CN105543824B - A kind of method for preparing the compound conversion film of zirconium/selenium in aluminum alloy surface - Google Patents
A kind of method for preparing the compound conversion film of zirconium/selenium in aluminum alloy surface Download PDFInfo
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- CN105543824B CN105543824B CN201610040827.4A CN201610040827A CN105543824B CN 105543824 B CN105543824 B CN 105543824B CN 201610040827 A CN201610040827 A CN 201610040827A CN 105543824 B CN105543824 B CN 105543824B
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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
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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
- C23C22/68—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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Abstract
A kind of method for preparing the colorful compound conversion film of zirconium/selenium in aluminum alloy surface, it is mainly pressed per liter into 0.1~5g containing zirconates in film liquid, 0.1~10g of selenium type oxide or selenate, 0.1~15g of organic acid, 0.1~10g of cooxidant, 0.1~15g of film forming accelerating, surplus is that deionized water is configured to film liquid, aluminium after pre-grinding is closed and carries out degreasing and activation process, aluminium alloy is placed in temperature again it is 10 60 DEG C and takes out into after carrying out the 30min of conversion processing 5 in film liquid, cleaned with distilled water, after natural wind drying the colorful compound conversion films of Zr Se are obtained in aluminum alloy surface.The present invention is simple to operate, and cost is low, can form compound conversion film uniform, that compactness is excellent, improve the decay resistance of aluminium alloy, have the very high value of environmental protection, be readily produced.
Description
Technical field
The present invention relates to a kind of processing method of metal surface, particularly a kind of side that conversion film is prepared in aluminum alloy surface
Method.
Background technology
Aluminium and aluminium alloy are more and more extensive in the application of national economy every field, especially to decorative surface and anti-corrosion
Property proposes higher requirement.The oxide-film of aluminium has a protective effect for aluminum substrate, but the protection of the native oxide of aluminium
Act on very limited, humidity and salt branch in air substantially accelerate corrosiveness, and are because the line of aluminium and its alloy expands
Number is larger, and metal active is higher, and general more methods using oxidation are handled its surface.Chemical oxidation treatment is aluminium alloy
One of technology of surface oxidation treatment, more extensive chromate chemical oxidation technology is applied at present, pollution big there is toxicity
The serious problems such as environment, in today that resource and environmental problem are increasingly serious, such as how the cost of the resource environment of minimum obtains
Maximum social benefit oneself be No.1 problem.By external Experience in Development apparently, clean manufacturing and Sustainable Development Road are walked
It is trend of the times.With increasingly strict, the aluminium alloy industry being had a large capacity and a wide range for application of environmental requirement, aluminium alloy non-chromium oxygen
The development of change film is very promising, and the research and application of Chrome-free chemical oxidation process are more and more.
Silanes chemically transformed film technique be with appropriate precursor compound through hydrolyze, polymerize, produce organic polymer or
Metal oxide microparticle, colloidal solution is formed, gel occurs through further reaction, passes through dip-coating method.In metal collective
Form powdered or laminar film layer.The film layer not only has good chemical stability, and has cross-linked structure, because
This can effectively prevent destruction of the corrosive medium to parent metal, make the decay resistance of material and wearability has and carried greatly very much
It is high.Sol-gel film layer has that cost is low, can be with the 26S Proteasome Structure and Function of manual control film the advantages of.At present, sol-gel into
Study more in membrane technology, it is SiO to be in progress larger2Type coating.Organic-philic and inorganic parent two in silane molecule simultaneously be present
Kind functional group, it is by silane coupler can that the very big material of organic material and both nature differences of inorganic material is firm
It is combined together.For aluminium alloy, silane can form extremely strong Me-O-Si keys with substrate aluminium alloy, and silane is organic
Part can form chemical bonds with face coat again.Therefore, silane treatment is greatly improved face coat and aluminum matrix alloy
Adhesion, so as to improve the corrosion resistance of aluminium alloy.Sol-gel film technique is environment-friendly, effective aluminum alloy surface
Treatment technology, there is extremely important environment protection significance.The subject matter that presently, there are has：The stability problem of colloidal sol；Colloidal sol group
The compounding divided；Application mode, coating equipment and the technological process of sol-gel are still needed improvement.
The research of molybdic acid salt chemical composition coating start it is more early, as corrosion inhibiter, the corrosion inhibition and film-forming machine of molybdate
Reason is extensively studied by domestic and foreign scholars, a kind of its chromic acid salt treatment traditional as small toxicity, potential replacement
Inorganic acid salt.Chen Hong etc. has obtained molybdate Conversion Coating on Al Alloy thickness and molybdenum acid ion concentration and pH value of solution by experiment
Relation between value, while find that adding sodium metasilicate or kodalk makees synergistic corrosion inhibitor, the anti-of aluminium alloy can be significantly improved
Erosion ability.King is into film liquid main component into waiting LY12 aluminium alloys using sodium molybdate as main salt：Na2MoO410g/L；NaF 1g/
L；Additive A 8g/L, control parameter are pH=3.0；Room temperature；T=56min.Prepared in aluminum alloy surface good anti-corrosion
The conversion film of property, the processing solution are free of Cr VI.Meet environmental requirement, and film forming speed is fast, can film forming at room temperature, film
Corrosion resisting property it is good, the spot corrosion to aluminium alloy has good inhibiting effect.Ce-Mo conversion films are the 1990s by American South
What the Mansfeld of University of California put forward first, it combines high temperature immersion and electrochemical method.Such a technique obtains
Although the oxide-film corrosion resistance obtained is preferable, treatment temperature is too high, complex steps, and needs solution maintaining fluidized state,
Thus it is difficult to use in actual production.Li Guoqiang etc. proposes improved Ce-Mo techniques, i.e., aluminium alloy is placed in by 2.5g/L,
NaKC4H4O6·4H2O 7.5g/L, Na2CO32.5g/L, (NH4)2Ce(NO3)61.5g/L and Na2MoO45.0g/L compositions
In solution (pH is 9~10), 20min is handled at 95~100 DEG C.LF6 aluminium alloys by this PROCESS FOR TREATMENT, its corrosion resisting property surpass
Alodine 1200S conversion films are crossed.
Aluminium alloy zirconium system conversion film, zirconates, titanium salt class chemical conversion membrane process by U.S. Amchem ProductsInc in
Early 1980s propose that the company such as subsequent Henkel KGaA, Japanese Parker has carried out substantial amounts of research first.It is to be at present
One of few technique for obtaining industrial applications of number, it is used for the surface treatment of pop can, gradually expands to vapour later earliest
The industries such as car, electronics, aviation, architectural shape.Aluminium alloy containing the treatment fluid of zirconates or titanate with occurring a series of chemistry
After reaction and hydrolysis, the conversion film generated is by alundum (Al2O3), hydrated alumina, aluminium hydroxide, zirconium or titanium and fluorine
The composition such as complex compound mixing field trash film, the technique has film layer and the knot of organic polymer simple to operate, to be obtained
The advantages that strong with joint efforts.But its corrosion resisting property is still below chromate film, and it is almost colourless be difficult to distinguish, brought to industrial operation
Certain difficulty.
These existing aluminium and aluminium alloy non-chromium passivating methods always there is some shortcomings, such as：Corrosion resistance can not
The needs, the passivation effect that meet actual production and living be bad, passivating solution cost height is unfavorable for production of scale etc..
The content of the invention
It is an object of the invention to provide a kind of preparation technology is simple, low production cost, technological parameter are easily controllable, conversion
Time is short, repeats the strong method for preparing the compound conversion film of zirconium/selenium in aluminum alloy surface.
Technical scheme is as follows：
(1) prepare aluminum alloy surface conversion film into film liquid
Per liter into film liquid containing 0.1~10g of 0.1~5g of zirconates, selenium type oxide or selenate, organic acid 0.1~
15g, 0.1~10g of cooxidant, 0.1~15g of film forming accelerating, surplus are deionized water, by above-mentioned each material mixing,
Among corrosion resistant container, after stirring, filtering i.e. can obtain film forming liquid, this into the pH of film liquid be 1.0-7.0；
The zirconates includes potassium zirconium, sodium zirconate, a kind of in magnesium zirconate or at least two mixture, its ratio
1-2:1-2, preferably potassium zirconium, sodium zirconate, the mixture of magnesium zirconate three, its ratio added are 1:1:1.
The selenium type oxide or selenate are one or two kinds of in selenium dioxide, selenium trioxide, selenous acid
Mixture, its ratio are 1-3:1-2, preferably selenium dioxide, selenium trioxide, the mixture of selenous acid three, its ratio added
For 1:1-2:3.
A kind of in toluenesulfonic acid, carboxylic acid, tannic acid of the organic acid or at least two mixture, its ratio
For 1-3:1-7, preferably toluenesulfonic acid, carboxylic acid, the mixture of tannic acid three, its ratio added are 1:1:1.
The cooxidant selects the one or two kinds of mixture of sodium fluoride, potassium fluoride, and its ratio added is 1-2:
1-3。
The film forming accelerating selects magnesium sulfate, ferric sulfate, copper sulphate a kind of or at least two mixture, its ratio
For 1-2:1, preferably sulfuric acid magnesium, ferric sulfate, the mixture of copper sulphate three, its ratio added are 1:1:1-3.
(2) method for preparing the colorful compound conversion film of zirconium/selenium in aluminum alloy surface：
1. aluminium alloy is subjected to surface preparation：
Pre-grinding processing is carried out to aluminum alloy surface using 600#, 800#, 1000#, 1200# and 2000# sand paper successively；Will
Aluminium alloy intrusion temperature after pre-grinding is in 30-70 DEG C of alkaline degreaser, carries out ungrease treatment 5-20min；Again by after degreasing
Aluminium alloy as temperature be to activate 10-30s among 20-50 DEG C of activated solution；
The alkaline degreaser mixes by sodium metasilicate, sodium hydroxide, sodium carbonate and deionized water, wherein sodium metasilicate
Concentration 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 activated solution
In the concentration of hydrofluoric acid solution be 10~100ml/L, the concentration of hydrochloric acid is 5~120ml/L；
2. prepare the colorful compound conversion film of zirconium/selenium in aluminum alloy surface：
It is 10-60 DEG C into carrying out conversion processing 5- in film liquid that aluminium alloy after step 1. surface preparation is placed in into temperature
Take out after 30min, cleaned with distilled water, the colorful compound conversion films of Zr-Se are obtained in aluminum alloy surface after natural wind drying.
According to the deposition theory of conversion film, aluminium alloy is placed into progress conversion processing process, aluminium alloy among conversion fluid
Surface can form small battery electrochemical reaction occurs, dissolving reaction can occur for metal Al in micro anode：
Al=Al3++3e- (1)
The reaction can occur in micro cathode：
O2+2H2O+4e-=4OH- (2)
2H++2e-=H2 (3)
The reaction of micro cathode reaction zone can cause the OH in micro cathode area-Concentration increase pH value rise, unprecipitated formation
With aluminum alloy surface Al2O3Dissolving also create advantage；When the micro cathode area reaction of aluminum alloy surface has reached certain
Can form precipitation film layer after degree, but due to the alkalescence in the region relatively force aluminum alloy surface Al2O3It is constantly molten
Solution, so this tiny area for just appearing in aluminum alloy surface can constantly carry out precipitation and constantly Al2O3Dissolving.With
The time increase of conversion, the Al of aluminum alloy surface2O3Film layer can be deposited at leisure to be substituted, form the colorful compound conversions of Zr-Se
Film；At the same time the formation of the colorful compound conversion films of Zr-Se improves the hydrogen reduction overpotential at negative electrode position, the raising of overpotential
Effectively suppress the anodic solution of alloy matrix aluminum, make the alloy matrix aluminum of the colorful compound conversion film coverings of Zr-Se be had
Effect ground protection, so as to improve the corrosion resistance of aluminium alloy.
The present invention has the following advantages compared with prior art：
1st, the colorful compound conversion films of aluminium alloy Zr-Se prepared cause the corrosion potential of aluminium alloy to greatly improve, from
And improve the decay resistance of aluminium alloy.
2nd, compound conversion film uniform, that compactness is excellent can be formed, while there is good binding ability, can be extensive
Be applied among aluminium alloy processing market, not only met the requirement of corrosion resistance but also met the strong industrial requirements of conjugation.
3rd, preparation technology is relatively easy, it is only necessary to which different Zr, Se can just be obtained by controlling the concentration of material among conversion fluid
The colorful compound conversion films of Zr-Se of content distribution；The different-thickness and different colours of the colorful compound conversion films of Zr-Se of preparation are also
It can be obtained by activating process and the regulation factor such as conversion processing temperature and time.
4th, using the conversion treating solution without environmentally harmful Cr VI or trivalent chromium and other harmful substances, together
Micro- necessary to Shi Hanyou human bodies, preparation method is also a kind of green film build method.
5th, production cost is low, can be with room temperature film-forming, and transformation time is shorter, and technological parameter is easily controllable, conversion treating solution pH
It is wider to be worth scope, is easy to regular maintenance in production, repeats and utilizes, can be widely used in Al-alloy products, casting, section bar
Deng the conversion processing of material.
Brief description of the drawings
Fig. 1 is the surface topography SEM figures of the compound conversion films of aluminium alloy Zr-Se prepared by present example 1.
Fig. 2 is the EDS figures of the compound conversion films of aluminium alloy Zr-Se prepared by present example 1.
Fig. 3 is that the compound conversion films of aluminium alloy Zr-Se prepared by present example 1 are respectively placed in quality hundred with blank aluminium alloy
The AC impedance figure divided in the NaCl solution that specific concentration is 3.5%.
Fig. 4 is that the compound conversion films of aluminium alloy Zr-Se prepared by present example 1 are respectively placed in quality hundred with blank aluminium alloy
The polarization curve divided in the NaCl solution that specific concentration is 3.5%.
Instantiation mode
Embodiment 1
A6016 aluminium using 600#, 800#, 1000#, 1200# and 2000# sand paper to size for 20mmX10mmX3mm
Alloy surface carries out pre-grinding processing；Aluminium alloy after pre-grinding is placed in the alkaline degreaser that temperature is 50 DEG C and carries out degreasing operation
10min；The composition of the alkaline degreaser is every liter 5g containing sodium metasilicate, sodium hydroxide 10g, sodium carbonate 10g, remaining for go from
Sub- water；Aluminium alloy after degreasing is placed in the activating solution that temperature is 25 DEG C and activates 30s, the activating solution is per the hydrogeneous fluorine of liter
Acid solution 20ml, hydrochloric acid solution 20ml；By every liter into 0.1g containing potassium zirconium, selenium dioxide 0.1g, toluenesulfonic acid in film liquid
0.1g, sodium fluoride 10g, magnesium sulfate 15g, surplus is the ratio of deionized water, by above-mentioned each material mixing, in corrosion resistant container
It is central, stirring until uniformly after, then filtering i.e. can obtain film forming liquid, this into film liquid pH be 5.0；After surface preparation
Aluminium alloy is placed in 25 DEG C and is washed with deionized water after 10min net into handling in film liquid, is obtained after natural air drying in aluminum alloy surface
The golden yellow compound conversion films of aluminium alloy Zr-Se.
The surface topography of the red compound conversion films of aluminium alloy Zr-Se of the present embodiment is measured using S4700 type ESEMs
As shown in Figure 1, it can be seen that the red compound conversion films of aluminium alloy Zr-Se are fine and close and are firmly combined with alloy matrix aluminum.Such as Fig. 2
It is shown, it can be seen that the distribution of the multiple element such as Se, O and Al, because Zr addition is less so that EDS can not be measured.Utilize
The red compound conversion films of aluminium alloy Zr-Se that CHI660A electrochemical workstations are prepared to present example 1 enter with aluminium alloy blank
Row chemical property contrast test, test process is central to use three-electrode system, respectively with the aluminium alloy Zr-Se of present example 1
Red compound conversion film and aluminium alloy blank are as working electrode, using saturated calomel electrode as reference electrode, with platinum electrode
As auxiliary electrode；Electrolyte is the NaCl solution that mass percent concentration is 3.5%, and effectively area of detection is
1cm2；Stabilization time is 20min, is carried out under OCP, and measurement frequency scope is 0.01~1.00 × 105Hz, measurement letter
Number for amplitude 10mV sine wave test under obtain AC impedance spectroscopy as shown in figure 3, the diameter of the capacitive reactance arc from high band
Size may determine that film layer resistance and film layer capacitance size, the film layer resistance and film layer electric capacity of the aluminum alloy specimen of inverted processing
The resistance and electric capacity of the aluminium alloy of significantly greater than unconverted processing, polarization resistance increase when illustrating corrosion reaction occurs, turn
Erosion infiltration of migration and suppression corrosive medium of the electronics in film layer to alloy matrix aluminum can effectively be slowed down by changing film, be improved
The corrosion resisting property of aluminium alloy under the same conditions, sweep speed 0.01V/S, obtain polarization curve as shown in figure 4, the present invention
The corrosion potential of the colorful compound conversion films of aluminium alloy Zr-Se greatly improves, and illustrates that the aluminium alloy Zr-Se of the present invention is colorful
Compound conversion film has excellent decay resistance.
Embodiment 2
A6016 aluminium using 600#, 800#, 1000#, 1200# and 2000# sand paper to size for 15mmX10mmX5mm
Alloy surface carries out pre-grinding processing；Aluminium alloy after pre-grinding is placed in the alkaline degreaser that temperature is 35 DEG C and carries out degreasing operation
10min；The composition of the alkaline degreaser is every liter 4g containing sodium metasilicate, sodium hydroxide 15g, sodium carbonate 15g, remaining for go from
Sub- water；Aluminium alloy after degreasing is placed in the activating solution that temperature is 30 DEG C and activates 25s, the activating solution is per the hydrogeneous fluorine of liter
Acid solution 30ml, hydrochloric acid solution 25ml；By every liter into 5g containing sodium zirconate in film liquid, selenium trioxide 10g, carboxylic acid 0.1g, fluorination
Potassium 0.1g, ferric sulfate 15g, surplus are the ratio of deionized water, and above-mentioned each material mixing among corrosion resistant container, is stirred
Mix until uniformly after, then filtering i.e. can obtain film forming liquid, this into film liquid pH be 7.0；By the aluminium alloy after surface preparation
It is placed in 25 DEG C and is washed with deionized water after 5min net into handling in film liquid, aluminium alloy is obtained in aluminum alloy surface after natural air drying
The compound conversion film of Zr-Se pale reds.
Embodiment 3
A6016 aluminium using 600#, 800#, 1000#, 1200# and 2000# sand paper to size for 20mmX15mmX3mm
Alloy surface carries out pre-grinding processing；Aluminium alloy after pre-grinding is placed in the alkaline degreaser that temperature is 35 DEG C and carries out degreasing operation
12min；The composition of the alkaline degreaser is every liter 10g containing sodium metasilicate, sodium hydroxide 11g, sodium carbonate 13g, remaining is goes
Ionized water；Aluminium alloy after degreasing is placed in the activating solution that temperature is 35 DEG C and activates 30s, the activating solution is hydrogeneous per liter
Fluorspar acid solution 50ml, hydrochloric acid solution 35ml；By every liter into 0.1g containing magnesium zirconate in film liquid, selenous acid 0.1g, tannic acid 0.1g,
Sodium fluoride and potassium fluoride press 1:The common 0.1g mixing of 1 mixing, copper sulphate 0.1g, surplus is the ratio of deionized water, by above-mentioned each thing
Matter mixes, and among corrosion resistant container, stirring is until after uniformly, and then filtering can obtain film forming liquid, the pH into film liquid
For 5.0；By the aluminium alloy after surface preparation be placed in 25 DEG C into handle in film liquid be washed with deionized water after 10min it is net, it is natural
After air-drying the compound conversion film of aluminium alloy Zr-Se pink is obtained in aluminum alloy surface.
Embodiment 4
6063 aluminium that size is 15mmX15mmX5mm are closed using 600#, 800#, 1000#, 1200# and 2000# sand paper
Gold surface carries out pre-grinding processing；Aluminium alloy after pre-grinding is placed in the alkaline degreaser that temperature is 60 DEG C and carries out degreasing operation
5min；The composition of the alkaline degreaser is every liter 15g containing sodium metasilicate, sodium hydroxide 13g, sodium carbonate 14g, remaining for go from
Sub- water；Aluminium alloy after degreasing is placed in the activating solution that temperature is 40 DEG C and activates 20s, the activating solution is per the hydrogeneous fluorine of liter
Acid solution 60ml, hydrochloric acid solution 5ml；By every liter 1 is pressed into film liquid containing potassium zirconium, sodium zirconate:The 2 common 1g mixing of ratio, two
Selenium oxide, selenium trioxide press 1:The 1 common 1g mixing of ratio, toluenesulfonic acid, carboxylic acid press 2:The 1 common 4g mixing of ratio, sodium fluoride, fluorine
Change potassium and press 1:The 2 common 1g mixing of ratio, magnesium sulfate, ferric sulfate press 1:The 1 common 1g mixing of ratio, surplus is the ratio of deionized water
Example, by above-mentioned each material mixing, among corrosion resistant container, stirring until after uniformly, then filtering can obtain film forming liquid,
This into film liquid pH be 5.0；Aluminium alloy after surface preparation is placed in 25 DEG C and into after handling 5min in film liquid uses deionization
Water is cleaned, and the golden yellow compound conversion films of aluminium alloy Zr-Se are obtained in aluminum alloy surface after natural air drying.
Embodiment 5
2019 aluminium that size is 25mmX15mmX5mm are closed using 600#, 800#, 1000#, 1200# and 2000# sand paper
Gold surface carries out pre-grinding processing；Aluminium alloy after pre-grinding is placed in the alkaline degreaser that temperature is 50 DEG C and carries out degreasing operation
15min；The composition of the alkaline degreaser is every liter 17g containing sodium metasilicate, sodium hydroxide 18g, sodium carbonate 25g, remaining is goes
Ionized water；Aluminium alloy after degreasing is placed in the activating solution that temperature is 30 DEG C and activates 30s, the activating solution is hydrogeneous per liter
Fluorspar acid solution 70ml, hydrochloric acid solution 55ml；By every liter 2 are pressed into film liquid containing sodium zirconate, magnesium zirconate:The 1 common 1g mixing of ratio,
Selenium trioxide, selenous acid press 1：The 2 common 8g mixing of ratio, carboxylic acid, tannic acid press 1:The 1 common 4g mixing of ratio, sodium fluoride 4g, sulphur
Sour iron, magnesium sulfate, copper sulphate press 1:1:The 1 common 1g mixing of ratio, surplus is the ratio of deionized water, and above-mentioned each material is mixed
Close, among corrosion resistant container, stirring is until after uniformly, and then filtering can obtain film forming liquid, and this is into the pH of film liquid
1.0；Aluminium alloy after surface preparation is placed in 25 DEG C and into after 5min is handled in film liquid net, natural air drying is washed with deionized water
Afterwards the golden yellow compound conversion films of aluminium alloy Zr-Se are obtained in aluminum alloy surface.
Embodiment 6
2019 aluminium using 600#, 800#, 1000#, 1200# and 2000# sand paper to size for 25mmX15mmX10mm
Alloy surface carries out pre-grinding processing；Aluminium alloy after pre-grinding is placed in the alkaline degreaser that temperature is 50 DEG C and carries out degreasing operation
15min；The composition of the alkaline degreaser is every liter 20g containing sodium metasilicate, sodium hydroxide 20g, sodium carbonate 20g, remaining is goes
Ionized water；Aluminium alloy after degreasing is placed in the activating solution that temperature is 20 DEG C and activates 15s, the activating solution is hydrogeneous per liter
Fluorspar acid solution 10ml, hydrochloric acid solution 45ml；By every liter 1 is pressed into film liquid containing potassium zirconium, sodium zirconate, magnesium zirconate:1:1 ratio
Common 1g mixing, selenium dioxide, selenium trioxide, selenous acid press 1:2:The 3 common 9g mixing of ratio, toluenesulfonic acid, carboxylic acid, tannic acid are pressed
1:1:The 1 common 1g mixing of ratio, potassium fluoride 1g, magnesium sulfate, ferric sulfate, copper sulphate press 1:1:3 common 4g mixing, surplus is deionization
The ratio of water, by above-mentioned each material mixing, among corrosion resistant container, stirring until after uniformly, then filtering is i.e. available
Into film liquid, this into the pH of film liquid be 4.0；Aluminium alloy after surface preparation is placed in into 25 DEG C to use into after handling 5min in film liquid
Deionized water is cleaned, and the golden yellow compound conversion films of aluminium alloy Zr-Se are obtained in aluminum alloy surface after natural air drying.
Embodiment 7
A6016 aluminium using 600#, 800#, 1000#, 1200# and 2000# sand paper to size for 15mmX10mmX5mm
Alloy surface carries out pre-grinding processing；Aluminium alloy after pre-grinding is placed in the alkaline degreaser that temperature is 40 DEG C and carries out degreasing operation
10min；The composition of the alkaline degreaser is every liter 4g containing sodium metasilicate, sodium hydroxide 15g, sodium carbonate 15g, remaining for go from
Sub- water；Aluminium alloy after degreasing is placed in the activating solution that temperature is 30 DEG C and activates 25s, the activating solution is per the hydrogeneous fluorine of liter
Acid solution 30ml, hydrochloric acid solution 25ml；By every liter 1 is pressed into film liquid containing sodium zirconate, magnesium zirconate:The 1 common 4g mixing of ratio, three
Selenium oxide, selenous acid press 3:The 1 common 5g mixing of ratio, toluenesulfonic acid, tannic acid press 1:The 3 common 4g mixing of ratio, sodium fluoride, fluorine
Change potassium and press 2:The 3 common 4g mixing of ratio, magnesium sulfate, copper sulphate press 1:1 ratio 4g is total to, and surplus is the ratio of deionized water, will
Above-mentioned each material mixing, among corrosion resistant container, stirring until uniformly after, then filtering i.e. can obtain film forming liquid, this into
The pH of film liquid is 3.0；Aluminium alloy after surface preparation is placed in into 35 DEG C to be washed with deionized water into after handling 10min in film liquid
Only, the golden yellow compound conversion films of aluminium alloy Zr-Se are obtained in aluminum alloy surface after natural air drying.
Embodiment 8
A6016 aluminium using 600#, 800#, 1000#, 1200# and 2000# sand paper to size for 15mmX10mmX5mm
Alloy surface carries out pre-grinding processing；Aluminium alloy after pre-grinding is placed in the alkaline degreaser that temperature is 50 DEG C and carries out degreasing operation
10min；The composition of the alkaline degreaser is every liter 10g containing sodium metasilicate, sodium hydroxide 15g, sodium carbonate 15g, remaining is goes
Ionized water；Aluminium alloy after degreasing is placed in the activating solution that temperature is 30 DEG C and activates 25s, the activating solution is hydrogeneous per liter
Fluorspar acid solution 80ml, hydrochloric acid solution 75ml；By every liter into 5g containing sodium zirconate, selenium dioxide, selenium trioxide, selenous acid in film liquid
By 1:1:The 3 common 5g mixing of ratio, toluenesulfonic acid, tannic acid press 3:The 7 common 10g mixing of ratio, sodium fluoride 8g, magnesium sulfate, sulphur
Sour copper presses 2:The common 4g mixing of 1 ratio, surplus is the ratio of deionized water, by above-mentioned each material mixing, in corrosion resistant container
It is central, stirring until uniformly after, then filtering i.e. can obtain film forming liquid, this into film liquid pH be 6.0；After surface preparation
Aluminium alloy is placed in 55 DEG C and is washed with deionized water after 15min net into handling in film liquid, is obtained after natural air drying in aluminum alloy surface
The compound conversion film of aluminium alloy Zr-Se pink colours.
Embodiment 9
A6016 aluminium using 600#, 800#, 1000#, 1200# and 2000# sand paper to size for 15mmX10mmX5mm
Alloy surface carries out pre-grinding processing；Aluminium alloy after pre-grinding is placed in the alkaline degreaser that temperature is 60 DEG C and carries out degreasing operation
15min；The composition of the alkaline degreaser is every liter 10g containing sodium metasilicate, sodium hydroxide 15g, sodium carbonate 15g, remaining is goes
Ionized water；Aluminium alloy after degreasing is placed in the activating solution that temperature is 30 DEG C and activates 20s, the activating solution is hydrogeneous per liter
Fluorspar acid solution 100ml, hydrochloric acid solution 100ml；By every liter into 5g containing magnesium zirconate in film liquid, selenium dioxide 10g, tannic acid 5g,
Sodium fluoride, potassium fluoride press 1:The 1 common 10g of ratio is mixed, copper sulphate 10g, and surplus is the ratio of deionized water, by above-mentioned each material
Mixing, among corrosion resistant container, stirring is until after uniformly, and then filtering can obtain film forming liquid, and this is into the pH of film liquid
2.0；Aluminium alloy after surface preparation is placed in 60 DEG C and into after 10min is handled in film liquid net, natural wind is washed with deionized water
After dry the golden yellow compound conversion films of aluminium alloy Zr-Se are obtained in aluminum alloy surface.
Embodiment 10
A6016 aluminium using 600#, 800#, 1000#, 1200# and 2000# sand paper to size for 15mmX10mmX5mm
Alloy surface carries out pre-grinding processing；Aluminium alloy after pre-grinding is placed in the alkaline degreaser that temperature is 70 DEG C and carries out degreasing operation
20min；The composition of the alkaline degreaser is every liter 25g containing sodium metasilicate, sodium hydroxide 25g, sodium carbonate 30g, remaining is goes
Ionized water；Aluminium alloy after degreasing is placed in the activating solution that temperature is 50 DEG C and activates 10s, the activating solution is hydrogeneous per liter
Fluorspar acid solution 20ml, hydrochloric acid solution 120ml；By every liter into 5g containing magnesium zirconate, selenium dioxide 8g, tannic acid 15g, fluorine in film liquid
Change sodium, potassium fluoride presses 1:The 1 common 10g of ratio is mixed, copper sulphate 10g, and surplus is the ratio of deionized water, and above-mentioned each material is mixed
Close, among corrosion resistant container, stirring is until after uniformly, and then filtering can obtain film forming liquid, and this is into the pH of film liquid
1.0；Aluminium alloy after surface preparation is placed in 10 DEG C and into after 30min is handled in film liquid net, natural wind is washed with deionized water
After dry the golden yellow compound conversion films of aluminium alloy Zr-Se are obtained in aluminum alloy surface.
