CN101892477B - Treatment solution for preparing aluminum alloy surface amorphous composite passivation film, preparation method and application - Google Patents
Treatment solution for preparing aluminum alloy surface amorphous composite passivation film, preparation method and application Download PDFInfo
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- CN101892477B CN101892477B CN2010102066607A CN201010206660A CN101892477B CN 101892477 B CN101892477 B CN 101892477B CN 2010102066607 A CN2010102066607 A CN 2010102066607A CN 201010206660 A CN201010206660 A CN 201010206660A CN 101892477 B CN101892477 B CN 101892477B
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Abstract
The invention discloses treatment solution for preparing an aluminum alloy surface amorphous composite passivation film, a preparation method and application. A formula of the treatment solution comprises 5 to 15g/L of corrosion inhibiting negative ion-containing rare earth salt, 3 to 10g/L of catalyst type composite oxidant, 1 to 3g/L of auxiliary oxidant, 0.1 to 0.5g/L of buffering film-forming accelerator and 0.5 to 1.5g/L of composite stabilizer. The treatment solution does not contain any toxic chromium or organic substances, does not need heating during conversion treatment of 2 to 5 minutes, and can prepare the golden amorphous 'rare earth-manganese' composite passivation film with excellent performance on the aluminum alloy surface. The treatment solution well solves environmental pollution and human harm caused by the present hexavalent chromium treatment, and can overcome the defects that a zirconium titanate series conversion film is colorless and field judgment cannot be realized. The preparation method has the advantages of simple process, simple and convenient operation and low cost, and is easy to realize industrialization.
Description
Technical field
The present invention relates to corrosion of aluminium alloy and guard technology field, be specifically related to a kind of treatment solution and method for making and application for preparing aluminum alloy surface amorphous composite passivation film.Based on the amorphous substance characteristic, the conversion film that obtains has the superior corrosion resistance ability, and rete is golden yellow, is beneficial to and realizes online judgement.
Background technology
The duraluminum amount of being to use is only second to the second largest metallic substance of iron and steel.Duraluminum is under the atmospheric environment condition, and the surface can form one deck oxide film as thin as a wafer makes it have certain corrosion resistance nature.But this spontaneous oxidation film is damaged easily, is especially containing Cl
-Environment in, various destructions such as spot corrosion, crevice corrosion, stress corrosion are very easily taken place.For improving the corrosion resistance nature of aluminum alloy surface, further enlarge its range of application, increase the service life, the aluminum alloy surface protection is extremely important.
In common protective treatment technology, aluminium alloy anode oxide technology and chromic salt oxidation technology are used widely.Especially one important surface treatment procedure of widespread use before the latter sprays as duraluminum especially.But chromic salt chemistry conversion processing all produces harm to environment and HUMAN HEALTH.Beginning in 2007, Europe, North America have been completely forbidden the various product of aluminum alloy surface chromate treating, like aluminium section bar, electronic product etc.The research and development of chromate conversion treatments substitute technology receive extensive concern, many generations the chromium technology occur in succession, like phosphatization, zinc phosphatization, based on the complex compound treatment process (CARBDOBOND) of titanium zirconium and fluorine, Envirox series of processes technology etc.Application number is that 200410021031.1,200480031392.2,200510100993.0,20058002127.6,200610046292.8,200610046516.5,200680002318.7 serial Chinese invention patent application all relates to these technology.Though some in these technology have got into operational phase, their anti-corrosion effect still has certain gap with traditional chromate conversion treatments.Though with titanium-zirconium system is that the treatment technology of representative has certain application aborning, its subject matter is that its rete is colourless, is unfavorable for the online judgement in the production process.
