CN105463549B - A kind of anodization process for improving aluminium and aluminium alloy barrier propterty - Google Patents
A kind of anodization process for improving aluminium and aluminium alloy barrier propterty Download PDFInfo
- Publication number
- CN105463549B CN105463549B CN201510882094.4A CN201510882094A CN105463549B CN 105463549 B CN105463549 B CN 105463549B CN 201510882094 A CN201510882094 A CN 201510882094A CN 105463549 B CN105463549 B CN 105463549B
- Authority
- CN
- China
- Prior art keywords
- anodization
- aluminium
- concentration
- aluminum alloy
- solution
- 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
Links
Classifications
-
- 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
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The present invention is a kind of anodization process for improving aluminium and aluminium alloy barrier propterty, anodization solution used is mixed in proportion by at least one inorganic salts and water of sulfuric acid, Boratex, malic acid and cerium, anodization carries out anodization using control voltage system to aluminum or aluminum alloy material.Anodization membranous layer corrosion resistance prepared by the present invention is good, excellent with organic Film Adhesion, low to matrix Influence of Fatigue Properties, has the characteristics that simple for process, performance is stable, film forming efficiency is high, environmental pollution is small.The Chrome-free enclosure method of organic inorganic hybridization is selected after anodization, which is entirely free of chromium and other poisonous and harmful substances, discharging of waste liquid is not generated in closed process.Anodization film layer corrosion resisting property after closing is good, does not influence original anodization film layer film adhesion.Above-mentioned anodization process and enclosure method can be used for substituting traditional chromic acid anodizing, sulfur acid anodizing and bichromate sealing technique, the aluminum and aluminum alloy mateial surfacecti proteon applied to every profession and trades such as aviations.
Description
Technical field
The present invention is a kind of anodization process for improving aluminium and aluminium alloy barrier propterty, belongs to metallic surface treatment technology
Field.
Background technology
Aluminium and aluminium alloy are one of widest structural metallic materials of current application amount.Select suitable aluminium and aluminium alloy table
Surface treatment technique is for improving the corrosion resistance of aluminium and aluminium alloy, enhancing its binding force with organic coating, ensure basis material
Fatigue behaviour important role.Traditional aluminium and aluminum alloy surface process for protecting generally use sulfur acid anodizing or chromic acid anode
Chemical industry skill.Although sulfur acid anodizing has good corrosion resisting property, but very big for the Influence of Fatigue Properties of matrix, it is impossible to meet
Al and Al-alloy safety, the requirement of long-life；Chromic acid anodizing is smaller to the Influence of Fatigue Properties of matrix, but due to
Film layer is relatively thin, and corrosion resistance is poor, it is impossible to meet the requirement of Al and Al-alloy barrier propterty, while chromate can also to environment
Generate very big pollution.
Closing process must be used just to can guarantee the corrosion resisting property of film layer after anodization.Widely used at present is weight chromium
Hydrochlorate or the closing of dilute chromic acid.This method not only contains Cr VI, and generates a large amount of flushing waste waters, there is serious pollution to environment.
In addition, the technique must be heated to 90 DEG C or more, not only waste of energy, will also generate a large amount of chromium-containing waste gas.
Invention content
Exactly design provides a kind of raising aluminium to the present invention in view of the above-mentioned deficiencies in the prior art and aluminium alloy is prevented
The anodization process of performance is protected, the purpose is to utilize sulfuric acid-boric acid salt-malic acid-cerium salt solution to aluminum and aluminum alloy mateial
Part carries out electrolysis anodization, realizes that relatively low environment influences, subsequent corrosion resistance of surface treatment process is supplemented with sun
The deficiency for the film layer corrosion resisting property that polarizes.The corrosion resistance of aluminum and aluminum alloy mateial piece surface is improved without reducing fatigability
Energy.
