CN105463549A - Anodizing method improving protection performance of aluminum and aluminum alloy - Google Patents
Anodizing method improving protection performance of aluminum and aluminum alloy Download PDFInfo
- Publication number
- CN105463549A CN105463549A CN201510882094.4A CN201510882094A CN105463549A CN 105463549 A CN105463549 A CN 105463549A CN 201510882094 A CN201510882094 A CN 201510882094A CN 105463549 A CN105463549 A CN 105463549A
- Authority
- CN
- China
- Prior art keywords
- anodization
- anodizing
- concentration
- aluminum
- alalloy
- 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.)
- Granted
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)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides an anodizing method improving protection performance of aluminum and aluminum alloy. An anodizing solution is formed by mixing at least one of inorganic salt of sulfuric acid, sodium borate, malic acid and cerium and water according to the proportion. A voltage control manner is adopted in anodizing for anodizing treatment on aluminum or aluminum alloy materials. An anodized film layer prepared through the method is good in corrosion resistance, good in combining performance with an organic paint film and low in fatigue performance on a base body and has the beneficial effects of being simple in technology, stable in performance, high in film forming efficiency and small in environment pollution. Organic-inorganic hybrid chromium-free closing method is selected after anodizing, chromium and other poisonous and harmful substances are not contained in confining liquid completely, and waste liquid discharging does not exist in the sealing process. The sealed anodized film layer is good in corrosion resistance, and the combining force of an original anodized film layer paint film is not influenced. The anodizing method and the sealing method can be used for replacing traditional chromic acid anodizing, sulfuric acid anodizing and dichromate sealing technologies and is applied to protection of aluminum and aluminum material surfaces of various industries such as aviation.
Description
Technical field
The present invention is a kind of anodization process improving Al and Alalloy barrier propterty, belongs to metallic surface processing technology field.
Background technology
Al and Alalloy is current application quantity one of structural metallic materials the most widely.Select suitable Al and Alalloy process of surface treatment for improve Al and Alalloy solidity to corrosion, strengthen the bonding force of itself and organic coating, ensure the fatigue property important role of body material.Traditional Al and Alalloy surface protection process adopts sulfur acid anodizing or chromic acid anodizing technique usually.Although sulfur acid anodizing has good corrosion resisting property, the Influence of Fatigue Properties for matrix is very large, can not meet Al and Al-alloy safety, long-life service requirements; The Influence of Fatigue Properties of chromic acid anodizing to matrix is less, but due to rete thinner, solidity to corrosion is poor, can not meet the requirement of Al and Al-alloy barrier propterty, and simultaneously chromic salt also can produce very large pollution to environment.
The corrosion resisting property of closing process guarantee rete must be adopted after anodizing.What extensively adopt at present is that dichromate or rare chromic acid are closed.The method not only containing sexavalent chrome, and produces a large amount of flushing waste water, has severe contamination to environment.In addition, this technique must be heated to more than 90 DEG C, not only wastes energy, and also will produce a large amount of containing chromium waste gas.
Summary of the invention
The present invention provides a kind of anodization process improving Al and Alalloy barrier propterty for above-mentioned the deficiencies in the prior art design just, its objective is and utilize sulfuric acid-boric acid salt-oxysuccinic acid-cerium salt solution to carry out electrolytic process anodizing to aluminum and aluminum alloy mateial part, realize lower environmental influence, follow-up corrosion resistance of surface treatment process supplements the deficiency of anodizing rete corrosion resisting property.Improve the corrosion resistance nature of aluminum and aluminum alloy mateial piece surface and do not reduce fatigue property.