In numerous chromic salt substitute technologies, the resistance to corrosion of rare earth chemistry conversion film can reach, even is confirmed by The experimental results above the conclusion of traditional chromic acid salt Passivation Treatment effect.But the composite passivated treatment technology of researching and developing at present; Soak and electrochemistry bonded cerium-molybdenum treatment process, fused salt soaking technology etc. like simply immersing technology, rare earth Baume layer treatment process, high temperature; Because the following shortcoming that self exists is difficult to be applied to actual production; As: (1) treatment time is long, technology that has even needs time in 2 week; (2) treatment temp is high, complex process.Compare with traditional chromate treating, film forming speed and processing cost have huge spread.In recent years, based on H
2O
2Composite passivated treatment process as the film forming oxygenant has been obtained remarkable progress, like Chinese patent ZL200510010441.0.There are many research reports to think that rare-earth salts-ydrogen peroxide 50 conversion treatment process only is suitable for the higher aluminum alloy series of copper content abroad.Use cerium salt as treatment solution master salt, ydrogen peroxide 50 (H in the above-mentioned technology
2O
2) as the oxygenant of composite passivated processing, though reached the purpose of low temperature (20～100 ℃) fast processing (5～20 minutes treatment times), this oxygenant very easily decomposes in open atmospheric environment, will lose its strong oxidizing property in a short period of time.Promptly lost efficacy after the treatment solution that configures possibly use once, handle other member, need reconfigure new treatment solution.With traditional chromate treating technology relatively, the long-acting stability of treatment solution and processing cost all remain further to be improved.Recently, Chinese patent CN101139708A has invented a kind of rare-earth salts-KMnO
4The system film-forming process, but the conversion fluid composition of this technology is very complicated, cost is higher, and its stability of solution of what is more important is relatively poor, can not satisfy the basic demand of Stability of Bath Solution in the production, thereby greatly limits its commercial application.The treatment solution component of Patent exploitation of the present invention is simple, easy good stability, and can obtain have amorphous golden yellow passive film in aluminum alloy surface, rete has excellent corrosion resisting performance, and is beneficial to the online judgement of production.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of treatment solution and method for making and application for preparing aluminum alloy surface amorphous composite passivation film is provided.Problems such as present chromium-free treating liquid film forming efficiency is low, stability of solution difference both can have been solved; Can obtain solidity to corrosion, moisture-proof heat, anti-boiling water, golden yellow amorphous composite passivation film that sticking power is good again; Thereby realize on-the-spot judgement, overcome the colourless defective of titanium zirconium system conversion film simultaneously.
The present invention can realize above-mentioned purpose through following technical scheme:
A kind of treatment solution for preparing aluminum alloy surface amorphous composite passivation film, major ingredient are inhibition negatively charged ion rare-earth salts, buffer-type film forming accelerating, catalyst type multiple oxygenant, secondary oxidizer and one package stabilizer, and the bulking value specific concentration of each composition is following:
Contain inhibition negatively charged ion rare-earth salts 5～15gL
-1
The multiple oxygenant 3～10gL of catalyst type
-
Buffer-type film forming accelerating 0.1～0.5gL
-1
One package stabilizer 0.5～1.5gL
-1
The said inhibition negatively charged ion rare-earth salts that contains is cerous nitrate or Lanthanum trinitrate.
Said buffer-type film forming accelerating is one or both the mixture in matt salt, sodium bifluoride, potassium hydrogen fluoride, Sodium Fluoride, Potassium monofluoride or the Neutral ammonium fluoride;
The multiple oxygenant of said catalyst type is sodium bismuthate or bismuthic acid potassium;
Said secondary oxidizer is permanganate or perchlorate;
Said one package stabilizer is the mixture of a kind of and boric acid or Sodium Tetraborate in acetic acid, Hydrocerol A or the Weibull.
The preparation method of said treatment solution is to be dissolved in the water containing inhibition negatively charged ion rare-earth salts, the multiple oxygenant of catalyst type, secondary oxidizer, buffer-type film forming accelerating and one package stabilizer, and the pH value of re-adjustment solution is 1.8～2.6; The bulking value specific concentration of each composition is following:
Contain inhibition negatively charged ion rare-earth salts 5～15gL
-1
The multiple oxygenant 3～10gL of catalyst type
-
Buffer-type film forming accelerating 0.1～0.5gL
-1
One package stabilizer 0.5～1.5gL
-1
The said inhibition negatively charged ion rare-earth salts that contains is cerous nitrate or Lanthanum trinitrate;
Said buffer-type film forming accelerating is one or both the mixture in matt salt, sodium bifluoride, potassium hydrogen fluoride, Sodium Fluoride, Potassium monofluoride or the Neutral ammonium fluoride;
The multiple oxygenant of said catalyst type is sodium bismuthate or bismuthic acid potassium;
Said secondary oxidizer is permanganate or perchlorate;
Said one package stabilizer is the mixture of a kind of and boric acid or Sodium Tetraborate in acetic acid, Hydrocerol A or the Weibull.