The purpose of the present invention is achieved through the following technical solutions：
This kind improves the anodization process of aluminium and aluminium alloy barrier propterty, and this method includes cleaning oil removing, at surface deoxidation
Reason, surface anodization handles and subsequent corrosion resistance of surface treatment process, in surface anodization treatment process, treats anodization
Aluminum and aluminum alloy mateial part as anode, using stainless steel or stereotype or graphite as cathode, it is characterised in that：
Anodization solution in above-mentioned surface anodization treatment process is the inorganic of sulfuric acid, Boratex, DL-malic acid and cerium
The aqueous solution of salt, wherein, a concentration of 0.3M~0.6M of sulfuric acid, a concentration of the 1 × 10 of Boratex-2M~2 × 10-1M, DL- apple
Fruit acid concentration is 2 × 10-2M~3 × 10-1M, a concentration of the 1 × 10 of the inorganic salts of cerium-2M~2.5 × 10-1M；
In above-mentioned surface anodization treatment process, between the temperature of anodization solution maintains 15 DEG C~30 DEG C, anode and
Apply the potential difference of 15V~25V between cathode, anodisation time is 20min~40min；
The corrosion resistance of surface processing solution that above-mentioned surface anodization is handled in subsequent corrosion resistance of surface treatment process is molten
Agent is glycerine and the colloid of methanol, and the wherein presoma of colloid is epoxy one type of silane, fluorine-containing one type of silane, zirconium metal alkoxide and cerium
Metal alkoxide, the weight percent of solvent is 40%~60% in colloid, and the atomic percent of four kinds of presomas is 1:1:1:1,
Also added with catalyst, hydrolysis stabilizer and surfactant in colloid, catalyst is malic acid, and hydrolysis stabilizer is acetyl
Ethyl acetate, surfactant OP-10, the weight percent that the contents of three kinds of ingredients accounts for colloid are 0.5%~1%；
Above-mentioned surface anodization is handled in subsequent corrosion resistance of surface treatment process, with the mode of spraying or dip-coating by colloid
Then anodized surface coated in aluminum and aluminum alloy mateial part is dried at room temperature for 20min~40min, is dried at 50 DEG C
20~40min.
It is characterized in that：A concentration of 0.5M of sulfuric acid in anodization solution, a concentration of 0.015M of Boratex, DL- apples
Acid concentration is 0.045M, a concentration of 0.02M of the inorganic salts of cerium, the temperature of the anodization solution in surface anodization processing procedure
25 DEG C ± 1 DEG C is maintained, applies the potential difference of 15V, anodisation time 20min between anode and cathode.
It is characterized in that：In surface anodization treatment process, treat anodized aluminum and aluminum alloy mateial part without
When electricity is entered in anodization solution, voltage need to be applied in 2min, initial voltage maximum value is 5V, then to be no more than 5V/min
Rate rise to 15V~25V, keep after anodisation time power-off 2min domestic demands by aluminum and aluminum alloy mateial part from anode
Change in solution and take out and clean.
The characteristics of anodization the method for the present invention is on the basis of conventional sulfuric acid anodic process, reduces sulfuric acid
Concentration, while increase borate, DL-malic acid and cerium salt.Due to the reduction of sulfuric acid concentration, anodizing process is reduced
In dissolving to anodization film layer, improve the thickness on anodic film barrier layer；Adding borate and malic acid simultaneously contributes to
The formation on barrier layer.Cerium salt and its complexing agent malic acid are added in anodization solution, reaction generation rare earth complex ion exists
Play the role of space blocking in anodizing process on the interface of anode reaction, so as to influence oxidation film generation and dissolving
Balance so that influencing the growth course of anodic film, makes the anodic films such as barrier layer thickness, Membrane pore density, the aperture of film microcosmic
Pattern changes, the final performance for improving anodization film layer.With traditional aluminium and aluminium alloy sulfur acid anodizing, chromic acid anodizing
Technique is compared, anodic process of the invention have it is simple for process, performance is stable, film forming efficiency is high, excellent combination property, to ring
The advantages that border pollution is small.
A kind of anodization postprocessing working procedures of the present invention use the colloid of hybrid inorganic-organic.In colloid before four kinds
It drives after hydrolysis and condensation reaction occur for body and is formed, wherein containing cerium in the hydrolysis condensation product and anodization of zirconium and ce metal alkoxide
Aluminium oxide has synergistic effect, and the two can form stable Covalent bonding together, and bond strength is very good.Other two presoma is
Siloxanes containing functional group, the siloxanes after condensation reaction can effectively fill the gap of anodic film, reach sealing effect.
And fluorine-containing siloxanes has the characteristic of surface hydrophobicity, greatly enhances the ability of film layer medium corrosion-resistant immersion, improves resistance to
Corrosion energy.Finally, the siloxanes containing epoxy group can be chemically reacted with common epoxy primer or polyurethanes paint film, film
Layer Covalent bonding together similary with paint film.So entire film layer and organic paint film Covalent bonding together, bond strength are fabulous.In addition, phase
Than in traditional enclosure method, which closes without flushing water, to environment without any pollution.