Claims (4)
- A kind of 1. method for preparing the compound conversion film of zirconium/selenium in aluminum alloy surface, it is characterised in that：It comprises the following steps：(1) prepare aluminum alloy surface conversion film into film liquidPer liter into film liquid containing 0.1~10g of 0.1~5g of zirconates, selenium type oxide or selenate, 0.1~15g of organic acid, 0.1~10g of cooxidant, 0.1~15g of film forming accelerating, surplus are deionized water, by above-mentioned each material mixing, in corrosion resistant Among the container of erosion, after stirring, filtering i.e. can obtain film forming liquid, this into the pH of film liquid be 1.0-7.0；(2) method for preparing the colorful compound conversion film of zirconium/selenium in aluminum alloy surface1. aluminium alloy is subjected to surface preparation：Pre-grinding processing is carried out to aluminum alloy surface using 600#, 800#, 1000#, 1200# and 2000# sand paper successively；By pre-grinding Aluminium alloy afterwards is immersed in the alkaline degreaser that temperature is 30-70 DEG C, carries out ungrease treatment 5-20min；Again by the aluminium after degreasing Alloy is to activate 10-30s among 20-50 DEG C of activated solution as temperature；2. prepare the colorful compound conversion film of zirconium/selenium in aluminum alloy surface：It is 10-60 DEG C into carrying out conversion processing 5- in film liquid that aluminium alloy after step 1. surface preparation is placed in into temperature Take out after 30min, cleaned with distilled water, the colorful compound conversion films of Zr-Se are obtained in aluminum alloy surface after natural wind drying.
- 2. the method according to claim 1 for preparing the compound conversion film of zirconium/selenium in aluminum alloy surface, it is characterised in that：Institute Stating zirconates includes potassium zirconium, sodium zirconate, a kind of in magnesium zirconate or at least two mixture, and its mass ratio is 1-2: 1-2, potassium zirconium, sodium zirconate, the mixture of magnesium zirconate three, its mass ratio added are 1:1:1；The one or two kinds of mixing of the selenium type oxide or selenate in selenium dioxide, selenium trioxide, selenous acid Thing, its mass ratio are 1-3:1-2, selenium dioxide, selenium trioxide, the mixture of selenous acid three, its mass ratio added For 1:1-2:3；A kind of in toluenesulfonic acid, carboxylic acid, tannic acid of the organic acid or at least two mixture, its mass ratio For 1-3:1-7, toluenesulfonic acid, carboxylic acid, the mixture of tannic acid three, its mass ratio added are 1:1:1；The cooxidant selects the one or two kinds of mixture of sodium fluoride, potassium fluoride, and its mass ratio added is 1-2: 1-3；The film forming accelerating selects magnesium sulfate, ferric sulfate, copper sulphate a kind of or at least two mixture, its mass ratio For 1-2:1, magnesium sulfate, ferric sulfate, the mixture of copper sulphate three, its mass ratio added are 1:1:1-3.
- 3. the method according to claim 1 for preparing the compound conversion film of zirconium/selenium in aluminum alloy surface, it is characterised in that：Institute Alkaline degreaser is stated to be mixed by sodium metasilicate, sodium hydroxide, sodium carbonate and deionized water, wherein the concentration of sodium metasilicate be 5~ 25g/L, the concentration of sodium hydroxide are 10~25g/L, the concentration of sodium carbonate is 10~30g/L.
- 4. the method according to claim 1 for preparing the compound conversion film of zirconium/selenium in aluminum alloy surface, it is characterised in that：Institute The concentration for stating the hydrofluoric acid solution in activated solution is 10~100mL/L, and the concentration of hydrochloric acid is 5~120mL/L.
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| CN103276387A (en) * | 2013-05-20 | 2013-09-04 | 华南理工大学 | Method for preparing cerium-manganese/molybdenum multi-element composite conversion coating on surface of aluminum alloy |
| CN103866311A (en) * | 2014-03-06 | 2014-06-18 | 武汉材料保护研究所 | Method for preparing chemical conversion film on aluminum alloy surface on basis of molybdate |
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| CN103276387A (en) * | 2013-05-20 | 2013-09-04 | 华南理工大学 | Method for preparing cerium-manganese/molybdenum multi-element composite conversion coating on surface of aluminum alloy |
| CN103866311A (en) * | 2014-03-06 | 2014-06-18 | 武汉材料保护研究所 | Method for preparing chemical conversion film on aluminum alloy surface on basis of molybdate |
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