CN105543824A - Method for preparing zirconium-selenium composite conversion film on surface of aluminum alloy - Google Patents

Method for preparing zirconium-selenium composite conversion film on surface of aluminum alloy Download PDF

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CN105543824A
CN105543824A CN201610040827.4A CN201610040827A CN105543824A CN 105543824 A CN105543824 A CN 105543824A CN 201610040827 A CN201610040827 A CN 201610040827A CN 105543824 A CN105543824 A CN 105543824A
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aluminum alloy
selenium
conversion film
aluminium alloy
film forming
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CN105543824B (en
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于升学
于强
邵光杰
邢茜
张鸣显
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Yanshan University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8

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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The invention provides a method for preparing a zirconium-selenium composite conversion film on the surface of aluminum alloy. The method is mainly characterized by comprising the steps of preparing film formation liquid, wherein each liter of film formation liquid is composed of 0.1-5 g of zirconate, 0.1-10 g of selenium type oxide or selenate, 0.1-15 g of organic acid, 0.1-10 g of auxiliary oxidizing agents, 0.1-15 g of film formation accelerants and the balance deionized water; carrying out degreasing treatment and activating treatment on the pre-ground aluminum alloy, placing the aluminum alloy into the film formation liquid with the temperature ranging from 10 DEG C to 60 DEG C for conversion treatment for 5-30 minutes, then taking out the aluminum alloy, washing the aluminum alloy through distilled water, air-drying the aluminum alloy and finally obtaining the zirconium-selenium colorful composite conversion film on the surface of aluminum alloy. The method has the advantages that the operation is simple, the cost is low, the composite conversion film high in uniformity and excellent in compactness can be formed, the corrosion resistance of the aluminum alloy is improved, the environmental friendliness is high, and production is easy.

Description

A kind of method preparing zirconium/selenium compound conversion film in aluminum alloy surface
Technical field
The present invention relates to a kind for the treatment of process of metallic surface, particularly a kind of method preparing conversion film in aluminum alloy surface.
Background technology
Al and Alalloy is more and more extensive in the application of national economy every field, and especially ornamental the and solidity to corrosion of effects on surface is had higher requirement.The oxide film of aluminium has provide protection for aluminum substrate; but the provide protection of the native oxide of aluminium is very limited; humidity in air and salt branch obviously accelerate corrosive nature; linear expansivity again due to Aluminum-aluminum alloy is larger; metal active is higher, and the general method of oxidation that adopts processes its surface more.Chemical oxidation treatment is one of technology of aluminum alloy surface oxide treatment, current Application comparison is chromic salt chemical oxidation process widely, there is toxicity large, the serious problems such as contaminate environment, in today that resources and environment problem is increasingly serious, the cost as how minimum resource environment obtains maximum social benefit, and oneself is a No.1 difficult problem.Be it seems by external Experience in Development, walk cleaner production and Sustainable Development Road is trend of the times.Along with the increasingly stringent of environmental requirement, for the aluminium alloy industry that range of application has a large capacity and a wide range, the development of aluminium alloy non-chromium oxide film is very promising, and the investigation and application of Chrome-free chemical oxidation process gets more and more.
Silicane chemically transformed film technique is that form colloidal solution, warp is reaction generation gel further, passes through dip-coating method with suitable precursor compound through hydrolysis, polymerization, generation organic polymer or metal oxide microparticle.Metal collective is formed Powdered or laminar rete.This rete not only has good chemical stability, and has cross-linked structure, corrosive medium therefore effectively can be stoped the destruction of matrix metal, the corrosion resistance nature of material and wear resistance are all improved a lot.It is low that sol-gel rete has cost, can the advantage of structure and function of manual control film.At present, study more in sol-gel film technique, being in progress larger is SiO 2type coating.There is the inorganic Liang Zhong functional group of the organic and parent of parent in silane molecule simultaneously, just can together with material mortise very large for these two kinds of nature differences of organic materials and inorganic materials by silane coupling agent.For aluminium alloy, silane can form extremely strong Me-O-Si key with substrate aluminium alloy, and the organic moiety of silane can form chemical bonds with top coat.Therefore, silane treatment can improve the bonding force of top coat and aluminum matrix alloy greatly, thus improves the solidity to corrosion of aluminium alloy.Sol-gel film technique is environmental friendliness, effective aluminum alloy surface treatment technology, has extremely important environment protection significance.The subject matter of current existence has: the stability problem of colloidal sol; Sol ingredient composite; The application mode of sol-gel, coating equipment and technical process are still needed improvement.