Specific embodiment
Technical solution of the present invention is further described below with reference to embodiment：
Embodiment 1
Process using anodization process of the present invention is as follows：
1st, test material is 2024 naked aluminium plates, and heat treating regime T3, size is 75mm × 150mm × 2mm；
2nd, aluminium and aluminum alloy specimen are immersed in acetone, ultrasonic oil removal 8min, takes out 50 DEG C of hot blast dryings；
3rd, aluminium and aluminum alloy specimen dress are hung on aluminium alloy hanger；
4th, aluminium and aluminum alloy specimen are placed in progress specimen surface oil removing in the detergent solution of 50g/L, in 60 DEG C of cleanings
Oil removing is no less than 10min in agent；Circulating water washed samples are used after oil removing；
5th, deoxidation is carried out to aluminium and aluminum alloy specimen at 25 DEG C, deaeration time 3min is clear with deionized water after taking-up
Wash specimen surface；Chromic anhydride (CrO in deoxidizing solution3) a concentration of 45g/L, nitric acid (HNO3, ρ=1.42g/mL) and a concentration of 100g/L,
Hydrofluoric acid concentration is 9mL/L；
6th, aluminium and aluminum alloy specimen carry out anodization, in anodization aqueous solution, sulfuric acid (H2SO4, ρ=1.84g/mL) and concentration
For 0.5M, a concentration of 0.015M of Boratex, a concentration of 0.04M of DL-malic acid, a concentration of 0.02M of cerous sulfate, sample is at 25 DEG C
Anodization is carried out in solution；Using 1Cr18Ni9Ti stainless steels as cathode, aluminium and aluminum alloy specimen are as anode；In anodization
In the process using clean compressed air stirring；Slot 1min applies voltage under sample, and 15V is risen to the rate of 5V/min, keeps
Anodising time 20min；Sample is taken out simultaneously washed samples by 0.5min from slot after power-off；
7th, the aluminium after anodization and aluminum alloy specimen carry out anodization subsequent processing process in colloid.The presoma of colloid
It is γ-glycerine ether oxygen propyl trimethoxy silicane, triethoxy fluoric silane, zirconium-n-propylate and nitre respectively comprising four kinds of ingredients
Sour cerium, solvent use glycerine, and catalyst uses malic acid, and hydrolysis stabilizer uses ethyl acetoacetate.Treat four kinds of presomas
After the completion of reaction, Surfactant OP -10 is finally added.The atomic percent for adding above-mentioned four kinds of presomas is 1:1:1:1, water
Addition be all presoma complete hydrolysis calculated value.Solvent content is 40%~60%, catalyst hydrolysis-stable
The content of agent and surfactant is 0.5%~1%.Sample after anodization is immersed in confining liquid, after 1~2min of waiting slowly
It takes out, at room temperature dry 20~40min, dry 20~40min under the conditions of 50 DEG C；
8th, it is 20 μm of epoxy primer in the aluminium and aluminum alloy specimen surface spraying thickness of test binding force, carries out as required
Fully curing.
Embodiment 2
The process of anodization process is as follows：
1st, test material is 7075 naked aluminium plates, and heat treating regime T6, size is 75mm × 150mm × 2mm；
2nd, aluminium and aluminum alloy specimen are immersed in acetone, ultrasonic oil removal 8min, takes out 50 DEG C of hot blast dryings；
3rd, aluminium and aluminum alloy specimen dress are hung on aluminium alloy hanger；
4th, aluminium and aluminum alloy specimen are placed in progress specimen surface oil removing in the detergent solution of 50g/L, in 60 DEG C of cleanings
Oil removing is no less than 10min in agent；Circulating water washed samples are used after oil removing；
5th, deoxidation is carried out to aluminium and aluminum alloy specimen at 25 DEG C, deaeration time 3min is clear with deionized water after taking-up
Wash specimen surface；Deoxidizing solution is chromic anhydride (CrO3) a concentration of 45g/L, nitric acid (HNO3, ρ=1.42g/mL) and a concentration of 100g/L,
Hydrofluoric acid concentration is 9mL/L；
6th, aluminium and aluminum alloy specimen carry out anodization, and anodization solution is sulfuric acid (H2SO4, ρ=1.84g/mL) and it is a concentration of
0.45M, a concentration of 0.02M of Boratex, a concentration of 0.06M of DL-malic acid, the aqueous solution of a concentration of 0.015M of cerous sulfate；Sample
Anodization is carried out in 27 DEG C of solution；Using 1Cr18Ni9Ti stainless steels as cathode, aluminium and aluminum alloy specimen are as anode；
Using clean compressed air stirring in anodizing process；Slot 1min applies voltage under sample, is risen to the rate of 4V/min
16V keeps anodising time 20min；Sample is taken out simultaneously washed samples by 0.5min from slot after power-off；
7th, the aluminium after anodization and aluminum alloy specimen carry out anodization subsequent processing process in colloid.The presoma of colloid
It is γ-glycerine ether oxygen propyl trimethoxy silicane, triethoxy fluoric silane, zirconium-n-propylate and nitre respectively comprising four kinds of ingredients
Sour cerium, solvent use glycerine, and catalyst uses malic acid, and hydrolysis stabilizer uses ethyl acetoacetate.Treat four kinds of presomas
After the completion of reaction, Surfactant OP -10 is finally added.The atomic percent for adding above-mentioned four kinds of presomas is 1:1:1:1, water
Addition be all presoma complete hydrolysis calculated value.Solvent content is 40%~60%, catalyst hydrolysis-stable
The content of agent and surfactant is 0.5%~1%.Sample after anodization is immersed in confining liquid, after 1~2min of waiting slowly
It takes out, at room temperature dry 20~40min, dry 20~40min under the conditions of 50 DEG C；
8th, it is 20 μm of epoxy primer in test binding force aluminium and aluminum alloy specimen surface spraying thickness, is filled as required
Divide curing.
