CN104831328A - Integrated hole sealing method for anodic oxide films of aluminum alloys - Google Patents
Integrated hole sealing method for anodic oxide films of aluminum alloys Download PDFInfo
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Abstract
The invention discloses an integrated hole sealing method for anodic oxide films of aluminum alloys. The integrated hole sealing method is excellent in hole sealing effect and high in timeliness and includes the steps: firstly, preparing phosphate solution and cerium salt solution; secondly, putting the anodic oxide films of the aluminum alloy into the cerium salt solution to carry out cerium salt hole sealing; thirdly, uniformly brushing the phosphate solution onto the anodic oxide films subjected to cerium salt hole sealing, curing for a while in the air, and carrying out thermal treatment at the temperature ranging from 150 DEG C to 350 DEG C; finally, forming a compact phosphate coating on the surface of the anodic oxide films after the steps are repeated for 2-8 times. Corrosion resistance and abrasion resistance of the anodic oxide films subjected to integrated hole sealing are much higher than those of anodic oxide films subjected to single hole sealing, and effects of integrated hole sealing are much higher than additive effects of single cerium salt hole sealing and phosphate hole sealing. In addition, cerium salt and phosphate integrated hole sealing method is high in timeliness and suitable for popularization and application in the technical field of hole sealing.
Description
Technical field
The present invention relates to hole sealing technology field, especially a kind of aluminium alloy anode oxide film compound hole sealing treatment process.
Background technology
Fine aluminium is more soft, has good ductility, but its intensity is lower, when require to have more high strength, its application is restricted.For this reason, the industrial alloying elements that usually adds is to obtain the aluminium alloy of different performance.Aluminium alloy tool specific tenacity is higher, excellent heat conductivity, and corrosion resistance is better, the advantage that plasticity is good, and in addition, the high-temperature behavior of aluminium alloy, forming property and surface treatment properties are also relatively good, and it is a kind of non-ferrous metal of high comprehensive performance.Therefore Aluminum-aluminum alloy is obtained for widespread use in every field such as space flight and aviation, automobile, building, bridge, boats and ships, chemical industry, packaging, mechanical means, and its usage quantity is only second to steel.
Solidity to corrosion but due to aluminium alloy is poor, often anodizing technology process need be adopted to form one deck anode oxide film to meet requirement to anti-corrosion aspect, anode oxide film due to aluminium alloy is porous, it can adsorb the corrosive medium in surrounding environment, greatly reduces the corrosion resistance of oxide film.Therefore the aluminium alloy after also needing antianode to be oxidized carries out sealing pores.The sealing quality of anode oxide film is extremely important, and it is directly connected to the work-ing life of Al-alloy products, and the product surface of sealing quality difference is easily corroded or produces other adverse consequencess.
At present, the cold seal hole of the normal method for sealing adopted to be dichromic acid sealing of hole, boiling water sealing hole and nickelous fluoride be main body, and the dichromic acid that dichromic acid sealing of hole uses is a kind of carcinogenic substance; It is large and easily produce the shortcomings such as pollen that boiling water sealing hole has energy consumption; Nickelous fluoride is that nickel ion in the cold seal hole of main body and fluorochemical very easily cause larger pollution to environment.Because above-mentioned three kinds of methods have respectively, energy consumption is large, carcinogenic, the shortcoming such as not environmentally, therefore, is necessary developing green, less energy-consumption and the hole-sealing technology of process stabilizing.Develop the Green Sealing Method of some Be very effective at present, mainly comprise magnesium acetate pore sealing method, cerium salt pore sealing method, rare earth sealing method and sol-gel pore sealing method.In above method, the effect of rare earth sealing method is better, and its sealing quality is suitable with dichromic acid pore sealing method.But rare earth sealing method and boiling water sealing hole, dichromic acid sealing of hole, nickelous fluoride are the same, subject to corrosion when oxide film is subject to slight damage, meanwhile, some sealing of hole material may be lost sealing of hole effect in wet environment by rinsing.Therefore, develop sealing of hole excellent effect and ageing good compound hole sealing treatment process to be significant.
Summary of the invention
Technical problem to be solved by this invention is to provide the better and ageing also good aluminium alloy anode oxide film compound hole sealing treatment process of a kind of sealing of hole effect.
The technical solution adopted for the present invention to solve the technical problems is: this aluminium alloy anode oxide film compound hole sealing treatment process, comprises the following steps:
A, prepare hole sealing agent, described hole sealing agent has two kinds, and the first hole sealing agent is the phosphate solution of solubility, and the second hole sealing agent is the cerium solution of solubility;
B, the cerium solution of putting into of aluminium alloy anode oxide film is carried out cerium salt sealing pores, described cerium salt sealing pores is carry out in the environment of 30-100 DEG C in temperature, and the time of cerium salt sealing pores is 30-150min.
C, the phosphate solution prepared is brushed equably on the aluminium alloy anode oxide film of step B process, and after being placed on air set for some time, then will be brushed with aluminium alloy anode oxide film thermal treatment for some time at 150-350 DEG C of phosphate solution;
D, will after heat treated aluminium alloy anode oxide film room temperature naturally cooling, again the phosphate solution prepared is brushed on aluminium alloy anode oxide film equably, and after being placed on air set for some time, then aluminium alloy anode oxide film thermal treatment for some time at 150-350 DEG C of phosphate solution will be brushed with, when after repetition 2-8 time, form the fine and close phosphate coating of one deck on aluminium alloy anode oxide film surface.
Further, described phosphate solution is Al (H
2pO
4)
3solution.
Further, described Al (H
2pO
4)
3the preparation method of solution is as described below: weigh a certain amount of H
3pO
4solution also heats, according to the ratio Al/P=1:3 of amount of substance, to H
3pO
4the Al (OH) of solid state is slowly added in solution
3, and be stirred to the Al (OH) of solid state
3dissolve completely and then form Al (H
2pO
4)
3solution, then utilizes the Al (H that deionized water will prepare
2pO
4)
3solution dilution, the Al (H after described dilution
2pO
4)
3the massfraction of solution is 5-20%.
Further, the Al (H after described dilution
2pO
4)
3the massfraction of solution is 10%.
Further, described cerium solution consist of 6gL
-1ce (NO
3)
36H
2o and 3gL
-1h
2o
2mixing solutions.
Further, in stepb, described cerium salt sealing pores is carry out in the environment of 60 DEG C in temperature, and the time of sealing pores is 150min.
Further, in step C and step D, described set time is 12 hours.
Further, in step C and step D, aluminium alloy anode oxide film thermal treatment for some time at 250 DEG C of phosphate solution will be brushed with.
Further, in step D, the number of times repeating to brush is 4 times.
The invention has the beneficial effects as follows: this aluminium alloy anode oxide film compound hole sealing treatment process first adopts cerium salt sealing of hole, Ce (OH) 3 is made to be deposited in fenestra, blocking fenestra, and then phosphoric acid salt sealing of hole is carried out to it, cerium salt-phosphoric acid salt compound hole sealing the process of one deck phosphate coating is formed at rete skin, dual sealing of hole can be realized, with single cerium salt sealing of hole, phosphoric acid salt sealing of hole and traditional boiling water sealing hole are compared, the corrosion resistance of its compound hole sealing and wear resistance are all considerably beyond corrosion resistance and the wear resistance of single sealing of hole, and superpose considerably beyond the effect of independent cerium salt sealing of hole and phosphoric acid salt sealing of hole, simultaneously cerium salt-phosphoric acid salt compound hole sealing process also has excellent ageing, the method is that anode oxide film sealing pores provides a kind of new way, and aluminum phosphate is a kind of nontoxic, compared with environmental protection and material, can not to environment.
Accompanying drawing explanation
Fig. 1 is the surface topography map of aluminium alloy anode oxide film under 3000 times after cerium salt sealing pores;
Fig. 2 is the surface topography map of aluminium alloy anode oxide film under 50000 times after cerium salt sealing pores;
Fig. 3 is the surface topography map of aluminium alloy anode oxide film under 3000 times after superphosphate sealing pores;
Fig. 4 is the surface topography map of aluminium alloy anode oxide film under 50000 times after superphosphate sealing pores;
Fig. 5 is the surface topography map of aluminium alloy anode oxide film under 3000 times after cerium salt-phosphoric acid salt compound hole sealing process;
Fig. 6 is the surface topography map of aluminium alloy anode oxide film under 50000 times after cerium salt-phosphoric acid salt compound hole sealing process;
Fig. 7 is the surface topography map of aluminium alloy anode oxide film under 3000 times after boiling water sealing hole process;
Fig. 8 is the surface topography map of aluminium alloy anode oxide film under 50000 times after the process of boiling water compound hole sealing;
Fig. 9 is non-sealing of hole oxide film and the electrochemical impedance spectrogram of aluminium alloy anode oxide film in 3.5%NaCl solution after cerium salt sealing of hole, phosphoric acid salt sealing of hole and cerium salt-phosphoric acid salt compound hole sealing process;
Figure 10 is non-sealing of hole oxide film and the electrochemical impedance spectrogram of aluminium alloy anode oxide film in 3.5%NaCl solution after boiling water sealing hole and cerium salt-phosphoric acid salt compound hole sealing process;
Figure 11 is aluminium alloy anode oxide film after cerium salt sealing of hole, phosphoric acid salt sealing of hole and cerium salt-phosphoric acid salt compound hole sealing process R in immersion process in 3.5%NaCl solution
pvariation diagram;
Figure 12 is aluminium alloy anode oxide film after boiling water sealing hole and cerium salt-phosphoric acid salt compound hole sealing process R in immersion process in 3.5%NaCl solution
pvariation diagram.
Embodiment
This aluminium alloy anode oxide film compound hole sealing treatment process, comprises the following steps:
A, prepare hole sealing agent, described hole sealing agent has two kinds, and the first hole sealing agent is the phosphate solution of solubility, and the second hole sealing agent is the cerium solution of solubility;
B, the cerium solution of putting into of aluminium alloy anode oxide film is carried out cerium salt sealing pores, described cerium salt sealing pores is carry out in the environment of 30-100 DEG C in temperature, and the time of cerium salt sealing pores is 30-150min.
C, the phosphate solution prepared is brushed equably on the aluminium alloy anode oxide film of step B process, and after being placed on air set for some time, then will be brushed with aluminium alloy anode oxide film thermal treatment for some time at 150-350 DEG C of phosphate solution;
D, will after heat treated aluminium alloy anode oxide film room temperature naturally cooling, again the phosphate solution prepared is brushed on aluminium alloy anode oxide film equably, and after being placed on air set for some time, then aluminium alloy anode oxide film thermal treatment for some time at 150-350 DEG C of phosphate solution will be brushed with, when after repetition 2-8 time, form the fine and close phosphate coating of one deck on aluminium alloy anode oxide film surface.The mechanism of phosphoric acid salt sealing of hole is form phosphate coating on anode oxide film surface, and this coating can cover the large size corrosion pit of anode oxide film effectively.Therefore, repeatedly in coating procedure, in the coating formed before phosphate solution can infiltrate, the crackle formed can be covered in last coating due to thermal treatment.Therefore, the anode oxide film of phosphoric acid salt sealing pores can show excellent corrosion resisting property.Therefore, spread coating is adopted to be brushed equably on aluminium alloy anode oxide film by phosphate solution, both the last phosphate coating thickness uniformity formed can have been ensured, also phosphate coating can be made finer and close simultaneously, thus improve its erosion resistance and wear resistance further, also be not easy to be rinsed, be less likely to occur to come off, it is better ageing simultaneously.
This aluminium alloy anode oxide film compound hole sealing treatment process first adopts cerium salt sealing of hole, Ce (OH) 3 is made to be deposited in fenestra, blocking fenestra, and then phosphoric acid salt sealing of hole is carried out to it, cerium salt-phosphoric acid salt compound hole sealing the process of one deck phosphate coating is formed at rete skin, dual sealing of hole can be realized, with single cerium salt sealing of hole, phosphoric acid salt sealing of hole and traditional boiling water sealing hole are compared, the corrosion resistance of its compound hole sealing and wear resistance are all considerably beyond corrosion resistance and the wear resistance of single sealing of hole, and superpose considerably beyond the effect of independent cerium salt sealing of hole and phosphoric acid salt sealing of hole, simultaneously cerium salt-phosphoric acid salt compound hole sealing process also has excellent ageing, the method is that anode oxide film sealing pores provides a kind of new way, and aluminum phosphate is a kind of nontoxic, compared with environmental protection and material, can not to environment.
In the above-described embodiment, as long as described phosphate solution solubility can, in order to ensure sealing of hole effect, described phosphate solution is preferably Al (H
2pO
4)
3solution.Described Al (H
2pO
4)
3the preparation method of solution is as described below: weigh a certain amount of H
3pO
4solution also heats, according to the ratio Al/P=1:3 of amount of substance, to H
3pO
4the Al (OH) of solid state is slowly added in solution
3, and be stirred to the Al (OH) of solid state
3dissolve completely and then form Al (H
2pO
4)
3solution, then utilizes the Al (H that deionized water will prepare
2pO
4)
3solution dilution, the Al (H after described dilution
2pO
4)
3the massfraction of solution is 5-20%.Utilize the Al (H of this concentration
2pO
4)
3the phosphate coating stable chemical performance that solution is formed, coating is comparatively fine and close, and sealing of hole effect is better.Further, under the prerequisite ensureing coating result, minimum in order to make cost drop to, the Al (H after described dilution
2pO
4)
3the massfraction of solution is 10%.
Further, described cerium solution consist of 6gL
-1ce (NO
3)
36H
2o and 3gL
-1h
2o
2mixing solutions.The cerium solution of this proportioning can make the effect of cerium salt sealing of hole best.
In stepb, in order to make the effect of cerium salt sealing of hole reach best, described cerium salt sealing pores is carry out in the environment of 60 DEG C in temperature, and the time of sealing pores is 150min.
Further, in step C and step D, described set time determines according to practical situation, as long as can ensure that phosphate coating solidifies completely, is preferably 12 hours described set time under normal circumstances and phosphate coating can be made to solidify completely.In order to ensure that the last phosphate coating densification formed should not come off, in step C and step D, will aluminium alloy anode oxide film thermal treatment for some time at 250 DEG C of phosphate solution be brushed with, can ensure that heat treated effect reaches best.In addition, in step D, the number of times repeating to brush is preferably for 4 times, and after four brushings, just can be formed on aluminium alloy anode oxide film surface and be about 15 μm of thick fine and close phosphate coatings, sealing of hole effect is very good.
Specific embodiment
Test one: cerium salt-phosphoric acid salt compound hole sealing.First adopt cerium salt sealing of hole, the cerium solution used consists of: cerous nitrate 6g/L, hydrogen peroxide 3g/L, solution PH is 4.4, the anode oxide film prepared is placed in above-mentioned cerium salt pore-sealing liquid, constant temperature to 30 DEG C, sealing pores 90min, then adopts phosphoric acid salt sealing of hole, adopts Al (H
2pO
4)
3solution carries out sealing pores, the Al (H used
2pO
4)
3solution synthesis method is: weigh a certain amount of H
3pO
4solution is also heated to 85 DEG C, according to the ratio Al/P=1:3 of amount of substance, to H
3pO
4the Al (OH) of solid state is slowly added in solution
3, and be stirred to the Al (OH) of solid state
3dissolve completely and then form Al (H
2pO
4)
3solution, then utilizes the Al (H that deionized water will prepare
2pO
4)
3solution dilution, the Al (H after described dilution
2pO
4)
3the massfraction of solution is 10%.Then, the Al (H that brush will prepare is utilized
2pO
4)
3brush on aluminium alloy anode oxide film dissolution homogeneity, and be placed on air set 12 hours, then will be brushed with Al (H
2pO
4)
3the aluminium alloy of solution natural air drying after thermal treatment 30min at 20-250 DEG C, the Al (H that recycling brush will prepare
2pO
4)
3brush on the aluminium alloy anode oxide film crossed through cerium salt sealing pores dissolution homogeneity, repeat above-mentioned steps 4 times, form the fine and close phosphate coating of one deck on aluminium alloy anode oxide film surface.
Simultaneous test one: phosphoric acid salt sealing of hole.Adopt Al (H
2pO
4)
3solution carries out sealing pores, the Al (H used
2pO
4)
3solution synthesis method is: weigh a certain amount of H
3pO
4solution is also heated to 85 DEG C, according to the ratio Al/P=1:3 of amount of substance, to H
3pO
4the Al (OH) of solid state is slowly added in solution
3, and be stirred to the Al (OH) of solid state
3dissolve completely and then form Al (H
2pO
4)
3solution, then utilizes the Al (H that deionized water will prepare
2pO
4)
3solution dilution, the Al (H after described dilution
2pO
4)
3the massfraction of solution is 10%.Then, the Al (H that brush will prepare is utilized
2pO
4)
3brush on aluminium alloy anode oxide film dissolution homogeneity, and be placed on air set 12 hours, then will be brushed with Al (H
2pO
4)
3the aluminium alloy of solution natural air drying after thermal treatment 30min at 20-250 DEG C, the Al (H that recycling brush will prepare
2pO
4)
3brush on aluminium alloy anode oxide film dissolution homogeneity, repeat above-mentioned steps 4 times, form the fine and close phosphate coating of one deck on aluminium alloy anode oxide film surface.
Simultaneous test two: boiling water sealing hole.Boiling water sealing hole is deionized water sealing of hole 30min anode oxide film being placed in boiling.
Simultaneous test three: cerium salt sealing of hole.The cerium solution used consists of: cerous nitrate 6g/L, hydrogen peroxide 3g/L, and solution PH is 4.4.The anode oxide film prepared is placed in above-mentioned cerium salt pore-sealing liquid, constant temperature to 30 DEG C, sealing pores 90min.
Draw the following conclusions after overtesting:
Fig. 1 is the surface topography map of aluminium alloy anode oxide film under 3000 times after cerium salt sealing pores; Fig. 2 is the surface topography map of aluminium alloy anode oxide film under 50000 times after cerium salt sealing pores; Fig. 3 is the surface topography map of aluminium alloy anode oxide film under 3000 times after superphosphate sealing pores; Fig. 4 is the surface topography map of aluminium alloy anode oxide film under 50000 times after superphosphate sealing pores; Fig. 5 is the surface topography map of aluminium alloy anode oxide film under 3000 times after cerium salt-phosphoric acid salt compound hole sealing process; Fig. 6 is the surface topography map of aluminium alloy anode oxide film under 50000 times after cerium salt-phosphoric acid salt compound hole sealing process; Fig. 7 is the surface topography map of aluminium alloy anode oxide film under 3000 times after boiling water sealing hole process; Fig. 8 is the surface topography map of aluminium alloy anode oxide film under 50000 times after the process of boiling water compound hole sealing; As shown in Figure 1, the corrosion pit that after cerium salt sealing of hole, aluminium alloy anode oxide film surface is larger is not completely by shutoff, and as can be seen from Figure 2, the micropore major part of aluminium alloy anode oxide film is by the particle plugging of superficial deposit, but still the micropore of non-shutoff can be observed, illustrate that cerium salt sealing of hole is not thorough.Can be found out by Fig. 3 and Fig. 5, all there is a large amount of crackle in the anode oxide film surface after phosphoric acid salt sealing of hole and cerium salt-phosphoric acid salt compound hole sealing, this coating produces larger thermal stresses owing to expanding and produces in heat treatment process, and the anode oxide film surface crack size of cerium salt-phosphoric acid salt compound hole sealing is less than the anode oxide film of phosphoric acid salt sealing of hole.Fig. 4 and Fig. 6 shows, and the coating formed on anode oxide film surface after phosphoric acid salt sealing pores and cerium salt-phosphoric acid salt compound hole sealing process is fine and close, and the micropore on anode oxide film top layer is by complete shutoff.Fig. 7 Fig. 8 shows, the corrosion pit major part that anode oxide film surface after boiling water sealing hole is caused by second-phase defect is blocked, because boiling water sealing hole mechanism is the filling of hydrated product boehmite to fenestra, therefore the anode oxide film surface observed forms reticulated structure, and the micropore major part of porous layer is blocked.
Fig. 9 is non-sealing of hole oxide film and the electrochemical impedance spectroscopy of aluminium alloy anode oxide film in 3.5%NaCl solution after cerium salt sealing of hole, phosphoric acid salt sealing of hole and cerium salt-phosphoric acid salt compound hole sealing process.Figure 10 is non-sealing of hole oxide film and the electrochemical impedance spectroscopy of aluminium alloy anode oxide film in 3.5%NaCl solution after boiling water sealing hole and cerium salt-phosphoric acid salt compound hole sealing process.As can be seen from Figure 9, the aluminium alloy anode oxide film without sealing pores is about 2285 Ω cm at the resistance value at intermediate frequency place
2, the oxide film after cerium salt sealing of hole is about 1.4 × 104 Ω cm
2, the oxide film of phosphoric acid salt sealing of hole and cerium salt-phosphoric acid salt compound hole sealing is about 5 ~ 6 × 105 Ω cm
2, best through the oxide film corrosion resistance of phosphoric acid salt sealing of hole and cerium salt-phosphoric acid salt compound hole sealing, the effect of cerium salt-phosphoric acid salt compound hole sealing is slightly better than phosphoric acid salt sealing of hole.As can be seen from Figure 10, the anode oxide film without sealing pores is about 2285 Ω cm at the resistance value at intermediate frequency place
2, the oxide film of cerium salt-phosphoric acid salt compound hole sealing is about 5 ~ 6 × 105 Ω cm
2, the oxide film after boiling water sealing hole is about 1 × 104 Ω cm
2.It can thus be appreciated that the oxide film corrosion resistance of cerium salt-phosphoric acid salt compound hole sealing is best; The intermediate frequency resistance value of the oxide film after boiling water sealing hole improves nearly order of magnitude than non-sealing of hole oxide film, and the corrosion resistance of oxide film also tool improves a lot.
The anodic oxidation of aluminium alloy and sealing pores technology can improve its corrosion resistance widely, the solidity to corrosion of the aluminium alloy anode oxide film after sealing of hole should be able to keep long-term stability and ageing, therefore has great importance to the ageing research of sealing of hole effect.In test, adopt immersion test, aluminium alloy anode oxide film after sealing of hole is placed in and takes out after 3.5%NaCl solution soaks different time and to test its electrochemical behavior at 3.5%NaCl solution, observe the change of its surface topography in immersion process, Figure 11 is aluminium alloy anode oxide film after cerium salt sealing of hole, phosphoric acid salt sealing of hole and cerium salt-phosphoric acid salt compound hole sealing process R in immersion process in 3.5%NaCl solution simultaneously
pchange, Figure 12 is aluminium alloy anode oxide film after boiling water sealing hole and cerium salt-phosphoric acid salt compound hole sealing process R in immersion process in 3.5%NaCl solution
pchange.From Figure 11, we can find out, the R of oxide film in whole soak cycle of cerium salt-phosphoric acid salt compound hole sealing
pvalue is all higher than the immersion single cerium salt of same time or the oxide film of phosphoric acid salt hole-sealing technology process.It can be said that compared with bright and single hole-sealing technology, the cerium salt-raising effect of phosphoric acid salt compound hole sealing process to oxide film corrosion resistance is best, meanwhile, also has the most excellent ageing.And during employing cerium salt-phosphoric acid salt compound hole sealing, the tendency that when pre-treatment of cerium salt effectively can reduce follow-up phosphoric acid salt sealing pores, oxide film ftractures in drying process, therefore, compared with single phosphoric acid salt, the corrosion resistance of the oxide film after cerium salt-phosphoric acid salt compound hole sealing is better.Can also find out from Figure 11, the oxide film of cerium salt-phosphoric acid salt compound hole sealing process and the oxide film of cerium salt sealing pores similar, along with the prolongation of soak time, R
pvalue presents first to reduce and raises afterwards, the phenomenon then reduced again.The appearance of this phenomenon is main relevant with the mechanism of cerium salt sealing of hole.Along with the prolongation of soak time, Cl
-destroy rete, the porous layer local dissolution of oxide film, oxide film local OH
-concentration raises, and pH increases, and now, the Ce changed does not occur the part that may exist in porous layer in sealing of hole process
3+will with OH
-effect, deposits Ce (OH) in fenestra
3, and then block partial pore, make the resistance value of oxide film increase, its erosion resistance improves, and sealing of hole effect is all effective in for a long time, and namely cerium salt-phosphoric acid salt compound hole sealing also has ageing preferably.From Figure 12, we can find out, the oxide film of the cerium salt-phosphoric acid salt compound hole sealing Rp value in whole soak cycle is all higher than the oxide film of boiling water sealing hole process soaking same time.It can be said that bright cerium salt-phosphoric acid salt compound hole sealing process to the raising effect of oxide film corrosion resistance comparatively boiling water sealing hole handle well, meanwhile, also have more excellent ageing, all effective to the raising of corrosion resistance within the long period.And through the sample Rp value of boiling water sealing hole sealing pores within the specific limits along with the prolongation of soak time reduces gradually.Illustrate that when soaking in NaCl solution, " pore self-sealing " phenomenon does not occur the oxide film after boiling water sealing hole process, and the corrosion resistance of oxide film reduces with the prolongation of soak time.
Claims (9)
1. an aluminium alloy anode oxide film compound hole sealing treatment process, is characterized in that comprising the following steps:
A, prepare hole sealing agent, described hole sealing agent has two kinds, and the first hole sealing agent is the phosphate solution of solubility, and the second hole sealing agent is the cerium solution of solubility;
B, the cerium solution of putting into of aluminium alloy anode oxide film is carried out cerium salt sealing pores, described cerium salt sealing pores is carry out in the environment of 30-100 DEG C in temperature, and the time of cerium salt sealing pores is 30-150min.
C, the phosphate solution prepared is brushed equably on the aluminium alloy anode oxide film of step B process, and after being placed on air set for some time, then will be brushed with aluminium alloy anode oxide film thermal treatment for some time at 150-350 DEG C of phosphate solution;
D, will after heat treated aluminium alloy anode oxide film room temperature naturally cooling, again the phosphate solution prepared is brushed on aluminium alloy anode oxide film equably, and after being placed on air set for some time, then aluminium alloy anode oxide film thermal treatment for some time at 150-350 DEG C of phosphate solution will be brushed with, when after repetition 2-8 time, form the fine and close phosphate coating of one deck on aluminium alloy anode oxide film surface.
2. aluminium alloy anode oxide film compound hole sealing treatment process as claimed in claim 1, is characterized in that: described phosphate solution is Al (H
2pO
4)
3solution.
3. aluminium alloy anode oxide film compound hole sealing treatment process as claimed in claim 2, is characterized in that: described Al (H
2pO
4)
3the preparation method of solution is as described below: weigh a certain amount of H
3pO
4solution also heats, according to the ratio Al/P=1:3 of amount of substance, to H
3pO
4the Al (OH) of solid state is slowly added in solution
3, and be stirred to the Al (OH) of solid state
3dissolve completely and then form Al (H
2pO
4)
3solution, then utilizes the Al (H that deionized water will prepare
2pO
4)
3solution dilution, the Al (H after described dilution
2pO
4)
3the massfraction of solution is 5-20%.
4. aluminium alloy anode oxide film compound hole sealing treatment process as claimed in claim 3, is characterized in that: the Al (H after described dilution
2pO
4)
3the massfraction of solution is 10%.
5. aluminium alloy anode oxide film compound hole sealing treatment process as claimed in claim 1, is characterized in that: described cerium solution consist of 6gL
-1ce (NO
3)
36H
2o and 3gL
-1h
2o
2mixing solutions.
6. aluminium alloy anode oxide film compound hole sealing treatment process as claimed in claim 5, it is characterized in that: in stepb, described cerium salt sealing pores is carry out in the environment of 60 DEG C in temperature, and the time of sealing pores is 150min.
7. aluminium alloy anode oxide film compound hole sealing treatment process as claimed in claim 1, it is characterized in that: in step C and step D, described set time is 12 hours.
8. aluminium alloy anode oxide film compound hole sealing treatment process as claimed in claim 1, is characterized in that: in step C and step D, will be brushed with aluminium alloy anode oxide film thermal treatment for some time at 250 DEG C of phosphate solution.
9. aluminium alloy anode oxide film compound hole sealing treatment process as claimed in claim 1, is characterized in that: in step D, and the number of times repeating to brush is 4 times.
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| CN111468705A (en) * | 2020-05-12 | 2020-07-31 | 东南大学 | Composite treatment process for manufacturing corrosion-resistant protective layer on surface of cast aluminum alloy |
| CN112779582A (en) * | 2020-12-24 | 2021-05-11 | 上海交通大学 | Method for repairing micro-arc oxidation damaged film of aluminum-based material |
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| CN106086988A (en) * | 2016-08-09 | 2016-11-09 | 天津工业大学 | A kind of laser melting coating closes the method for aluminium alloy anode oxide film |
| CN106086988B (en) * | 2016-08-09 | 2017-12-19 | 天津工业大学 | A kind of method of laser melting coating closing aluminium alloy anode oxide film |
| CN106637336B (en) * | 2016-10-21 | 2018-11-30 | 重庆南涪铝业有限公司 | A kind of method for oxidation of aluminum profile |
| CN107999347A (en) * | 2016-10-28 | 2018-05-08 | 郭向阳 | A kind of method for sealing for being used for metal oxide film and depositional coating |
| CN109457286A (en) * | 2018-12-10 | 2019-03-12 | 歌尔股份有限公司 | The surface treatment method of aluminum alloy materials |
| CN110923778A (en) * | 2019-11-28 | 2020-03-27 | 西安昆仑工业（集团）有限责任公司 | Die-casting aluminum surface treatment method |
| CN111468705A (en) * | 2020-05-12 | 2020-07-31 | 东南大学 | Composite treatment process for manufacturing corrosion-resistant protective layer on surface of cast aluminum alloy |
| CN112779582A (en) * | 2020-12-24 | 2021-05-11 | 上海交通大学 | Method for repairing micro-arc oxidation damaged film of aluminum-based material |
| CN112779582B (en) * | 2020-12-24 | 2021-11-02 | 上海交通大学 | Method for repairing micro-arc oxidation damaged film of aluminum-based material |
| CN113904039A (en) * | 2021-09-30 | 2022-01-07 | 蜂巢能源科技有限公司 | Anodic oxidation liquid, battery shell, and insulation protection method and application thereof |
| CN113904039B (en) * | 2021-09-30 | 2023-08-08 | 蜂巢能源科技有限公司 | Anodic oxidation liquid, battery shell, and insulation protection method and application thereof |
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