The application of described treatment solution in the preparation aluminum alloy surface amorphous composite passivation film may further comprise the steps:
(1) aluminum alloy surface is polished smooth; Aluminum alloy surface oil removing, pickling;
(2) duraluminum was inserted mixed acid solution after 1～5 minute, deionized water rinsing, the concentration of each composition is in the said mixed acid solution: H
2SO
430～50%wt, H
3PO
45～20%wt, HF 1～5%wt, all the other are water;
(3) duraluminum is placed the described treatment solution of claim 1, behind 2～5min, form golden yellow anti-corrosion film in aluminum alloy surface.
Form golden yellow anti-corrosion film in aluminum alloy surface and form sull by the complex compound of amorphous rare earth oxide compound or oxyhydroxide, manganese, Manganse Dioxide etc.;
For further understanding process characteristic of the present invention, set forth as follows in the face of the film forming mechanism of duraluminum in the composite passivated treatment solution of this institute invention down:
Before treatment solution of the present invention uses, need in air, to be stirred well to evenly.During conversion processing, according to cathode filming mechanism, because aluminum alloy surface exists different potentials to reach impurity atoms mutually, cause forming countless galvanic cells and electrochemical reaction taking place at surperficial microcell: dissolving metal: M-2e takes place in the micro anode district
-→ M
Z+(M represents the metallic element in the duraluminum), H takes place in the micro cathode district
2Separate out: 2H
++ 2e
-→ H
2Or O
2Reduction: O
2+ 2H
2O+4e → 4OH
-Thereby, OH-ionic concn in micro cathode district is increased, the pH value raises, and is Ce (OH)
3Or Ce (OH)
4Deposition create favorable conditions.
When adopting ammonium salt and sodium salt compound accelerant, there is NH in the solution
4 +, F
-, HF
2 -, BO
4 3-And the interaction between the disassociation matter.
HF
2 -→F
-+HF (1)
BO
4 3-+F
-+H
-→BF
4 -+H
2O (2)
BF
4 -+NH
4 +→NH
4BF
4 (3)
Because F
-Ionic radius is less, can carry out corrasion, the accelerating anode speed of response through the moisture film and the sheath entering matrix of aluminum alloy surface; Can combine with cerium ion on the other hand: Ce
3++ 3F
-→ CeF
3Or Ce
4++ 4F
-→ CeF
4Form hydrogen bond between can be when having hydroxyl and amino to exist in the solution and make CeF through amino
4 (3)Polymerization can be the sedimentary substrate that provides.But because CeF
4 (3)Ionic product is less, F
-Concentration is unsuitable too high, can come slowly to discharge F through the reaction between above-mentioned (1), (2), (3)
-, guaranteed F
-Ionic concn is in maintenance level.
As when selecting sodium bismuthate and potassium permanganate as oxygenant for use, (6), (7) reaction also take place in negative electrode except that (4), (5) reaction take place, therefore when quickening cathodic reaction, can promote MnO
4 -Recycle, make it and have the character of " catalyzer ", guarantee that solution reaches efficient recycling purpose.
MnO
4 -+8H
++5e→Mn
2++4H
2O (4)
MnO
4 -+2H
2O+2e→MnO
2↓+4OH
- (5)
Along with the carrying out of reaction, solution gradually becomes incarnadine, and the Mn valence state is mainly with [Mn (H
2O)
6]
2+And MnO
2Form exists.
2Mn
2++5NaBiO
3+14H
+→2MnO
4 -+5Bi
3++5Na
++7H
2O (6)
MnO
2+2KHF
2+2HF→K
2MnF
6+2H
2O (7)
K
2MnF
6Be a kind of golden yellow material, with (8), (9) reaction product golden yellow rete of aluminum alloy surface that is composited.