Embodiment 3
The process of anodization process is as follows：
1st, test material is 2024 alclad planks, and heat treating regime T3, size is 75mm × 150mm × 1.5mm；
2nd, aluminium and aluminum alloy specimen are immersed in acetone, ultrasonic oil removal 8min, takes out 50 DEG C of hot blast dryings；
3rd, aluminium and aluminum alloy specimen dress are hung on aluminium alloy hanger；
4th, aluminium and aluminum alloy specimen are placed in progress specimen surface oil removing in the detergent solution of 50g/L, in 60 DEG C of cleanings
Oil removing is no less than 10min in agent；Circulating water washed samples are used after oil removing；
5th, deoxidation is carried out to aluminium and aluminum alloy specimen at 25 DEG C, deaeration time 3min is clear with deionized water after taking-up
Wash specimen surface；Deoxidizing solution is chromic anhydride (CrO3) a concentration of 45g/L, nitric acid (HNO3, ρ=1.42g/mL) and a concentration of 100g/L,
Hydrofluoric acid concentration is 9mL/L；
6th, aluminium and aluminum alloy specimen carry out anodization, and anodization solution is sulfuric acid (H2SO4, ρ=1.84g/mL) and it is a concentration of
0.55M, a concentration of 0.015M of Boratex, a concentration of 0.045M of DL-malic acid, the aqueous solution of a concentration of 0.025M of cerous sulfate；Examination
Sample carries out anodization in 25 DEG C of solution；Using 1Cr18Ni9Ti stainless steels as cathode, aluminium and aluminum alloy specimen as sun
Pole；Using clean compressed air stirring in anodizing process；Slot 1min applies voltage under sample, with the rate liter of 5V/min
To 15V, anodising time 20min is kept；Sample is taken out simultaneously washed samples by 0.5min from slot after power-off；
7th, the aluminium after anodization and aluminum alloy specimen carry out anodization subsequent processing process in colloid.The presoma of colloid
It is γ-glycerine ether oxygen propyl trimethoxy silicane, triethoxy fluoric silane, zirconium-n-propylate and nitre respectively comprising four kinds of ingredients
Sour cerium, solvent use glycerine, and catalyst uses malic acid, and hydrolysis stabilizer uses ethyl acetoacetate.Treat four kinds of presomas
After the completion of reaction, Surfactant OP -10 is finally added.The atomic percent for adding above-mentioned four kinds of presomas is 1:1:1:1, water
Addition be all presoma complete hydrolysis calculated value.Solvent content is 40%~60%, catalyst hydrolysis-stable
The content of agent and surfactant is 0.5%~1%.Sample after anodization is immersed in confining liquid, after 1~2min of waiting slowly
It takes out, at room temperature dry 20~40min, dry 20~40min under the conditions of 50 DEG C；
8th, it is 20 μm of epoxy primer in test binding force aluminium and aluminum alloy specimen surface spraying thickness, is filled as required
Divide curing.