The research of molybdic acid salt chemical conversion film starts comparatively early, and as inhibiter, the corrosion inhibition of molybdate and membrane formation mechanism have been undertaken studying widely by Chinese scholars, and it is as little, the potential inorganic acid salt substituting traditional chromic salt process of a kind of toxicity.Chen Hong etc. obtain the relation between molybdate Conversion Coating on Al Alloy thickness and molybdenum acid ion concentration and solution ph by experiment, find to add Starso or sodium metaborate makes synergistic corrosion inhibitor simultaneously, can significantly improve the resistance to corrosion of aluminium alloy.The LY12 aluminium alloy film forming liquid main component that Wang Cheng etc. are main salt with Sodium orthomolybdate is: Na 2moO 410g/L; NaF1g/L; Additive A 8g/L, controling parameters is, pH=3.0; Room temperature; T=56min.Prepare the conversion film of good corrosion resistance in aluminum alloy surface, this treatment soln is not containing sexavalent chrome.Meet environmental requirement, and film forming speed is fast, can at room temperature film forming, the corrosion resisting property of film is good, has good restraining effect to the spot corrosion of aluminium alloy.The nineties in 20th century Ce – Mo conversion film first put forward by the Mansfeld of American South University of California, it combines high temperature and soak and electrochemical method.Although the oxide film solidity to corrosion of this kind of technique acquisition is better, treatment temp is too high, complex steps, and needs solution to maintain boiling state, is thus difficult to use in actual production.Li Guoqiang etc. propose the Ce-Mo technique of improvement, are placed in by 2.5g/L, NaKC by aluminium alloy 4h 4o 64H 2o7.5g/L, Na 2cO 32.5g/L, (NH 4) 2ce (NO 3) 61.5g/L and Na 2moO 4in the solution (pH is 9 ~ 10) of 5.0g/L composition, at 95 ~ 100 DEG C, process 20min.Through the LF6 aluminium alloy of this art breading, its corrosion resisting property has exceeded Alodine1200S conversion film.
Aluminium alloy zirconium system conversion film, first zirconates, titanium salt class chemical conversion membrane process are proposed in early 1980s by U.S. AmchemProductsInc, and the company such as Henkel KGaA, Japanese Parker has carried out large quantifier elimination subsequently.Be one of few in number at present technique obtaining industrial applications, it, the earliest for the surface treatment of pop can, expanded to the industries such as automobile, electronics, aviation, architectural shape afterwards gradually.After there is a series of chemical reaction and hydrolytic action in aluminium alloy and the treatment solution containing zirconate or titanate, what the conversion film generated was made up of with the complex compound etc. of fluorine aluminium sesquioxide, hydrated aluminum oxide, aluminium hydroxide, zirconium or titanium mixes inclusion film, this technique has simple to operate, the rete obtained and the advantage such as the bonding force of organic polymer is strong.But its corrosion resisting property is still lower than chromate film, and almost colourless being difficult to distinguish, bring certain difficulty to industrial operation.
These existing aluminum and its alloy chromium-free deactivation methods always also exist some shortcomings, such as: erosion resistance can not meet the needs, the high production being unfavorable for mass-producing of passivation effect cost that is bad, passivating solution etc. of actual productive life.
Summary of the invention
The object of this invention is to provide that a kind of preparation technology is simple, low production cost, processing parameter are easy to control, transformation time is short, can repeat the strong method preparing zirconium/selenium compound conversion film in aluminum alloy surface.
Technical scheme of the present invention is as follows:
(1) the film forming liquid of aluminum alloy surface conversion film is prepared
Containing zirconate 0.1 ~ 5g, selenium type oxide or selenate 0.1 ~ 10g, organic acid 0.1 ~ 15g, secondary oxidizer 0.1 ~ 10g, film forming accelerating 0.1 ~ 15g in every liter film forming liquid, surplus is deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, after stirring, filtration can obtain film forming liquid, and the pH of this film forming liquid is 1.0-7.0;
Described zirconates comprises the mixture of a kind of in potassium zirconium, sodium zirconate, magnesium zirconate or at least two kinds, and its ratio is 1-2:1-2, the mixture of preferred potassium zirconium, sodium zirconate, magnesium zirconate three, and its ratio of adding is 1:1:1.
Described selenium type oxide or selenate are selected from the mixture of a kind of in tin anhydride, selenium trioxide, selenous acid or two kinds, and its ratio is 1-3:1-2, the mixture of preferred tin anhydride, selenium trioxide, selenous acid three, and its ratio of adding is 1:1-2:3.
Described organic acid is selected from the mixture of a kind of in toluenesulphonic acids, carboxylic acid, Weibull or at least two kinds, and its ratio is 1-3:1-7, the mixture of preferred toluenesulphonic acids, carboxylic acid, Weibull three, and its ratio of adding is 1:1:1.
Described secondary oxidizer selects a kind of or mixture of two kinds of Sodium Fluoride, Potassium monofluoride, and its ratio of adding is 1-2:1-3.
Described film forming accelerating selects the mixture of a kind of of magnesium sulfate, ferric sulfate, copper sulfate or at least two kinds, and its ratio is 1-2:1, the mixture of preferably sulfuric acid magnesium, ferric sulfate, copper sulfate three, and its ratio of adding is 1:1:1-3.
(2) method of the colorful compound conversion film of zirconium/selenium is prepared in aluminum alloy surface:
1. aluminium alloy is carried out surface preparation:
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to aluminum alloy surface successively; It is in the alkaline degreasing fluid of 30-70 DEG C that aluminium alloy after pre-grinding is invaded temperature, carries out skimming treatment 5-20min; Be activate 10-30s in the middle of the activated solution of 20-50 DEG C again as temperature by the aluminium alloy after degreasing;
Described alkaline degreasing fluid is mixed by water glass, sodium hydroxide, sodium carbonate and deionized water, and wherein the concentration of water glass is 5 ~ 25g/L, and the concentration of sodium hydroxide is 10 ~ 25g/L, and the concentration of sodium carbonate is 10 ~ 30g/L; The concentration of the hydrofluoric acid solution in described activated solution is 10 ~ 100ml/L, and the concentration of hydrochloric acid is 5 ~ 120ml/L;
2. the colorful compound conversion film of zirconium/selenium is prepared in aluminum alloy surface:
Aluminium alloy after step 1. surface preparation being placed in temperature is take out after the film forming liquid of 10-60 DEG C carries out conversion processing 5-30min, cleans, obtain the colorful compound conversion film of Zr-Se after natural wind dries up in aluminum alloy surface with distilled water.
According to the deposition theory of conversion film, be placed into by aluminium alloy in the middle of conversion fluid and carry out conversion process, the surface of aluminium alloy can form small battery generation electrochemical reaction, and in micro anode, metal A l solubilizing reaction can occur:
Al＝Al 3++3e -(1)
This reaction can be there is at micro cathode:
O 2+2H 2O+4e -＝4OH -(2)
2H ++2e -＝H 2(3)
The reaction of micro cathode reaction zone can make the OH in micro cathode district -concentration increase pH value raise, unprecipitated formation and aluminum alloy surface Al 2o 3dissolving also create favourable condition; Precipitation rete can be formed after the micro cathode district reaction of aluminum alloy surface reaches certain degree, but comparatively force to obtain the Al of aluminum alloy surface due to the alkalescence in this region 2o 3this tiny area just appearing in aluminum alloy surface constantly dissolves, so constantly can carry out precipitation and constantly Al 2o 3dissolve.Along with the time transformed increases, the Al of aluminum alloy surface 2o 3can replace by precipitated rete at leisure, form the colorful compound conversion film of Zr-Se; The meanwhile formation of the colorful compound conversion film of Zr-Se improves the hydrogen reduction overpotential at negative electrode position; the raising of overpotential suppresses the anode dissolution of alloy matrix aluminum effectively; the alloy matrix aluminum that the colorful compound conversion film of Zr-Se is covered obtains to be protected effectively, thus improves the erosion resistance of aluminium alloy.
The present invention has the following advantages compared with prior art:
1, the colorful compound conversion film of aluminium alloy Zr-Se of preparation makes the corrosion potential of aluminium alloy improve greatly, thus improves the corrosion resistance nature of aluminium alloy.
2, the compound conversion film even, compactness is excellent can be formed, there is good binding ability simultaneously, can be applied to widely in the middle of aluminium alloy processing market, not only meet the requirement of erosion resistance but also meet the strong industrial requirements of conjugation.
3, preparation technology is relatively simple, only needs the concentration controlling material in the middle of conversion fluid just can obtain the colorful compound conversion film of Zr-Se of different Zr, Se content distribution; The different thickness of the colorful compound conversion film of Zr-Se of preparation and different colours also transform the factor such as treatment temp and time by activating process and adjustment and obtain.
4, adopt the conversion treating solution not containing environmentally harmful sexavalent chrome or trivalent chromium and other objectionable impuritiess, simultaneously containing the necessary trace element of human body, preparation method is also a kind of film of green.
5, production cost is low, can room temperature film-forming, and transformation time is shorter, processing parameter is easy to control, and conversion treating solution pH value range is comparatively wide, is convenient to routine maintenance in production, can reuse, can be widely used in the conversion processing of the materials such as Al-alloy products, foundry goods, section bar.
Accompanying drawing explanation
Fig. 1 is that the surface topography SEM of the aluminium alloy Zr-Se compound conversion film of example 1 of the present invention preparation schemes.
Fig. 2 is the EDS figure of the aluminium alloy Zr-Se compound conversion film of example 1 of the present invention preparation.
Fig. 3 be example 1 of the present invention preparation aluminium alloy Zr-Se compound conversion film and blank aluminium alloy be placed in the alternating-current impedance figure that mass percent concentration is the NaCl solution of 3.5% respectively.
Fig. 4 be example 1 of the present invention preparation aluminium alloy Zr-Se compound conversion film and blank aluminium alloy be placed in the polarization curve that mass percent concentration is the NaCl solution of 3.5% respectively.
Specific examples mode
Embodiment 1
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to the A6016 aluminum alloy surface being of a size of 20mmX10mmX3mm; Aluminium alloy after pre-grinding being placed in temperature is that the alkaline degreasing fluid of 50 DEG C carries out degreasing operation 10min; The composition of described alkaline degreasing fluid is every liter containing water glass 5g, sodium hydroxide 10g, sodium carbonate 10g, all the other are deionized water; Aluminium alloy after degreasing being placed in temperature is that the activation solution of 25 DEG C activates 30s, and described activation solution is every liter hydrofluoric acid containing solution 20ml, hydrochloric acid soln 20ml; Potassium zirconium 0.1g, tin anhydride 0.1g, toluenesulphonic acids 0.1g, Sodium Fluoride 10g, magnesium sulfate 15g is contained by every liter film forming liquid, surplus is the ratio of deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, stir until evenly, then filter and can obtain film forming liquid, the pH of this film forming liquid is 5.0; Clean with deionized water after film forming liquid aluminium alloy after surface preparation being placed in 25 DEG C processes 10min, after natural air drying, obtain the golden yellow compound conversion film of aluminium alloy Zr-Se in aluminum alloy surface.
Adopt S4700 type scanning electron microscope to record the surface topography of the red compound conversion film of aluminium alloy Zr-Se of the present embodiment as shown in Figure 1, the red compound conversion film densification of aluminium alloy Zr-Se can be found out and be combined firmly with alloy matrix aluminum.As shown in Figure 2, can find out the distribution of the multiple elements such as Se, O and Al, the less EDS of making of the addition due to Zr cannot measure.The red compound conversion film of the aluminium alloy Zr-Se utilizing CHI660A electrochemical workstation to prepare example 1 of the present invention and aluminium alloy blank carry out chemical property contrast test, three-electrode system is adopted in the middle of test process, respectively using the red compound conversion film of example 1 aluminium alloy Zr-Se of the present invention with aluminium alloy blank as working electrode, be all reference electrode with saturated calomel electrode, all using platinum electrode as supporting electrode, electrolytic solution is the NaCl solution that mass percent concentration is 3.5%, and area of detection is 1cm2 effectively, steady time is 20min, carry out under open circuit potential, survey frequency scope is 0.01 ~ 1.00 × 105Hz, measurement signal is obtain alternating-current impedance spectrogram as shown in Figure 3 under the test of the sine wave of amplitude 10mV, rete resistance and rete capacitance size can be judged from the diameter of the capacitive reactance arc of high band, resistance and the electric capacity of the aluminium alloy of unconverted process is obviously greater than through the rete resistance of the aluminum alloy specimen of conversion processing and rete electric capacity, illustrate that polarization resistance when there is corrosion reaction increases, conversion film effectively can slow down the migration of electronics in rete and suppress corrosive medium to permeate the erosion of alloy matrix aluminum, improve the corrosion resisting property of aluminium alloy under the same conditions, scanning speed is 0.01V/S, obtain polarization curve as shown in Figure 4, the corrosion potential of the colorful compound conversion film of aluminium alloy Zr-Se of the present invention improves greatly, illustrate that aluminium alloy Zr-Se of the present invention colorful compound conversion film has excellent corrosion resistance nature.
Embodiment 2
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to the A6016 aluminum alloy surface being of a size of 15mmX10mmX5mm; Aluminium alloy after pre-grinding being placed in temperature is that the alkaline degreasing fluid of 35 DEG C carries out degreasing operation 10min; The composition of described alkaline degreasing fluid is every liter containing water glass 4g, sodium hydroxide 15g, sodium carbonate 15g, all the other are deionized water; Aluminium alloy after degreasing being placed in temperature is that the activation solution of 30 DEG C activates 25s, and described activation solution is every liter hydrofluoric acid containing solution 30ml, hydrochloric acid soln 25ml; Sodium zirconate 5g, selenium trioxide 10g, carboxylic acid 0.1g, Potassium monofluoride 0.1g, ferric sulfate 15g is contained by every liter film forming liquid, surplus is the ratio of deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, stir until evenly, then filter and can obtain film forming liquid, the pH of this film forming liquid is 7.0; Clean with deionized water after film forming liquid aluminium alloy after surface preparation being placed in 25 DEG C processes 5min, after natural air drying, obtain aluminium alloy Zr-Se incarnadine compound conversion film in aluminum alloy surface.
Embodiment 3
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to the A6016 aluminum alloy surface being of a size of 20mmX15mmX3mm; Aluminium alloy after pre-grinding being placed in temperature is that the alkaline degreasing fluid of 35 DEG C carries out degreasing operation 12min; The composition of described alkaline degreasing fluid is every liter containing water glass 10g, sodium hydroxide 11g, sodium carbonate 13g, all the other are deionized water; Aluminium alloy after degreasing being placed in temperature is that the activation solution of 35 DEG C activates 30s, and described activation solution is every liter hydrofluoric acid containing solution 50ml, hydrochloric acid soln 35ml; 1:1 mixing 0.1g mixing altogether, copper sulfate 0.1g is pressed containing magnesium zirconate 0.1g, selenous acid 0.1g, Weibull 0.1g, Sodium Fluoride and Potassium monofluoride by every liter film forming liquid, surplus is the ratio of deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, stir until evenly, then filter and can obtain film forming liquid, the pH of this film forming liquid is 5.0; Clean with deionized water after film forming liquid aluminium alloy after surface preparation being placed in 25 DEG C processes 10min, after natural air drying, obtain aluminium alloy Zr-Se pink compound conversion film in aluminum alloy surface.
Embodiment 4
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to 6063 aluminum alloy surface being of a size of 15mmX15mmX5mm; Aluminium alloy after pre-grinding being placed in temperature is that the alkaline degreasing fluid of 60 DEG C carries out degreasing operation 5min; The composition of described alkaline degreasing fluid is every liter containing water glass 15g, sodium hydroxide 13g, sodium carbonate 14g, all the other are deionized water; Aluminium alloy after degreasing being placed in temperature is that the activation solution of 40 DEG C activates 20s, and described activation solution is every liter hydrofluoric acid containing solution 60ml, hydrochloric acid soln 5ml; In in every liter film forming liquid containing potassium zirconium, sodium zirconate by the ratio altogether 1g mixing of 1:2, tin anhydride, selenium trioxide by the ratio 1g mixing altogether of 1:1, toluenesulphonic acids, carboxylic acid is total to 4g mixing in the ratio of 2:1, Sodium Fluoride, Potassium monofluoride are total to 1g mixing in the ratio of 1:2, magnesium sulfate, ferric sulfate are total to 1g in the ratio of 1:1 and mix, surplus is the ratio of deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, stir until evenly, then filter and can obtain film forming liquid, the pH of this film forming liquid is 5.0; Clean with deionized water after film forming liquid aluminium alloy after surface preparation being placed in 25 DEG C processes 5min, after natural air drying, obtain the golden yellow compound conversion film of aluminium alloy Zr-Se in aluminum alloy surface.
Embodiment 5
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to 2019 aluminum alloy surface being of a size of 25mmX15mmX5mm; Aluminium alloy after pre-grinding being placed in temperature is that the alkaline degreasing fluid of 50 DEG C carries out degreasing operation 15min; The composition of described alkaline degreasing fluid is every liter containing water glass 17g, sodium hydroxide 18g, sodium carbonate 25g, all the other are deionized water; Aluminium alloy after degreasing being placed in temperature is that the activation solution of 30 DEG C activates 30s, and described activation solution is every liter hydrofluoric acid containing solution 70ml, hydrochloric acid soln 55ml; In being total to 4g mixing by the ratio 8g mixing altogether of 1:2, carboxylic acid, Weibull in the ratio of 1:1 by the ratio altogether 1g mixing of 2:1, selenium trioxide, selenous acid containing sodium zirconate, magnesium zirconate in every liter film forming liquid, Sodium Fluoride 4g, ferric sulfate, magnesium sulfate, copper sulfate is total to 1g in the ratio of 1:1:1 and mixes, surplus is the ratio of deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, stir until evenly, then filter and can obtain film forming liquid, the pH of this film forming liquid is 1.0; Clean with deionized water after film forming liquid aluminium alloy after surface preparation being placed in 25 DEG C processes 5min, after natural air drying, obtain the golden yellow compound conversion film of aluminium alloy Zr-Se in aluminum alloy surface.
Embodiment 6
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to 2019 aluminum alloy surface being of a size of 25mmX15mmX10mm; Aluminium alloy after pre-grinding being placed in temperature is that the alkaline degreasing fluid of 50 DEG C carries out degreasing operation 15min; The composition of described alkaline degreasing fluid is every liter containing water glass 20g, sodium hydroxide 20g, sodium carbonate 20g, all the other are deionized water; Aluminium alloy after degreasing being placed in temperature is that the activation solution of 20 DEG C activates 15s, and described activation solution is every liter hydrofluoric acid containing solution 10ml, hydrochloric acid soln 45ml; In being total to 1g mixing by the ratio 9g mixing altogether of 1:2:3, toluenesulphonic acids, carboxylic acid, Weibull in the ratio of 1:1:1 by the ratio altogether 1g mixing of 1:1:1, tin anhydride, selenium trioxide, selenous acid containing potassium zirconium, sodium zirconate, magnesium zirconate in every liter film forming liquid, Potassium monofluoride 1g, magnesium sulfate, ferric sulfate, copper sulfate presses 1:1:3 and is total to 4g and mixes, surplus is the ratio of deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, stir until evenly, then filter and can obtain film forming liquid, the pH of this film forming liquid is 4.0; Clean with deionized water after film forming liquid aluminium alloy after surface preparation being placed in 25 DEG C processes 5min, after natural air drying, obtain the golden yellow compound conversion film of aluminium alloy Zr-Se in aluminum alloy surface.
Embodiment 7
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to the A6016 aluminum alloy surface being of a size of 15mmX10mmX5mm; Aluminium alloy after pre-grinding being placed in temperature is that the alkaline degreasing fluid of 40 DEG C carries out degreasing operation 10min; The composition of described alkaline degreasing fluid is every liter containing water glass 4g, sodium hydroxide 15g, sodium carbonate 15g, all the other are deionized water; Aluminium alloy after degreasing being placed in temperature is that the activation solution of 30 DEG C activates 25s, and described activation solution is every liter hydrofluoric acid containing solution 30ml, hydrochloric acid soln 25ml; In in every liter film forming liquid containing sodium zirconate, magnesium zirconate by the ratio altogether 4g mixing of 1:1, selenium trioxide, selenous acid by the ratio 5g mixing altogether of 3:1, toluenesulphonic acids, Weibull is total to 4g mixing in the ratio of 1:3, Sodium Fluoride, Potassium monofluoride are total to 4g mixing in the ratio of 2:3, magnesium sulfate, copper sulfate are total in the ratio 4g of 1:1, surplus is the ratio of deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, stir until evenly, then filter and can obtain film forming liquid, the pH of this film forming liquid is 3.0; Clean with deionized water after film forming liquid aluminium alloy after surface preparation being placed in 35 DEG C processes 10min, after natural air drying, obtain the golden yellow compound conversion film of aluminium alloy Zr-Se in aluminum alloy surface.
Embodiment 8
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to the A6016 aluminum alloy surface being of a size of 15mmX10mmX5mm; Aluminium alloy after pre-grinding being placed in temperature is that the alkaline degreasing fluid of 50 DEG C carries out degreasing operation 10min; The composition of described alkaline degreasing fluid is every liter containing water glass 10g, sodium hydroxide 15g, sodium carbonate 15g, all the other are deionized water; Aluminium alloy after degreasing being placed in temperature is that the activation solution of 30 DEG C activates 25s, and described activation solution is every liter hydrofluoric acid containing solution 80ml, hydrochloric acid soln 75ml; In being total to 10g mixing by the ratio altogether 5g mixing of 1:1:3, toluenesulphonic acids, Weibull by the ratio of 3:7 containing sodium zirconate 5g, tin anhydride, selenium trioxide, selenous acid in every liter film forming liquid, Sodium Fluoride 8g, magnesium sulfate, copper sulfate is total to 4g in the ratio of 2:1 and mixes, surplus is the ratio of deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, stir until evenly, then filter and can obtain film forming liquid, the pH of this film forming liquid is 6.0; Clean with deionized water after film forming liquid aluminium alloy after surface preparation being placed in 55 DEG C processes 15min, after natural air drying, obtain aluminium alloy Zr-Se pink colour compound conversion film in aluminum alloy surface.
Embodiment 9
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to the A6016 aluminum alloy surface being of a size of 15mmX10mmX5mm; Aluminium alloy after pre-grinding being placed in temperature is that the alkaline degreasing fluid of 60 DEG C carries out degreasing operation 15min; The composition of described alkaline degreasing fluid is every liter containing water glass 10g, sodium hydroxide 15g, sodium carbonate 15g, all the other are deionized water; Aluminium alloy after degreasing being placed in temperature is that the activation solution of 30 DEG C activates 20s, and described activation solution is every liter hydrofluoric acid containing solution 100ml, hydrochloric acid soln 100ml; 10g mixing, copper sulfate 10g is total to containing magnesium zirconate 5g, tin anhydride 10g, Weibull 5g, Sodium Fluoride, Potassium monofluoride in the ratio of 1:1 in every liter film forming liquid, surplus is the ratio of deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, stir until evenly, then filter and can obtain film forming liquid, the pH of this film forming liquid is 2.0; Clean with deionized water after film forming liquid aluminium alloy after surface preparation being placed in 60 DEG C processes 10min, after natural air drying, obtain the golden yellow compound conversion film of aluminium alloy Zr-Se in aluminum alloy surface.
Embodiment 10
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to the A6016 aluminum alloy surface being of a size of 15mmX10mmX5mm; Aluminium alloy after pre-grinding being placed in temperature is that the alkaline degreasing fluid of 70 DEG C carries out degreasing operation 20min; The composition of described alkaline degreasing fluid is every liter containing water glass 25g, sodium hydroxide 25g, sodium carbonate 30g, all the other are deionized water; Aluminium alloy after degreasing being placed in temperature is that the activation solution of 50 DEG C activates 10s, and described activation solution is every liter hydrofluoric acid containing solution 20ml, hydrochloric acid soln 120ml; 10g mixing, copper sulfate 10g is total to containing magnesium zirconate 5g, tin anhydride 8g, Weibull 15g, Sodium Fluoride, Potassium monofluoride in the ratio of 1:1 in every liter film forming liquid, surplus is the ratio of deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, stir until evenly, then filter and can obtain film forming liquid, the pH of this film forming liquid is 1.0; Clean with deionized water after film forming liquid aluminium alloy after surface preparation being placed in 10 DEG C processes 30min, after natural air drying, obtain the golden yellow compound conversion film of aluminium alloy Zr-Se in aluminum alloy surface.