Ce
3++3OH
-→Ce(OH)
3↓ (8)
Ce
4++4OH
-→Ce(OH)
4↓ (9)
Ce (OH) wherein
4Be through (10), (11), reaction process acquisition as follows:
2Ce
3++2H
2O+2O
2+2e
-→2Ce(OH)
2 2+ (10)
Ce(OH)
2 2++2OH
-→Ce(OH)
4→CeO
2·2H
2O (11)
Perhaps through following approach:
2H
2O+2O
2 +2e
-→H
2O
2+2OH
- (12)
2Ce(OH)3
+3H
2O
2→2Ce(OH)
3OOH+2H
2O (13)
Ce(OH)
3OOH+2Ce(OH)
3+H
2O→3Ce(OH)
4 (14)
Treatment solution of the present invention amounts of components aspect explanation: cushion the promotor F that ionization goes out in solution certainly by what weak acid and weak base was formed
-Ce can take place
3++ 3F
-→ CeF
3Or Ce
4++ 4F
-→ CeF
4Reaction generates the less CeF of ionic product
3 (4)Therefore when its consumption is higher, make CeF
3 (4)Moment covers workpiece surface, forms tectorium, and the formation, the length that hinder amorphous film are thick, can reduce main salt concentration simultaneously; DeGrain when too low.The suitable formed CeF of F-concentration
3 (4)When being deposited on workpiece surface, CeF can take place
3 (4)+ 3 (4) OH
-→ Ce (OH)
3 (4)+ 3 (4) F
-Reaction makes the oxide compound of cerium or complex compound, the Manganse Dioxide of oxyhydroxide and manganese directly be deposited on workpiece surface, improves its over-all properties.
KMnO in the multiple oxygenant
4When consumption is too high, have a strong impact on the surface quality of rete, make conversion film overstrike and uneven thickness; When too low, oxidisability is not strong, influences film forming speed and membranous layer corrosion resistance, so its consumption should be controlled at 1gL
-1～3gL
-1NaBiO
4Can add (in theory with MnO according to actual life cycle situation
4 -Be consumed fully and be one-period), cause the solution total ion concentration too high when too high, influence ion-transfer, be unfavorable for the growth of rete.
Contain the anionic rare-earth salts of inhibition, be used to into golden yellow rare earth film on the one hand, rely on anionic effect on the other hand, be adsorbed on matrix surface, suppress the too fast dissolving of matrix, quicken the deposition of conversion film.But when main salt cation too high levels, can the promote the oxidation agent aging, so its content should be at 5gL
-1～15gL
-1
Boric acid and acetic acid are to be used for bonding force between stabilizing solution, the visual appearance that improves rete and rete and matrix, the outer layer coating.
Be main with the oxide compound (or oxyhydroxide) of 4 valency ceriums and the oxide compound of manganese in the rete.
It is following that technology according to the invention compared with prior art can reach beneficial effect:
(1) conversion processing liquid formula and technology are simple, need not extra interpolation secondary oxidizer, inhibiter, wetting agent and the agent of pH dash adjustment, make system component simple, and influence factor is easy to control;
(2) treatment solution need not heating, gets final product fast filming under the room temperature, and film formation time is 2min～5min;
(3) can obtain golden yellow non-crystalline state passivation film, help online judgement, film surface is fine and close, does not have obvious crack defect, and corrosion resistance nature is high, and is good with basal body binding force;
(4) contain in the solution from the buffering and the material of cyclic oxidation, can guarantee that the solution long term uses agingly, treatment solution stability height can guarantee 1 month duration of service;
(5) rete does not contain chromium and organic substance, and material discharging that treating processes is pollution-free belongs to environmentally friendly technology, alternative chromate treating technology.
Description of drawings
The SEM picture of Fig. 1 embodiment 1 prepared rete;
The XRD figure spectrum of Fig. 2 embodiment 1 prepared rete;
The polarization curve of naked sample of Fig. 3 and composite passivation film;
The XRD figure spectrum of Fig. 4 embodiment 2 prepared retes;
The XRD figure spectrum of Fig. 5 embodiment 3 prepared retes;
The XRD figure spectrum of Fig. 6 embodiment 4 prepared retes.