Embodiment 4 (comparative example)
The process of anodization process is as follows：
1st, test material is 2024 naked aluminium plates, and heat treating regime T3, size is 75mm × 150mm × 2mm；
2nd, aluminium and aluminum alloy specimen are immersed in acetone, ultrasonic oil removal 8min, takes out 50 DEG C of hot blast dryings；
3rd, aluminium and aluminum alloy specimen dress are hung on aluminium alloy hanger；
4th, aluminium and aluminum alloy specimen are placed in progress specimen surface oil removing in the detergent solution of 50g/L, in 60 DEG C of cleanings
Oil removing is no less than 10min in agent；Circulating water washed samples are used after oil removing；
5th, deoxidation is carried out to aluminium and aluminum alloy specimen at 25 DEG C, deaeration time 3min is clear with deionized water after taking-up
Wash specimen surface；Chromic anhydride (CrO in deoxidizing solution3) a concentration of 45g/L, nitric acid (HNO3, ρ=1.42g/mL) and a concentration of 100g/L,
Hydrofluoric acid concentration is 9mL/L；
6th, aluminium and aluminum alloy specimen carry out anodization, in anodization aqueous solution, sulfuric acid (H2SO4, ρ=1.84g/mL) and concentration
For 0.5M, a concentration of 0.015M of Boratex, a concentration of 0.04M of DL-malic acid, a concentration of 0.02M of cerous sulfate, sample is at 25 DEG C
Anodization is carried out in solution；Using 1Cr18Ni9Ti stainless steels as cathode, aluminium and aluminum alloy specimen are as anode；In anodization
In the process using clean compressed air stirring；Slot 1min applies voltage under sample, and 15V is risen to the rate of 5V/min, keeps
Anodising time 20min；Sample is taken out simultaneously washed samples by 0.5min from slot after power-off；
7th, the aluminium after anodization and aluminum alloy specimen close 25min, dilute chromate envelope in 90 DEG C of dilute chromatedsolution
Solution is closed as chromium anhydride concentration 70mg/L, the aqueous solution of chromic acid na concn 48mg/L；
8th, it is 20 μm of epoxy primer in the aluminium and aluminum alloy specimen surface spraying thickness of test binding force, carries out as required
Fully curing.
Embodiment 5 (comparative example)
The process of anodization process is as follows：
1st, test material is 2024 naked aluminium plates, and heat treating regime T3, size is 75mm × 150mm × 1.5mm；
2nd, aluminium and aluminum alloy specimen are immersed in acetone, ultrasonic oil removal 8min, takes out 50 DEG C of hot blast dryings；
3rd, aluminium and aluminum alloy specimen dress are hung on aluminium alloy hanger；
4th, aluminium and aluminum alloy specimen are placed in progress piece surface oil removing in the detergent solution of 50g/L, in 60 DEG C of cleanings
Oil removing is no less than 10min in agent；Circulating water washed samples are used after oil removing；
5th, deoxidation is carried out to aluminium and aluminum alloy specimen at 25 DEG C, deaeration time 3min is clear with deionized water after taking-up
Wash specimen surface；Three sour deoxidizing solutions are chromic anhydride (CrO3) a concentration of 45g/L, nitric acid (HNO3, ρ=1.42g/mL) and it is a concentration of
100g/L, hydrofluoric acid concentration 9mL/L；
6th, aluminium and aluminum alloy specimen carry out anodization, and anodization solution is sulfuric acid (H2SO4, ρ=1.84g/mL) and concentration
1.93M aqueous solution；Sample carries out anodization in 20 DEG C of solution；Made using stereotype as cathode, aluminium and aluminum alloy specimen
For anode；Using clean compressed air stirring in anodizing process；Sample is in 1A/dm2Anodization is kept under current density
40min；Sample is taken out simultaneously washed samples by 0.5min from slot after power-off；
7th, the aluminium after anodization and aluminum alloy specimen close 20min, bichromate envelope in 95 DEG C of dichromate solution
Solution is closed as potassium bichromate (K2Cr2O7) concentration 50g/L the aqueous solution sample of binding force (test without this step)；
8th, it is 20 μm of epoxy primer in test binding force aluminium and aluminum alloy specimen surface spraying thickness, is filled as required
Divide curing.
