaming agent;
0.1-2.0 parts of film-forming assistant;
0.2-1.0 part of wetting dispersant;
0.1-0.3 part of mildew preventive;
(8) thermosetting and drying.
2. The method of claim 1, wherein the hydrophobic powder stearate is one or more of sodium stearate, magnesium stearate, aluminum stearate, and zinc stearate; the defoaming agent is selected from mineral oil or organic silicon defoaming agents; the film forming auxiliary agent is selected from one or more of ethylene glycol butyl ether, propylene glycol butyl ether and dodecyl alcohol ester; the wetting and dispersing agent is selected from one of digao 760W, 762W, BYK 193; the mildew preventive is isothiazolinone bactericidal mildew preventive.
3. The method according to claim 1, wherein the aluminum alloy is a 2-series or 7-series aluminum alloy.
4. The method of claim 1, wherein the anodic oxidation electrolyte comprises 280g/L sulfuric acid, 20-25 g/L oxalic acid, 30-35g/L citric acid, 10-15g/L tetrabutylammonium bromide, and 5-7g/L benzotriazole.
5. The method according to claim 1, wherein the degreasing liquid is 35-40g/LNaOH and 10-15g/LNa2CO3Soaking for 1-3min at 40-50 deg.C, and washing with deionized water; the pickling solution of pickling is 15-20vol.% of HNO3Pickling and soaking at 25-30 deg.c for 20-30 sec.
6. The method of claim 1, wherein the hot set drying: drying at 40-45 deg.C for 8-10 h.
CN202111650362.1A 2021-12-30 2021-12-30 Super-hydrophobic antifouling paint composition Active CN114133797B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111650362.1A CN114133797B (en) 2021-12-30 2021-12-30 Super-hydrophobic antifouling paint composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111650362.1A CN114133797B (en) 2021-12-30 2021-12-30 Super-hydrophobic antifouling paint composition

Publications (2)

Publication Number Publication Date
CN114133797A CN114133797A (en) 2022-03-04
CN114133797B true CN114133797B (en) 2022-07-05

Family

ID=80383752

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111650362.1A Active CN114133797B (en) 2021-12-30 2021-12-30 Super-hydrophobic antifouling paint composition

Country Status (1)

Country Link
CN (1) CN114133797B (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105506705A (en) * 2015-12-31 2016-04-20 江苏大学 Preparing method of aluminum alloy hard anode oxide film
CN105886976B (en) * 2016-04-21 2018-04-03 湖南人文科技学院 A kind of thermo-mechanical treatment process for improving aluminium alloy combination property
CN107740107A (en) * 2017-10-30 2018-02-27 珠海市智宝化工有限公司 A kind of etching solution recycling accelerator
CN108034860B (en) * 2017-11-06 2019-07-16 安徽福瑞尔铝业科技有限公司 A kind of production technology of anticorrosion aluminium ally section for building
CN109679438A (en) * 2018-12-25 2019-04-26 沈阳化工研究院有限公司 A kind of environment-friendly type hydrophobicity fluorine-containing clear coat composition and preparation method thereof
CN111410910A (en) * 2020-05-19 2020-07-14 苏州德加画材科技有限公司 Antifouling self-cleaning coating and preparation method thereof

Also Published As

Publication number Publication date
CN114133797A (en) 2022-03-04

Similar Documents

Publication Publication Date Title
JP4125765B2 (en) Method of coating ceramic film of metal, electrolytic solution used therefor, ceramic film and metal material
KR101195458B1 (en) Method for treating the surface of metal
CN103498179B (en) Aluminum or aluminum alloy surface oxide film and method for preparing same
CN106757264B (en) A kind of wide temperature anodic oxidation electrolyte of aluminum alloy environment-friendly type and method for oxidation
JPWO2010073916A1 (en) Metal electrolytic ceramic coating method, metal electrolytic ceramic coating electrolyte and metal material
CN103060881B (en) Titanium alloy surface black high temperature coatings preparation method
CN102154673A (en) Method for preparing environment-friendly micro-arc oxidation black ceramic film on aluminum alloy surface
CN100577891C (en) Anodic oxidation method for raising rigidity and corrosion resistance of plated aluminum on surface of metal base
CN111005050B (en) Preparation method of double coating for improving corrosion resistance of sintered neodymium-iron-boron magnet
CN102021632A (en) Method for preparing protective film on copper alloy surface
CN105040071A (en) Micro-arc oxidation electrolyte and magnesium alloy surface treatment method with same
CN106757260A (en) A kind of composite Nano electrolyte for preparing micro-arc oxidation of aluminum alloy surface film its application
CN107190299A (en) Hardening oxidation method for compressor of air conditioner rotary compression disk aluminium alloy
CN114133797B (en) Super-hydrophobic antifouling paint composition
CN114369773B (en) Treatment method of aluminum alloy material
CN114316693B (en) Preparation method of super-hydrophobic coating
JP5694351B2 (en) Method of applying diffusion treatment to the coating layer of construction members that can withstand the marine climate
CN109161951B (en) Magnesium alloy micro-arc oxidation electrolyte and application thereof
JP2004035930A (en) Aluminum alloy material and anodization treatment method therefor
Breslin et al. Influence of rare-earth metal passivation treatments on the dissolution of tin-zinc coatings
US11486051B2 (en) Durable white inorganic finish for aluminium articles
CN113584542A (en) Method for plating nickel on surface of aluminum alloy
JPH07207467A (en) Surface treatment of aluminum alloy
CN106591626B (en) A kind of TA18 titanium alloy composite material and its preparation method and application
KR20210125001A (en) Method for manufacturing corrosion-resistant aluminum-silicon alloy castings, such corrosion-resistant aluminum-silicon alloy castings and uses thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20220617

Address after: 100089 room 205, second floor, building 16, Chuangke town community supporting commercial building, Wenquan Town, Haidian District, Beijing

Applicant after: BEIJING CHUANYUE TECHNOLOGY CO.,LTD.

Address before: 510641 School of chemistry and chemical engineering, South China University of technology, 381 Wushan Road, Tianhe District, Guangzhou City, Guangdong Province

Applicant before: Wang Yongqin

GR01 Patent grant
GR01 Patent grant