Embodiment
In order to understand technical characterstic of the present invention better, the present invention is further described below in conjunction with embodiment.
The composite passivated processing of embodiment 1:6063 aluminium alloy section surface
The composite passivated treatment process of aluminum alloy surface comprises the steps:
(1) pre-treatment
(a) from 6063 large-sized aluminium alloy section bar intercepting coupons, with SiC liquid honing to surfaceness at 10 microns;
(b) at first sample being inserted temperature is that 50 ℃, concentration are 40gL
-1Sodium hydroxide solution oil removing, degreasing 1 minute, clean with rinsed with deionized water afterwards;
(c) dedust in 1 minute of the rare nitric acid liquid of 15% (weight) dipping is put in test piece, clean with rinsed with deionized water then, and dry with hair dryer;
(d) (the mixed acid solution weight percent is: 40%H mixed acid solution to be inserted in test piece
2SO
4, 10%H
3PO
4, 3%HF, all the other are deionized water) in 1 minute, clean with rinsed with deionized water afterwards, and utilize right wind to dry or hair dryer dries up and gets final product.
(2) composite passivated treatment solution configuration: dispose composite passivated treatment solution 1000ml, wherein the weightmeasurement ratio of various compositions is following in the treatment solution: cerous nitrate 10gL
-1, sodium bismuthate 6gL
-1, potassium permanganate 2gL
-1Matt salt 0.3gL
-1, one package stabilizer 1gL
-1(its mesoboric acid 0.5gL
-1, acetic acid 0.5gL
-1), above material is soluble in water, and disposing composite passivated treatment solution volume is 1000ml, the treatment solution pH value of initial configuration is 2.4, transfers to pH2.2 with rare nitric acid.
(3) the composite passivated processing of aluminum alloy surface: will in the pretreated duraluminum of step (1) is inserted the stainless steel clean container that fills the described treatment solution of step (2) of hanger, at room temperature flood, film forming was accomplished in 3 minutes.Duraluminum is suspended on the hanger with aluminium wire and immerses in the treatment solution of configuration, floods after 3 minutes, takes out test piece, rinses well and dries with hair dryer with tap water.
Present embodiment is to place after 1 hour after the solution allocation to carry out composite passivated processing again.Its outward appearance of the rete that obtains as shown in Figure 1, even film layer, color and luster is golden yellow.Show that through ESEM (SEM) observation rete is fine and close, does not have tangible micro-flaw.As shown in Figure 2 through X-ray diffraction (XRD) analysis surface; This rete has amorphous structure; SEM observation is carried out in the rete cross section, 3 microns of its rete mean thicknesss, shown in Figure 3 is the dynamic electrochemical tests of sample in 3.5% sodium-chlor neutral electrolyte after naked aluminium sample and the Passivation Treatment.For 6063 duraluminums without composite passivated processing, its corrosion electric current density 6.78 μ A/cm
2, and its corrosion current of 6063 duraluminums of handling through present embodiment is 0.15 μ A/cm
2, be 1/40 of coating alloy not.
The composite passivated processing of embodiment 2:6063 aluminium alloy section surface
The treatment process of present embodiment is with embodiment 1,
Composite passivated treatment solution configuration: dispose composite passivated treatment solution 1000ml, wherein the bulking value specific concentration of various compositions is following in the treatment solution: cerous nitrate 5gL
-1, sodium bismuthate 3gL
-1, potassium permanganate 1gL
-1Matt salt 0.1gL
-1, one package stabilizer 0.5gL
-1(its mesoboric acid 0.2gL
-1, acetic acid 0.3gL
-1), transfer to pH1.8 with rare nitric acid.
The composite passivated treatment process of aluminum alloy surface is similar with embodiment 1, but the treatment time is slightly longer than embodiment 1, is 5 minutes.Wherein treatment solution began to carry out conversion processing in 1 hour for configuring the back placement.
Also for golden yellow, its film surface state, component property and crystalline structure thereof are all similar with embodiment 1 for the rete that present embodiment obtained.Difference is that rete is thinner relatively, makes that the intensity of non-crystalline state diffraction peak is relatively low, and is as shown in Figure 4.
The composite passivated processing of embodiment 3:6063 aluminium alloy section surface
The treatment process of present embodiment is with embodiment 1, and composite passivated treatment solution configuration: dispose composite passivated treatment solution 1000ml, wherein the bulking value specific concentration of various compositions is following in the treatment solution: cerous nitrate 15gL
-1, sodium bismuthate 10gL
-1, potassium permanganate 3gL
-1Matt salt 0.5gL
-1, one package stabilizer 1.5gL
-1(its mesoboric acid 0.5gL
-1, acetic acid 1gL
-1), it is 2.5 that passivating solution uses pH.
The composite passivated treatment process of aluminum alloy surface is similar with embodiment 1, but treatment solution carries out conversion processing for configuring the back placement after 15 days, and the treatment time is 5 minutes.
After the long-time passivating solution of placing was to 6063 duraluminum Passivation Treatment, still for golden yellow, its film surface state, composition and crystalline structure thereof were all similar with embodiment 1 for the rete that is obtained.Be illustrated in figure 5 as the XRD figure spectrum of this embodiment gained rete, this rete presents tangible amorphous diffractive features.Its performance of gained rete is also suitable with embodiment 1.
The composite passivated processing of embodiment 4:6063 aluminium alloy section surface
(1) pre-treatment
(a) from 6063 large-sized aluminium alloy section bar intercepting coupons, with SiC liquid honing to surfaceness at 6 microns;
(b) at first sample being inserted temperature is that 50 ℃, concentration are 40gL
-1Sodium hydroxide solution oil removing, degreasing 3 minutes, clean with rinsed with deionized water afterwards;
(c) dedust in 1 minute of the rare nitric acid liquid of 15% (weight) dipping is put in test piece, clean with rinsed with deionized water then, and dry with hair dryer;
(d) (the mixed acid solution weight percent is: 30%H mixed acid solution to be inserted in test piece
2SO
4, 20%H
3PO
4, 1%HF, all the other are deionized water) in 5 minutes, clean with rinsed with deionized water afterwards, and utilize right wind to dry or hair dryer dries up and gets final product.
(2) composite passivated treatment solution configuration: dispose composite passivated treatment solution 1000ml, wherein the weight or meausurement percentage concentration of various compositions is following in the treatment solution: Lanthanum trinitrate 8gL
-1, sodium bismuthate 3gL
-1, potassium permanganate 1gL
-1Matt salt 0.1gL
-1, one package stabilizer 0.5gL
-1(its mesoboric acid 0.2gL
-1, acetic acid 0.3gL
-1), transfer to pH1.8 with rare nitric acid.
(3) the composite passivated processing of aluminum alloy surface: will in the pretreated duraluminum of step (1) is inserted the stainless steel clean container that fills the described treatment solution of step (2) of hanger, at room temperature flood, film forming was accomplished in 3 minutes.Duraluminum is suspended on the hanger with aluminium wire and immerses in the treatment solution of configuration, floods after 3 minutes, takes out test piece, rinses well and dries with hair dryer with tap water.
The composite passivated treatment process of aluminum alloy surface is similar with embodiment 1, but the treatment time is slightly longer than embodiment 1, is 5 minutes.Wherein treatment solution began to carry out conversion processing in 1 hour for configuring the back placement.
The composite passivated processing of embodiment 5:6063 aluminium alloy section surface
(1) pre-treatment
(a) from 6063 large-sized aluminium alloy section bar intercepting coupons, with SiC liquid honing to surfaceness at 10 microns;
(b) at first sample being inserted temperature is that 50 ℃, concentration are 40gL
-1Sodium hydroxide solution oil removing, degreasing 2 minutes, clean with rinsed with deionized water afterwards;
(c) dedust in 1 minute of the rare nitric acid liquid of 15% (weight) dipping is put in test piece, clean with rinsed with deionized water then, and dry with hair dryer;
(d) (the mixed acid solution weight percent is: 50%H mixed acid solution to be inserted in test piece
2SO
4, 5%H
3PO
4, 5%HF, all the other are deionized water) in 1 minute, clean with rinsed with deionized water afterwards, and utilize right wind to dry or hair dryer dries up and gets final product.