Embodiment 6 (comparative example)
The process of anodization process is as follows：
1st, test material is 2024 naked aluminium plates, and heat treating regime T3, size is 75mm × 150mm × 1.5mm；
2nd, aluminium and aluminum alloy specimen are immersed in acetone, ultrasonic oil removal 8min, takes out 50 DEG C of hot blast dryings；
3rd, aluminium and aluminum alloy specimen dress are hung on aluminium alloy hanger；
4th, aluminium and aluminum alloy specimen are placed in progress piece surface oil removing in the detergent solution of 50g/L, in 60 DEG C of cleanings
Oil removing is no less than 10min in agent；Circulating water washed samples are used after oil removing；
5th, deoxidation is carried out to aluminium and aluminum alloy specimen at 25 DEG C, deaeration time 3min is clear with deionized water after taking-up
Wash specimen surface；Deoxidizing solution is chromic anhydride (CrO3) a concentration of 45g/L, nitric acid (HNO3, ρ=1.42g/mL) and a concentration of 100g/L,
Hydrofluoric acid concentration is 9mL/L；
6th, aluminium and aluminum alloy specimen carry out anodization, and anodization solution is chromic anhydride (CrO3) a concentration of 45g/L；Sample is 35
DEG C solution in carry out anodization；Using stereotype as cathode, aluminium and aluminum alloy specimen are as anode；It is adopted in anodizing process
It is stirred with clean compressed air；Slot 1min applies voltage under sample, 20V is risen to the rate of 5V/min, when keeping anodization
Between 35min；Sample is taken out simultaneously washed samples by 0.5min from slot after power-off；
7th, the aluminium after anodization and aluminum alloy specimen close 40min, bichromate envelope in 96 DEG C of dichromate solution
Solution is closed as potassium bichromate (K2Cr2O7) concentration 1g/L the aqueous solution sample of binding force (test without this step)；
8th, it is 20 μm of epoxy primer in test binding force aluminium and aluminum alloy specimen surface spraying thickness, is filled as required
Divide curing.
The Nature comparison for the sample that table 1 is handled according to preceding embodiment
(1) the corrosion resistance examination of anodization film layer is carried out according to " 10125 artificial atmosphere corrosion test salt spray tests of GB/T "
It tests.
(2) knot of anodic film and organic paint film is carried out according to " cross cut test of 9286 paint and varnish paint films of GB/T "
Resultant force is tested.
(3) experiment on fatigue properties of anodization sample is carried out according to " 5287 metal material axial fatigue test methods of HB ".
Test parameters is：Maximum stress 240MPa；Stress ratio R=0.06；Test frequency 135HZ；25 DEG C of experimental temperature.
Referring to table 1, by can compared with comparative example sample anodic film the performance test results to sample of the embodiment of the present invention
To find out, corrosion resistance and organic film adhesion meet and exceed chromic acid sun after anodization film layer closing prepared by the present invention
Polarization, the performance indicator of sulfur acid anodizing, while the fatigue behaviour of sample is significantly higher than the fatigue behaviour of sulfur acid anodizing sample.
And Chrome-free enclosure method performance of the present invention also meets and exceeds traditional enclosure method containing chromium.
Compared with prior art, technical solution of the present invention proposes a kind of anodization side for improving aluminium and aluminium alloy barrier propterty
Method and enclosure method, using the anodization membranous layer corrosion resistance for preparing of the present invention it is good, with organic Film Adhesion it is excellent, to matrix
Influence of Fatigue Properties is low, has the characteristics that simple for process, performance is stable, film forming efficiency is high, environmental pollution is small.In addition, this kind
Anodization enclosure method, it is easy to use, to environment without any pollution.
Claims (3)
1. a kind of anodization process for improving aluminium and aluminium alloy barrier propterty, this method includes cleaning oil removing, surface deoxidation is handled,
Surface anodization handles and subsequent corrosion resistance of surface treatment process, in surface anodization treatment process, treats anodized
Aluminum and aluminum alloy mateial part is as anode, using stainless steel or stereotype or graphite as cathode, it is characterised in that：
Anodization solution in above-mentioned surface anodization treatment process is the inorganic salts of sulfuric acid, Boratex, DL-malic acid and cerium
Aqueous solution, wherein, a concentration of 0.3M~0.6M of sulfuric acid, a concentration of the 1 × 10 of Boratex-2M~2 × 10-1M, DL-malic acid
A concentration of 2 × 10-2M~3 × 10-1M, a concentration of the 1 × 10 of the inorganic salts of cerium-2M~2.5 × 10-1M；
In above-mentioned surface anodization treatment process, between the temperature of anodization solution maintains 15 DEG C~30 DEG C, anode and cathode
Between apply 15V~25V potential difference, anodisation time be 20min~40min；
The corrosion resistance of surface processing solution that above-mentioned surface anodization is handled in subsequent corrosion resistance of surface treatment process is that solvent is
The presoma of the colloid of glycerine and methanol, wherein colloid is epoxy one type of silane, fluorine-containing one type of silane, zirconium metal alkoxide and ce metal
Alkoxide, the weight percent of solvent is 40%~60% in colloid, and the atomic percent of four kinds of presomas is 1:1:1:1, in glue
Also added with catalyst, hydrolysis stabilizer and surfactant in body, catalyst is malic acid, and hydrolysis stabilizer is acetoacetate
Ethyl ester, surfactant OP-10, the weight percent that the contents of three kinds of ingredients accounts for colloid are 0.5%~1%；
Above-mentioned surface anodization is handled in subsequent corrosion resistance of surface treatment process, is coated colloid with the mode of spraying or dip-coating
In the anodized surface of aluminum and aluminum alloy mateial part, it is then dried at room temperature for 20min~40min, dry 20 at 50 DEG C~
40min。
2. the anodization process according to claim 1 for improving aluminium and aluminium alloy barrier propterty, it is characterised in that：Anodization
A concentration of 0.5M of sulfuric acid in solution, a concentration of 0.015M of Boratex, a concentration of 0.045M of DL-malic acid, the inorganic salts of cerium
A concentration of 0.02M, the temperature of the anodization solution in surface anodization processing procedure maintains 25 DEG C ± 1 DEG C, anode and the moon
Apply the potential difference of 15V, anodisation time 20min between pole.