The object of the invention is to be achieved through the following technical solutions:
This kind improves the anodization process of Al and Alalloy barrier propterty, the method comprises cleaning oil removing, surface deoxidation process, surface anodization process and follow-up corrosion resistance of surface treatment process, in surface anodization treatment process, treat that anodized aluminum and aluminum alloy mateial part is as anode, use stainless steel or stereotype or graphite as negative electrode, it is characterized in that:
Anodization solution in above-mentioned surface anodization treatment process is the aqueous solution of the inorganic salt of sulfuric acid, Sodium Tetraborate, DL-oxysuccinic acid and cerium, and wherein, the concentration of sulfuric acid is 0.3M ~ 0.6M, and the concentration of Sodium Tetraborate is 1 × 10
-2m ~ 2 × 10
-1m, DL-malic acid concentration is 2 × 10
-2m ~ 3 × 10
-1m, the concentration of the inorganic salt of cerium is 1 × 10
-2m ~ 2.5 × 10
-1m;
In above-mentioned surface anodization treatment process, the temperature of anodization solution maintains between 15 DEG C ~ 30 DEG C, applies the potential difference of 15V ~ 25V between anode and negative electrode, and anodisation time is 20min ~ 40min;
The colloid of to be solvent be glycerol and the methyl alcohol of the corrosion resistance of surface treatment soln in the corrosion resistance of surface treatment process that above-mentioned surface anodization process is follow-up, wherein the presoma of colloid is epoxies silane, fluorinated silane, titanium metal alkoxide and cerium metal alkoxide, in colloid, the weight percent of solvent is 40% ~ 60%, the atomic percent of four kinds of presomas is 1:1:1:1, also catalyzer is added with in colloid, hydrolysis stabilizer and tensio-active agent, catalyzer is oxysuccinic acid, hydrolysis stabilizer is methyl aceto acetate, tensio-active agent is OP-10, the weight percent that the content of these three kinds of compositions accounts for colloid is 0.5% ~ 1%,
In the corrosion resistance of surface treatment process that above-mentioned surface anodization process is follow-up, by spraying or the mode of dip-coating, colloid is coated in the anodized surface of aluminum and aluminum alloy mateial part, then at room temperature dry 20min ~ 40min, dry 20 ~ 40min at 50 DEG C.
It is characterized in that: in anodization solution, the concentration of sulfuric acid is 0.5M, the concentration of Sodium Tetraborate is 0.015M, DL-malic acid concentration is 0.045M, the concentration of the inorganic salt of cerium is 0.02M, the temperature of the anodization solution in surface anodization treating processes maintains 25 DEG C ± 1 DEG C, apply the potential difference of 15V between anode and negative electrode, anodisation time is 20min.
It is characterized in that: in surface anodization treatment process, until anodized aluminum and aluminum alloy mateial part is not charged enter in anodization solution time, voltage need be applied in 2min, initial voltage maximum value is 5V, then rise to 15V ~ 25V with the speed being no more than 5V/min, after the holding anode treatment time, aluminum and aluminum alloy mateial part takes out and cleans by power-off 2min domestic demand from anodization solution.
The feature of method described in anodizing of the present invention is on the basis of conventional sulfuric acid anodic process, reduces the concentration of sulfuric acid, adds borate, DL-oxysuccinic acid and cerium salt simultaneously.Due to the reduction of sulfuric acid concentration, reduce the dissolving of antianode rete in anodizing process, improve the thickness on anodic film blocking layer; Interpolation borate and oxysuccinic acid contribute to the formation on blocking layer simultaneously.Cerium salt and complexing agent oxysuccinic acid thereof is added in anodization solution, reaction generates the effect that rare earth complex ion serves space stop in anodizing process on the interface of anodic reaction, thus affect oxide film generation and the balance of dissolving, so that affect the process of growth of anodic film, the anodic film microscopic appearance such as the barrier layer thickness of film, Membrane pore density, aperture is changed, finally improves the performance of anodizing rete.Compared with traditional Al and Alalloy sulfur acid anodizing, chromic acid anodizing technique, anodic process of the present invention has the advantages such as technique is simple, stable performance, film forming efficiency is high, excellent combination property, environmental pollution are little.
A kind of anodizing postprocessing working procedures of the present invention uses the colloid of hybrid inorganic-organic.In colloid, four kinds of presomas are formed after there is hydrolysis and condensation reaction, and the aluminum oxide wherein containing cerium in the hydrolysis condensation product of zirconium and cerium metal alkoxide and anodizing has synergy, and both can form stable covalent bonds, and bonding strength is very good.Another two kinds of presomas are the siloxanes containing functional group, and the siloxanes after condensation reaction effectively can fill the space of anodic film, reaches sealing effect.And fluorine-containing siloxanes has the characteristic of surface hydrophobicity, greatly enhance the ability that rete medium corrosion-resistant immerses, improve corrosion resisting property.Finally, containing epoxide group siloxanes can with conventional epoxy primer or polyurethanes paint film generation chemical reaction, rete covalent bonds same with paint film.So whole rete and organic paint film covalent bonds, bonding strength is fabulous.In addition, compared to traditional enclosure method, this Chrome-free is closed without the need to wash-down water, to environment without any pollution.
Embodiment
Below with reference to embodiment, technical solution of the present invention is further described:
Embodiment 1
Adopt the process of anodization process of the present invention as follows:
1, test materials is 2024 naked aluminium plates, and heat treating regime is T3, is of a size of 75mm × 150mm × 2mm;
2, Al and Alalloy sample is immersed in acetone, ultrasonic oil removal 8min, take out with 50 DEG C of hot blast dryings;
3, Al and Alalloy sample dress is hung on aluminium alloy hanger;
4, detergent solution Al and Alalloy sample being placed in 50g/L carries out specimen surface oil removing, and in 60 DEG C of clean-out systems, oil removing is no less than 10min; Flowing water washed samples is used after oil removing;
5, at 25 DEG C, carry out deoxidation to Al and Alalloy sample, deaeration time is 3min, uses washed with de-ionized water specimen surface after taking out; Chromic anhydride (CrO in deoxidizing solution
3) concentration is 45g/L, nitric acid (HNO
3, ρ=1.42g/mL) and concentration is 100g/L, hydrofluoric acid concentration is 9mL/L;
6, Al and Alalloy sample carries out anodizing, in the anodizing aqueous solution, and sulfuric acid (H
2sO
4, ρ=1.84g/mL) and concentration is 0.5M, Sodium Tetraborate concentration is 0.015M, DL-malic acid concentration is 0.04M, and cerous sulfate concentration is 0.02M, and sample carries out anodizing in the solution of 25 DEG C; Adopt 1Cr18Ni9Ti stainless steel as negative electrode, Al and Alalloy sample is as anode; In anodizing process, adopt clean pressurized air to stir; Under sample, groove 1min applies voltage, rises to 15V, holding anode time 20min with the speed of 5V/min; After power-off, sample takes out and washed samples by 0.5min from groove;
7, the Al and Alalloy sample after anodizing carries out anodizing subsequent disposal operation in colloid.The presoma of colloid comprises four kinds of compositions, is γ-glyceryl ether oxygen propyl trimethoxy silicane, triethoxy fluoric silane, zirconium-n-propylate and cerous nitrate respectively, and solvent uses glycerol, and catalyzer uses oxysuccinic acid, and hydrolysis stabilizer uses methyl aceto acetate.After four kinds of presomas have reacted, finally add Surfactant OP-10.The atomic percent adding above-mentioned four kinds of presomas is 1:1:1:1, and the add-on of water is the calculated value of all presoma complete hydrolysis.Solvent is 40% ~ 60%, and the content of catalyzer hydrolysis stabilizer and tensio-active agent is 0.5% ~ 1%.Sample after anodizing is immersed in confining liquid, slowly take out after waiting for 1 ~ 2min, dry 20 ~ 40min under room temperature, dry 20 ~ 40min under 50 DEG C of conditions;
8, be the epoxy primer of 20 μm at the Al and Alalloy specimen surface coating thickness of test bonding force, fully solidify on request.
Embodiment 2
The process of anodization process is as follows:
1, test materials is 7075 naked aluminium plates, and heat treating regime is T6, is of a size of 75mm × 150mm × 2mm;
2, Al and Alalloy sample is immersed in acetone, ultrasonic oil removal 8min, take out with 50 DEG C of hot blast dryings;
3, Al and Alalloy sample dress is hung on aluminium alloy hanger;
4, detergent solution Al and Alalloy sample being placed in 50g/L carries out specimen surface oil removing, and in 60 DEG C of clean-out systems, oil removing is no less than 10min; Flowing water washed samples is used after oil removing;
5, at 25 DEG C, carry out deoxidation to Al and Alalloy sample, deaeration time is 3min, uses washed with de-ionized water specimen surface after taking out; Deoxidizing solution is chromic anhydride (CrO
3) concentration is 45g/L, nitric acid (HNO
3, ρ=1.42g/mL) and concentration is 100g/L, hydrofluoric acid concentration is 9mL/L;
6, Al and Alalloy sample carries out anodizing, and anodization solution is sulfuric acid (H
2sO
4, ρ=1.84g/mL) and concentration is 0.45M, Sodium Tetraborate concentration is 0.02M, DL-malic acid concentration is 0.06M, and cerous sulfate concentration is the aqueous solution of 0.015M; Sample carries out anodizing in the solution of 27 DEG C; Adopt 1Cr18Ni9Ti stainless steel as negative electrode, Al and Alalloy sample is as anode; In anodizing process, adopt clean pressurized air to stir; Under sample, groove 1min applies voltage, rises to 16V, holding anode time 20min with the speed of 4V/min; After power-off, sample takes out and washed samples by 0.5min from groove;
7, the Al and Alalloy sample after anodizing carries out anodizing subsequent disposal operation in colloid.The presoma of colloid comprises four kinds of compositions, is γ-glyceryl ether oxygen propyl trimethoxy silicane, triethoxy fluoric silane, zirconium-n-propylate and cerous nitrate respectively, and solvent uses glycerol, and catalyzer uses oxysuccinic acid, and hydrolysis stabilizer uses methyl aceto acetate.After four kinds of presomas have reacted, finally add Surfactant OP-10.The atomic percent adding above-mentioned four kinds of presomas is 1:1:1:1, and the add-on of water is the calculated value of all presoma complete hydrolysis.Solvent is 40% ~ 60%, and the content of catalyzer hydrolysis stabilizer and tensio-active agent is 0.5% ~ 1%.Sample after anodizing is immersed in confining liquid, slowly take out after waiting for 1 ~ 2min, dry 20 ~ 40min under room temperature, dry 20 ~ 40min under 50 DEG C of conditions;
8, testing the epoxy primer that bonding force Al and Alalloy specimen surface coating thickness is 20 μm, fully solidify on request.
Embodiment 3
The process of anodization process is as follows:
1, test materials is 2024 alclad sheet materials, and heat treating regime is T3, is of a size of 75mm × 150mm × 1.5mm;
2, Al and Alalloy sample is immersed in acetone, ultrasonic oil removal 8min, take out with 50 DEG C of hot blast dryings;
3, Al and Alalloy sample dress is hung on aluminium alloy hanger;
4, detergent solution Al and Alalloy sample being placed in 50g/L carries out specimen surface oil removing, and in 60 DEG C of clean-out systems, oil removing is no less than 10min; Flowing water washed samples is used after oil removing;
5, at 25 DEG C, carry out deoxidation to Al and Alalloy sample, deaeration time is 3min, uses washed with de-ionized water specimen surface after taking out; Deoxidizing solution is chromic anhydride (CrO
3) concentration is 45g/L, nitric acid (HNO
3, ρ=1.42g/mL) and concentration is 100g/L, hydrofluoric acid concentration is 9mL/L;
6, Al and Alalloy sample carries out anodizing, and anodization solution is sulfuric acid (H
2sO
4, ρ=1.84g/mL) and concentration is 0.55M, Sodium Tetraborate concentration is 0.015M, DL-malic acid concentration is 0.045M, and cerous sulfate concentration is the aqueous solution of 0.025M; Sample carries out anodizing in the solution of 25 DEG C; Adopt 1Cr18Ni9Ti stainless steel as negative electrode, Al and Alalloy sample is as anode; In anodizing process, adopt clean pressurized air to stir; Under sample, groove 1min applies voltage, rises to 15V, holding anode time 20min with the speed of 5V/min; After power-off, sample takes out and washed samples by 0.5min from groove;
7, the Al and Alalloy sample after anodizing carries out anodizing subsequent disposal operation in colloid.The presoma of colloid comprises four kinds of compositions, is γ-glyceryl ether oxygen propyl trimethoxy silicane, triethoxy fluoric silane, zirconium-n-propylate and cerous nitrate respectively, and solvent uses glycerol, and catalyzer uses oxysuccinic acid, and hydrolysis stabilizer uses methyl aceto acetate.After four kinds of presomas have reacted, finally add Surfactant OP-10.The atomic percent adding above-mentioned four kinds of presomas is 1:1:1:1, and the add-on of water is the calculated value of all presoma complete hydrolysis.Solvent is 40% ~ 60%, and the content of catalyzer hydrolysis stabilizer and tensio-active agent is 0.5% ~ 1%.Sample after anodizing is immersed in confining liquid, slowly take out after waiting for 1 ~ 2min, dry 20 ~ 40min under room temperature, dry 20 ~ 40min under 50 DEG C of conditions;
8, testing the epoxy primer that bonding force Al and Alalloy specimen surface coating thickness is 20 μm, fully solidify on request.
Embodiment 4 (comparative example)
The process of anodization process is as follows:
1, test materials is 2024 naked aluminium plates, and heat treating regime is T3, is of a size of 75mm × 150mm × 2mm;
2, Al and Alalloy sample is immersed in acetone, ultrasonic oil removal 8min, take out with 50 DEG C of hot blast dryings;
3, Al and Alalloy sample dress is hung on aluminium alloy hanger;
4, detergent solution Al and Alalloy sample being placed in 50g/L carries out specimen surface oil removing, and in 60 DEG C of clean-out systems, oil removing is no less than 10min; Flowing water washed samples is used after oil removing;
5, at 25 DEG C, carry out deoxidation to Al and Alalloy sample, deaeration time is 3min, uses washed with de-ionized water specimen surface after taking out; Chromic anhydride (CrO in deoxidizing solution
3) concentration is 45g/L, nitric acid (HNO
3, ρ=1.42g/mL) and concentration is 100g/L, hydrofluoric acid concentration is 9mL/L;
6, Al and Alalloy sample carries out anodizing, in the anodizing aqueous solution, and sulfuric acid (H
2sO
4, ρ=1.84g/mL) and concentration is 0.5M, Sodium Tetraborate concentration is 0.015M, DL-malic acid concentration is 0.04M, and cerous sulfate concentration is 0.02M, and sample carries out anodizing in the solution of 25 DEG C; Adopt 1Cr18Ni9Ti stainless steel as negative electrode, Al and Alalloy sample is as anode; In anodizing process, adopt clean pressurized air to stir; Under sample, groove 1min applies voltage, rises to 15V, holding anode time 20min with the speed of 5V/min; After power-off, sample takes out and washed samples by 0.5min from groove;
7, the Al and Alalloy sample after anodizing closes 25min in rare chromatedsolution of 90 DEG C, and rare cbromate seal solution is the aqueous solution of chromium anhydride concentration 70mg/L, Sodium chromate concentration 48mg/L;
8, be the epoxy primer of 20 μm at the Al and Alalloy specimen surface coating thickness of test bonding force, fully solidify on request.
Embodiment 5 (comparative example)
The process of anodization process is as follows:
1, test materials is 2024 naked aluminium plates, and heat treating regime is T3, is of a size of 75mm × 150mm × 1.5mm;
2, Al and Alalloy sample is immersed in acetone, ultrasonic oil removal 8min, take out with 50 DEG C of hot blast dryings;
3, Al and Alalloy sample dress is hung on aluminium alloy hanger;
4, detergent solution Al and Alalloy sample being placed in 50g/L carries out piece surface oil removing, and in 60 DEG C of clean-out systems, oil removing is no less than 10min; Flowing water washed samples is used after oil removing;
5, at 25 DEG C, carry out deoxidation to Al and Alalloy sample, deaeration time is 3min, uses washed with de-ionized water specimen surface after taking out; Three sour deoxidizing solution are chromic anhydride (CrO
3) concentration is 45g/L, nitric acid (HNO
3, ρ=1.42g/mL) and concentration is 100g/L, hydrofluoric acid concentration is 9mL/L;
6, Al and Alalloy sample carries out anodizing, and anodization solution is sulfuric acid (H
2sO
4, ρ=1.84g/mL) and the aqueous solution of concentration 1.93M; Sample carries out anodizing in the solution of 20 DEG C; Adopt stereotype as negative electrode, Al and Alalloy sample is as anode; In anodizing process, adopt clean pressurized air to stir; Sample is at 1A/dm
2holding anode 40min under current density; After power-off, sample takes out and washed samples by 0.5min from groove;
7, the Al and Alalloy sample after anodizing closes 20min in the dichromate solution of 95 DEG C, and dichromate lock solution is potassium bichromate (K
2cr
2o
7) aqueous solution sample of bonding force (test do not carry out this step) of concentration 50g/L;
8, testing the epoxy primer that bonding force Al and Alalloy specimen surface coating thickness is 20 μm, fully solidify on request.
Embodiment 6 (comparative example)
The process of anodization process is as follows:
1, test materials is 2024 naked aluminium plates, and heat treating regime is T3, is of a size of 75mm × 150mm × 1.5mm;
2, Al and Alalloy sample is immersed in acetone, ultrasonic oil removal 8min, take out with 50 DEG C of hot blast dryings;
3, Al and Alalloy sample dress is hung on aluminium alloy hanger;
4, detergent solution Al and Alalloy sample being placed in 50g/L carries out piece surface oil removing, and in 60 DEG C of clean-out systems, oil removing is no less than 10min; Flowing water washed samples is used after oil removing;
5, at 25 DEG C, carry out deoxidation to Al and Alalloy sample, deaeration time is 3min, uses washed with de-ionized water specimen surface after taking out; Deoxidizing solution is chromic anhydride (CrO
3) concentration is 45g/L, nitric acid (HNO
3, ρ=1.42g/mL) and concentration is 100g/L, hydrofluoric acid concentration is 9mL/L;
6, Al and Alalloy sample carries out anodizing, and anodization solution is chromic anhydride (CrO
3) concentration is 45g/L; Sample carries out anodizing in the solution of 35 DEG C; Adopt stereotype as negative electrode, Al and Alalloy sample is as anode; In anodizing process, adopt clean pressurized air to stir; Under sample, groove 1min applies voltage, rises to 20V, holding anode time 35min with the speed of 5V/min; After power-off, sample takes out and washed samples by 0.5min from groove;
7, the Al and Alalloy sample after anodizing closes 40min in the dichromate solution of 96 DEG C, and dichromate lock solution is potassium bichromate (K
2cr
2o
7) aqueous solution sample of bonding force (test do not carry out this step) of concentration 1g/L;
8, testing the epoxy primer that bonding force Al and Alalloy specimen surface coating thickness is 20 μm, fully solidify on request.
Table 1 is according to the Nature comparison of the sample of preceding embodiment process
(1) corrosion resistant test of anodizing rete is carried out according to " GB/T10125 artificial atmosphere corrosion test salt-fog test ".
(2) combining power test of anodic film and organic paint film is carried out according to " cross cut test of GB/T9286 paint and varnish paint film ".
(3) experiment on fatigue properties of anodizing sample is carried out according to " HB5287 metallic substance axial fatigue test method ".Test parameter is: maximum stress 240MPa; Stress ratio R=0.06; Test frequency 135HZ; Experimental temperature 25 DEG C.
See table 1, by comparing to embodiment of the present invention sample can find out with comparative example sample anodic film the performance test results, anodizing rete prepared by the present invention is closed rear solidity to corrosion, is is all met and exceeded the performance index of chromic acid anodizing, sulfur acid anodizing with organic varnish binding force of membrane, and the fatigue property of sample is significantly higher than the fatigue property of sulfur acid anodizing sample simultaneously.And Chrome-free enclosure method performance of the present invention also meets and exceeds tradition containing chromium enclosure method.
Compared with prior art, technical solution of the present invention proposes a kind of anodization process and enclosure method improving Al and Alalloy barrier propterty, adopt the anodizing membranous layer corrosion resistance prepared of the present invention good, excellent, low to matrix Influence of Fatigue Properties with organic Film Adhesion, have that technique is simple, stable performance, film forming efficiency is high, environmental pollution is little feature.In addition, this kind of anodizing enclosure method, easy to use, to environment without any pollution.
Claims (3)
1. one kind is improved the anodization process of Al and Alalloy barrier propterty, the method comprises cleaning oil removing, surface deoxidation process, surface anodization process and follow-up corrosion resistance of surface treatment process, in surface anodization treatment process, treat that anodized aluminum and aluminum alloy mateial part is as anode, use stainless steel or stereotype or graphite as negative electrode, it is characterized in that:
Anodization solution in above-mentioned surface anodization treatment process is the aqueous solution of the inorganic salt of sulfuric acid, Sodium Tetraborate, DL-oxysuccinic acid and cerium, and wherein, the concentration of sulfuric acid is 0.3M ~ 0.6M, and the concentration of Sodium Tetraborate is 1 × 10
-2m ~ 2 × 10
-1m, DL-malic acid concentration is 2 × 10
-2m ~ 3 × 10
-1m, the concentration of the inorganic salt of cerium is 1 × 10
-2m ~ 2.5 × 10
-1m;
In above-mentioned surface anodization treatment process, the temperature of anodization solution maintains between 15 DEG C ~ 30 DEG C, applies the potential difference of 15V ~ 25V between anode and negative electrode, and anodisation time is 20min ~ 40min;
The colloid of to be solvent be glycerol and the methyl alcohol of the corrosion resistance of surface treatment soln in the corrosion resistance of surface treatment process that above-mentioned surface anodization process is follow-up, wherein the presoma of colloid is epoxies silane, fluorinated silane, titanium metal alkoxide and cerium metal alkoxide, in colloid, the weight percent of solvent is 40% ~ 60%, the atomic percent of four kinds of presomas is 1:1:1:1, also catalyzer is added with in colloid, hydrolysis stabilizer and tensio-active agent, catalyzer is oxysuccinic acid, hydrolysis stabilizer is methyl aceto acetate, tensio-active agent is OP-10, the weight percent that the content of these three kinds of compositions accounts for colloid is 0.5% ~ 1%,
In the corrosion resistance of surface treatment process that above-mentioned surface anodization process is follow-up, by spraying or the mode of dip-coating, colloid is coated in the anodized surface of aluminum and aluminum alloy mateial part, then at room temperature dry 20min ~ 40min, dry 20 ~ 40min at 50 DEG C.
2. the anodization process of raising Al and Alalloy barrier propterty according to claim 1, it is characterized in that: in anodization solution, the concentration of sulfuric acid is 0.5M, the concentration of Sodium Tetraborate is 0.015M, DL-malic acid concentration is 0.045M, the concentration of the inorganic salt of cerium is 0.02M, the temperature of the anodization solution in surface anodization treating processes maintains 25 DEG C ± 1 DEG C, applies the potential difference of 15V between anode and negative electrode, and anodisation time is 20min.
3. the anodization process of raising Al and Alalloy barrier propterty according to claim 1, it is characterized in that: in surface anodization treatment process, until anodized aluminum and aluminum alloy mateial part is not charged enter in anodization solution time, voltage need be applied in 2min, initial voltage maximum value is 5V, then rise to 15V ~ 25V with the speed being no more than 5V/min, after the holding anode treatment time, aluminum and aluminum alloy mateial part takes out and cleans by power-off 2min domestic demand 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 true CN105463549A (en) | 2016-04-06 |
| CN105463549B 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) |
Cited By (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 |
| CN106835239A (en) * | 2017-03-06 | 2017-06-13 | 浙江工业大学 | A kind of surface anodization method of selective laser melting (SLM) molding titanium alloy |
| CN106917127A (en) * | 2017-03-06 | 2017-07-04 | 浙江工业大学 | A kind of laser is combined the method for preparing titanium alloy bionic coating with anodic oxidation |
| 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 |
| CN114540907A (en) * | 2022-02-27 | 2022-05-27 | 王传荣 | 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 (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1661398A (en) * | 2004-02-23 | 2005-08-31 | 佳能株式会社 | Film and antireflection film having fine irregularities on surface, production method for the same, and optical member using the same |
| 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 |
| US20120256224A1 (en) * | 2009-12-25 | 2012-10-11 | Fujifilm Corporation | Insulated substrate, process for production of insulated substrate, process for formation of wiring line, wiring substrate, and light-emitting element |
| JP2013033956A (en) * | 2011-07-04 | 2013-02-14 | Fujifilm Corp | Insulating reflection substrate and manufacturing method thereof |
| WO2013139899A2 (en) * | 2012-03-22 | 2013-09-26 | Nanogate Ag | Treatment of an anodically oxidized surface |
| 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 |
-
2015
- 2015-12-03 CN CN201510882094.4A patent/CN105463549B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1661398A (en) * | 2004-02-23 | 2005-08-31 | 佳能株式会社 | Film and antireflection film having fine irregularities on surface, production method for the same, and optical member using the same |
| 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 |
| US20120256224A1 (en) * | 2009-12-25 | 2012-10-11 | Fujifilm Corporation | Insulated substrate, process for production of insulated substrate, process for formation of wiring line, wiring substrate, and light-emitting element |
| 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 |
| JP2013033956A (en) * | 2011-07-04 | 2013-02-14 | Fujifilm Corp | Insulating reflection substrate and manufacturing 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 |
| WO2013139899A2 (en) * | 2012-03-22 | 2013-09-26 | Nanogate Ag | Treatment of an anodically oxidized surface |
| 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 |
Cited By (7)
| 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 |
| CN106835239A (en) * | 2017-03-06 | 2017-06-13 | 浙江工业大学 | A kind of surface anodization method of selective laser melting (SLM) molding titanium alloy |
| CN106917127A (en) * | 2017-03-06 | 2017-07-04 | 浙江工业大学 | A kind of laser is combined the method for preparing titanium alloy bionic coating with anodic oxidation |
| 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 |
| 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 |
| CN114540907A (en) * | 2022-02-27 | 2022-05-27 | 王传荣 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105463549B (en) | 2018-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105463549A (en) | Anodizing method improving protection performance of aluminum and aluminum alloy | |
| Pommiers et al. | Alternative conversion coatings to chromate for the protection of magnesium alloys | |
| Su et al. | Sol–gel coatings doped with organosilane and cerium to improve the properties of hot-dip galvanized steel | |
| Shang et al. | Electrochemical corrosion behavior of composite MAO/sol–gel coatings on magnesium alloy AZ91D using combined micro-arc oxidation and sol–gel technique | |
| Yu et al. | Effects of graphene oxide-filled sol-gel sealing on the corrosion resistance and paint adhesion of anodized aluminum | |
| CN102604509B (en) | Nanofiber heavy-duty anti-corrosive coating, preparation method and spraying method of nanofiber heavy-duty anti-corrosive coating | |
| CN101624718B (en) | Chromizing-free anodic oxidation treatment method of surface of aviation 2 department and 7 department aluminium alloy | |
| CN104233428A (en) | Method for improving alkaline resistance of anode oxide film on surface of aluminum or aluminum alloy material | |
| CN107012458B (en) | Aluminium alloy pretreatment liquid and its application method | |
| CN100497734C (en) | Chemical treatment method for aluminum alloy surface | |
| CN103205738A (en) | Non-chrome purified liquid | |
| CN106756968A (en) | Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film | |
| CN104264144A (en) | Aluminum alloy product chemical conversion treatment process and nonferrous chromium-free film-forming agent | |
| CN102732871A (en) | Neodymium iron boron magnet material phosphating treatment and organic coating double layers protection method | |
| CN108018591A (en) | A kind of aluminium and aluminium alloy anode oxide film are without nickel free-floride sealer | |
| CN108677175A (en) | A kind of aluminium and aluminum alloy surface permanganate/silane composite protection film and preparation method thereof | |
| CN103243371B (en) | Preparation method of zinc anode oxidation film layer | |
| CN106128744B (en) | A kind of Sintered NdFeB magnet surface temporary protection organic coating and preparation method | |
| CN105018915A (en) | Aluminum alloy ceramization solution | |
| CN110205613A (en) | A kind of chromium-free passivation liquid and its preparation and application | |
| Collazo et al. | Corrosion protection properties of anodized AA2024T3 alloy sealing with organic-based species | |
| CN103243290B (en) | Electric arc spraying pure aluminium coating sealant with high corrosion resistance, preparation process and application of sealant | |
| CN102605405A (en) | Anodization method for improving protection performance of aluminum and aluminum alloy | |
| Bahri et al. | Effect of silica ratio on the corrosion behavior of nano-silica potassium silicate coatings on aluminum alloy 2024 | |
| CN111074323B (en) | Normal-temperature nickel-free sealing liquid for aluminum and aluminum alloy anodic oxidation and sealing method |
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 |