(2) composite passivated treatment solution configuration: dispose composite passivated treatment solution 1000ml, wherein the bulking value specific concentration of various compositions is following in the treatment solution: cerous nitrate 5gL
-1, sodium bismuthate 3gL
-1, potassium permanganate 1gL
-1Matt salt 0.1gL
-1, one package stabilizer 0.5gL
-1(its mesoboric acid 0.2gL
-1, acetic acid 0.3gL
-1), transfer to pH1.8 with rare nitric acid.
(3) the composite passivated processing of aluminum alloy surface: will in the pretreated duraluminum of step (1) is inserted the stainless steel clean container that fills the described treatment solution of step (2) of hanger, at room temperature flood, film forming was accomplished in 3 minutes.Duraluminum is suspended on the hanger with aluminium wire and immerses in the treatment solution of configuration, floods after 3 minutes, takes out test piece, rinses well and dries with hair dryer with tap water.
The composite passivated treatment process of aluminum alloy surface is similar with embodiment 1, but treatment solution carries out conversion processing for configuring the back placement after 30 days, and the treatment time is 3 minutes.
After the long-time passivating solution of placing was to 6063 duraluminum Passivation Treatment, still for golden yellow, its film surface state, composition and crystalline structure thereof were all similar with embodiment 1 for the rete that is obtained.Be illustrated in figure 6 as the XRD figure spectrum of this embodiment gained rete, this rete presents tangible amorphous diffractive features.Its performance of gained rete is also suitable with embodiment 1.
Embodiment 6: fine aluminium sheet (thickness 1mm) surface recombination Passivation Treatment
Present embodiment disposes composite passivated treatment solution 1000ml, and wherein the bulking value specific concentration of various compositions is following in the treatment solution: cerous nitrate 5gL
-1, sodium bismuthate 3gL
-1, potassium permanganate 1gL
-1Matt salt 0.1gL
-1, one package stabilizer 0.5gL
-1(its mesoboric acid 0.2gL
-1, acetic acid 0.3gL
-1), transfer to pH1.8 with rare nitric acid.Treatment solution configures the back placement and carries out conversion processing after 1 hour, and the treatment process of present embodiment is with embodiment 1, and the treatment time is 3 minutes.
Sample after the film forming carries out the polyester spray treatment according to chromic salt on-line spray order and technological standards.And the spraying rete required to carry out punching press, anti-waste water, hundred lattice, intensity, cupping, corrosion-resistant experiment according to the chromating GB, each item index all meets the requirements.
Claims (3)
1. treatment solution for preparing aluminum alloy surface amorphous composite passivation film; It is characterized in that; Major ingredient is inhibition negatively charged ion rare-earth salts, buffer-type film forming accelerating, catalyst type multiple oxygenant, secondary oxidizer and one package stabilizer, and the bulking value specific concentration of each composition is following:
The said inhibition negatively charged ion rare-earth salts that contains is cerous nitrate or Lanthanum trinitrate;
Said buffer-type film forming accelerating is one or both the mixture in matt salt, sodium bifluoride, potassium hydrogen fluoride, Sodium Fluoride, Potassium monofluoride or the Neutral ammonium fluoride;
The multiple oxygenant of said catalyst type is sodium bismuthate or bismuthic acid potassium;
Said secondary oxidizer is permanganate or perchlorate;
Said one package stabilizer is the mixture of a kind of and boric acid or Sodium Tetraborate in acetic acid, Hydrocerol A or the Weibull.
2. the method for preparing the said treatment solution of claim 1; It is characterized in that; Be will contain inhibition negatively charged ion rare-earth salts, the multiple oxygenant of catalyst type, secondary oxidizer, buffer-type film forming accelerating and one package stabilizer to be dissolved in the water, the pH value of re-adjustment solution is 1.8-2.6; The bulking value specific concentration of each composition is following:
3. the application of the described treatment solution of claim 1 in the preparation aluminum alloy surface amorphous composite passivation film is characterized in that, may further comprise the steps:
(1) aluminum alloy surface is polished smooth; Aluminum alloy surface oil removing, pickling;
(2) duraluminum was inserted mixed acid solution after 1～5 minute, deionized water rinsing, the concentration of each composition is in the said mixed acid solution: H
2SO
430～50%wt, H
3PO
45～20%wt, HF 1～5%wt, all the other are water;
(3) duraluminum is placed the described treatment solution of claim 1, behind 2～5min, form golden yellow anti-corrosion film in aluminum alloy surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102066607A CN101892477B (en) | 2010-06-21 | 2010-06-21 | Treatment solution for preparing aluminum alloy surface amorphous composite passivation film, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102066607A CN101892477B (en) | 2010-06-21 | 2010-06-21 | Treatment solution for preparing aluminum alloy surface amorphous composite passivation film, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101892477A CN101892477A (en) | 2010-11-24 |
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| CN102433559B (en) * | 2011-10-24 | 2013-09-04 | 宁波科苑鑫泰表面处理新技术有限公司 | Rare earth cerium-containing metal treatment fluid and production method thereof |
| CN102808170A (en) * | 2012-08-01 | 2012-12-05 | 天津大学 | Treating fluid for corrosion-resistant rare earth conversion film on surface of aluminum alloy, and application method thereof |
| CN103276387B (en) * | 2013-05-20 | 2015-10-07 | 华南理工大学 | A kind of method preparing cerium manganese/molybdenum multiple elements design conversion film in aluminum alloy surface |
| CN103320780A (en) * | 2013-05-28 | 2013-09-25 | 太原双塔刚玉股份有限公司 | High-efficiency normal temperature aluminum alloy passivating solution and preparation technology thereof |
| CN105112973B (en) * | 2013-09-03 | 2017-07-07 | 天津大学 | A kind of preparation method of lemon acid doping Cerium conversion film |
| CN103866308A (en) * | 2014-04-03 | 2014-06-18 | 上海瑞尔实业有限公司 | Chromium-free passivating pretreatment method for mirror aluminum board |
| CN104878375A (en) * | 2015-06-19 | 2015-09-02 | 海安县申菱电器制造有限公司 | Stainless steel product surface passivation method |
| CN104894550B (en) * | 2015-06-29 | 2017-07-21 | 陈涛 | A kind of without phosphorus, floride-free, heavy metal free environmentally friendly film agent, its preparation method and its application being made up of Biological inositol |
| CN106086857B (en) * | 2016-08-25 | 2019-07-02 | 广州市泓硕环保科技有限公司 | A kind of film forming solution of aluminium based material surface collaboration Optimization-type Chrome-free yellow conversion film and its method for preparing conversion film |
| CN106676507A (en) * | 2016-12-20 | 2017-05-17 | 深圳市豪龙科技有限公司 | Aluminium alloy passivant without chromium and using method thereof |
| CN106966702B (en) * | 2017-04-12 | 2019-10-22 | 苏州轩朗塑料制品有限公司 | A kind of preparation method of biodegradable magnesium-base metal material |
| WO2019006626A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市盈恒科技有限公司 | Chromium-free passivator, aluminum workpiece and surface passivation process therefor |
| CN110042381B (en) * | 2019-02-25 | 2021-12-07 | 瑞上兴通信信号器材(连云港)有限公司 | Preparation method of aluminum alloy surface film |
| CN110565083A (en) * | 2019-10-24 | 2019-12-13 | 徐州市国艺铝合金包装箱有限公司 | Solution suitable for aluminum alloy passivation process |
Citations (2)
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| US4359346A (en) * | 1981-04-16 | 1982-11-16 | Occidental Chemical Corporation | Trivalent chromium passivate solution and process for yellow passivate film |
| CN101139708A (en) * | 2007-10-17 | 2008-03-12 | 陈东初 | Transformation liquid for preparation of corrosion-resistant oxidation film on aluminium alloy surface and method of use thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4359346A (en) * | 1981-04-16 | 1982-11-16 | Occidental Chemical Corporation | Trivalent chromium passivate solution and process for yellow passivate film |
| CN101139708A (en) * | 2007-10-17 | 2008-03-12 | 陈东初 | Transformation liquid for preparation of corrosion-resistant oxidation film on aluminium alloy surface and method of use thereof |
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