3. the anodization process according to claim 1 for improving aluminium and aluminium alloy barrier propterty, it is characterised in that：Surface sun
In polarization process process, when anodized aluminum and aluminum alloy mateial part is not charged enter in anodization solution when, need to be
Apply voltage in 2min, initial voltage maximum value is 5V, then rises to 15V~25V to be no more than the rate of 5V/min, keeps sun
It powers off 2min domestic demands after the polarization process time aluminum and aluminum alloy mateial part is taken out and cleaned from anodization solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510882094.4A CN105463549B (en) | 2015-12-03 | 2015-12-03 | A kind of anodization process for improving aluminium and aluminium alloy barrier propterty |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510882094.4A CN105463549B (en) | 2015-12-03 | 2015-12-03 | A kind of anodization process for improving aluminium and aluminium alloy barrier propterty |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105463549A CN105463549A (en) | 2016-04-06 |
| CN105463549B true CN105463549B (en) | 2018-06-26 |
Family
ID=55601695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510882094.4A Active CN105463549B (en) | 2015-12-03 | 2015-12-03 | A kind of anodization process for improving aluminium and aluminium alloy barrier propterty |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105463549B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106501480A (en) * | 2016-11-30 | 2017-03-15 | 江西洪都航空工业集团有限责任公司 | A kind of method for differentiating aluminium lithium alloy chromic acid anodizing deoxidation effect |
| CN106917127B (en) * | 2017-03-06 | 2019-02-01 | 浙江工业大学 | A kind of laser and the compound method for preparing titanium alloy bionic coating of anodic oxidation |
| CN106835239B (en) * | 2017-03-06 | 2019-02-01 | 浙江工业大学 | A kind of surface anodization method of selective laser melting (SLM) molding titanium alloy |
| CN110904487A (en) * | 2019-12-10 | 2020-03-24 | 福耀汽车铝件(福建)有限公司 | Aluminum alloy decorative part and surface treatment method thereof |
| CN114540907B (en) * | 2022-02-27 | 2024-09-06 | 山东振挺精工活塞有限公司 | Preparation method of fatigue-resistant aluminum alloy |
| WO2024098749A1 (en) * | 2022-11-11 | 2024-05-16 | 天津航天长征火箭制造有限公司 | Anodic oxidation process method for aluminum-based composite material of launch vehicle |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1661398A (en) * | 2004-02-23 | 2005-08-31 | 佳能株式会社 | Film having irregularities on surface, antireflection film, method for producing same, and optical member |
| CN101184866A (en) * | 2005-05-31 | 2008-05-21 | 法国空中客车公司 | Sol for sol-gel process coating of a surface and coating method by sol-gel process using same |
| CN102079947A (en) * | 2010-12-01 | 2011-06-01 | 北京航空航天大学 | Preparation method of titanium alloy surface sol-gel conversion film |
| CN102174289A (en) * | 2011-02-25 | 2011-09-07 | 上海交通大学 | Surface anti-corrosion sol for aeronautic aluminum alloy material and treatment method thereof |
| CN102605405A (en) * | 2011-12-20 | 2012-07-25 | 中国航空工业集团公司北京航空材料研究院 | Anodization method for improving protection performance of aluminum and aluminum alloy |
| CN105419631A (en) * | 2015-12-21 | 2016-03-23 | 中国航空工业集团公司北京航空材料研究院 | Composite sol coating material for surface of aluminum alloy, and preparation method and coating method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120109573A (en) * | 2009-12-25 | 2012-10-08 | 후지필름 가부시키가이샤 | Insulated substrate, process for production of insulated substrate, process for formation of wiring line, wiring substrate, and light-emitting element |
| CN103635611A (en) * | 2011-07-04 | 2014-03-12 | 富士胶片株式会社 | Insulating reflective substrate and method for producing same |
| DE102012204636A1 (en) * | 2012-03-22 | 2013-09-26 | Nanogate Ag | Treatment of anodized surface |
-
2015
- 2015-12-03 CN CN201510882094.4A patent/CN105463549B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1661398A (en) * | 2004-02-23 | 2005-08-31 | 佳能株式会社 | Film having irregularities on surface, antireflection film, method for producing same, and optical member |