Claims (4)

1. prepare a method for zirconium/selenium compound conversion film in aluminum alloy surface, it is characterized in that: it comprises the steps:
(1) the film forming liquid of aluminum alloy surface conversion film is prepared
Containing zirconate 0.1 ~ 5g, selenium type oxide or selenate 0.1 ~ 10g, organic acid 0.1 ~ 15g, secondary oxidizer 0.1 ~ 10g, film forming accelerating 0.1 ~ 15g in every liter film forming liquid, surplus is deionized water, by above-mentioned each material mixing, in the middle of corrosion resistant container, after stirring, filtration can obtain film forming liquid, and the pH of this film forming liquid is 1.0-7.0;
(2) method of the colorful compound conversion film of zirconium/selenium is prepared in aluminum alloy surface
1. aluminium alloy is carried out surface preparation:
The sand paper of 600#, 800#, 1000#, 1200# and 2000# is used to carry out pre-grinding process to aluminum alloy surface successively; It is in the alkaline degreasing fluid of 30-70 DEG C that aluminium alloy after pre-grinding is invaded temperature, carries out skimming treatment 5-20min; Be activate 10-30s in the middle of the activated solution of 20-50 DEG C again as temperature by the aluminium alloy after degreasing;
2. the colorful compound conversion film of zirconium/selenium is prepared in aluminum alloy surface:
Aluminium alloy after step 1. surface preparation being placed in temperature is take out after the film forming liquid of 10-60 DEG C carries out conversion processing 5-30min, cleans, obtain the colorful compound conversion film of Zr-Se after natural wind dries up in aluminum alloy surface with distilled water;
2. the method preparing zirconium/selenium compound conversion film in aluminum alloy surface according to claim 1, it is characterized in that: described zirconates comprises the mixture of a kind of in potassium zirconium, sodium zirconate, magnesium zirconate or at least two kinds, its mass ratio is 1-2:1-2, the mixture of preferred potassium zirconium, sodium zirconate, magnesium zirconate three, its mass ratio added is 1:1:1;
Described selenium type oxide or selenate are selected from the mixture of a kind of in tin anhydride, selenium trioxide, selenous acid or two kinds, its mass ratio is 1-3:1-2, the mixture of preferred tin anhydride, selenium trioxide, selenous acid three, its mass ratio added is 1:1-2:3;
Described organic acid is selected from the mixture of a kind of in toluenesulphonic acids, carboxylic acid, Weibull or at least two kinds, and its mass ratio is 1-3:1-7, the mixture of preferred toluenesulphonic acids, carboxylic acid, Weibull three, and its mass ratio added is 1:1:1;
Described secondary oxidizer selects a kind of or mixture of two kinds of Sodium Fluoride, Potassium monofluoride, and its mass ratio added is 1-2:1-3;
Described film forming accelerating selects the mixture of a kind of of magnesium sulfate, ferric sulfate, copper sulfate or at least two kinds, and its mass ratio is 1-2:1, the mixture of preferably sulfuric acid magnesium, ferric sulfate, copper sulfate three, and its mass ratio added is 1:1:1-3.
3. the method preparing zirconium/selenium compound conversion film in aluminum alloy surface according to claim 1, it is characterized in that: described alkaline degreasing fluid is mixed by water glass, sodium hydroxide, sodium carbonate and deionized water, wherein the concentration of water glass is 5 ~ 25g/L, the concentration of sodium hydroxide is 10 ~ 25g/L, the concentration of sodium carbonate is 10 ~ 30g/L.
4. the method preparing zirconium/selenium compound conversion film in aluminum alloy surface according to claim 1, it is characterized in that: the concentration of the hydrofluoric acid solution in described activated solution is 10 ~ 100ml/L, the concentration of hydrochloric acid is 5 ~ 120ml/L.
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