| CN101184866A (en) * | 2005-05-31 | 2008-05-21 | 法国空中客车公司 | Sol for sol-gel process coating of a surface and coating method by sol-gel process using same |
| CN102079947A (en) * | 2010-12-01 | 2011-06-01 | 北京航空航天大学 | Preparation method of titanium alloy surface sol-gel conversion film |
| CN102174289A (en) * | 2011-02-25 | 2011-09-07 | 上海交通大学 | Surface anti-corrosion sol for aeronautic aluminum alloy material and treatment method thereof |
| CN102605405A (en) * | 2011-12-20 | 2012-07-25 | 中国航空工业集团公司北京航空材料研究院 | Anodization method for improving protection performance of aluminum and aluminum alloy |
| CN105419631A (en) * | 2015-12-21 | 2016-03-23 | 中国航空工业集团公司北京航空材料研究院 | Composite sol coating material for surface of aluminum alloy, and preparation method and coating method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105463549A (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105463549B (en) | A kind of anodization process for improving aluminium and aluminium alloy barrier propterty | |
| CN104233428B (en) | A kind of method improving aluminum or aluminum alloy material surface anode oxide film alkaline resistance properties | |
| Pommiers et al. | Alternative conversion coatings to chromate for the protection of magnesium alloys | |
| Li et al. | A facile approach to fabricate superhydrophobic Zn surface and its effect on corrosion resistance | |
| CN104651908B (en) | The preparation method and method for sealing of a kind of Mg alloy surface ceramic film | |
| Yu et al. | Effects of graphene oxide-filled sol-gel sealing on the corrosion resistance and paint adhesion of anodized aluminum | |
| Ou et al. | Corrosion resistance of phytic acid/Ce (III) nanocomposite coating with superhydrophobicity on magnesium | |
| CN101624718B (en) | Chromizing-free anodic oxidation treatment method of surface of aviation 2 department and 7 department aluminium alloy | |
| CN107012458B (en) | Aluminium alloy pretreatment liquid and its application method | |
| CN108018591A (en) | A kind of aluminium and aluminium alloy anode oxide film are without nickel free-floride sealer | |
| CN104264144A (en) | Aluminum alloy product chemical conversion treatment process and nonferrous chromium-free film-forming agent | |
| CN109402699A (en) | A kind of aluminum alloy surface acid resistance corrosion function ceramic membrane preparation process | |
| CN102677039A (en) | Silane/rare-earth composite protective film on aluminum or aluminum alloy surface and preparation method thereof | |
| CN106756968A (en) | Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film | |
| CN108677175A (en) | A kind of aluminium and aluminum alloy surface permanganate/silane composite protection film and preparation method thereof | |
| CN105908204A (en) | Surface anti-corrosion treatment technology for aluminum fuel tanks | |
| CN106128744B (en) | A kind of Sintered NdFeB magnet surface temporary protection organic coating and preparation method | |
| CN103243371A (en) | Preparation method of zinc anode oxidation film layer | |
| Collazo et al. | Corrosion protection properties of anodized AA2024T3 alloy sealing with organic-based species | |
| Lei et al. | Performance and corrosion resistance mechanism of SA-Al composite hydrophobic coating on electrolytic manganese surface | |
| CN101638804A (en) | Chromium-free passivation solution for tin plate and method for using same | |
| CN102605405A (en) | Anodization method for improving protection performance of aluminum and aluminum alloy | |
| Pinheiro et al. | Influence of concentration and pH of hexafluorozirconic acid on corrosion resistance of anodized AA7075-T6 | |
| CN111074323B (en) | Normal-temperature nickel-free sealing liquid for aluminum and aluminum alloy anodic oxidation and sealing method | |
| Ji et al. | Effect of titanium sol on sulfuric-citric acids anodizing of 7150 aluminum alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |