CN104233273A - Chromium-free silicon passivation solution for passivating aluminum or aluminum alloy surface as well as preparation and using methods - Google Patents
Chromium-free silicon passivation solution for passivating aluminum or aluminum alloy surface as well as preparation and using methods Download PDFInfo
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Abstract
The invention relates to a chromium-free silicon passivation solution for passivating an aluminum or aluminum alloy surface, as well as preparation and using methods. The chromium-free silicon passivation solution is prepared by taking a silane coupling agent as a main agent, taking TEOS (tetraethyl orthosilicate) as an auxiliary agent, taking an inorganic salt or organic alkoxide acqueous solution of cobalt, zirconium, titanium and the like as a hydrolysis accelerator and adding an organic corrosion inhibitor. The passivation solution is free of chromium, fluorine or other toxic substances, a preparation process is simple, low in cost and suitable for industrial production, can be used instead of a chromate process, and has a wide application prospect, and a conversion coating after passivation is excellent in corrosion resistance.
Description
Technical field
The invention belongs to field of metal surface treatment, be specifically related to a kind of for aluminum or aluminum alloy surface passivation without chromium-silicon system passivating solution, method of preparation and use.
Background technology
Aluminum and aluminum alloy mateial has widespread use in fields such as building, chemical, aerospace, mechano-electronic, communications and transportation.Such material surface can form the very thin oxide film of one deck in atmosphere, but this tunic is still easy to make it be subject to heavy corrosion in various corrosive medium, seawater and atmospheric environment, cannot available protecting Al and Alalloy product.
Easily there are spot corrosion, intergranular corrosion, stress corrosion crack and Peeling Corrosion etc. in Al and Alalloy surface, so Al and Alalloy product must carry out rotproofing to its surface before the use.How to take effective measures a great problem suppressing the various corrosion of Al and Alalloy product to become current scientific research and industrial production application.Be most widely used at present and ripe be hexavalent chromate treatment technology, the erosion resistance of matrix can be significantly improved because of it and cheap price is used widely.But sexavalence or chromic strong carinogenicity have caused serious pollution to human body and environment, develop as one pleases and have endless trouble.Trend of Chrome-free treatment technology becomes current important research topic, realizes Trend of Chrome-free process completely and will benefit throughout the ages.
On February 13rd, 2003, European Union has issued " waste electronic andelectrical equipment instruction " and " using some Hazardous Substances Directive about restriction in electronic electric equipment ", and the use of chromic salt in metal treatment is prohibited the most at last.China also announces on March 6th, 2002, intend carrying out limitation to carcinogenic compound sexavalent chrome (chromic salt) from July, 2002 and use, and before 2006 year July cancel synchronous with European Union uses chromic salt.Therefore a kind of cheap, environmental friendliness, Trend of Chrome-free is sought and corrosion resisting property is better than focus and the difficult point that the material of chromic salt and production technique become research at present.
The Trend of Chrome-free passivating solution of current most study is zirconium titanium system's conversion film and silane system conversion film (see JP2004018992A, US6638369, CN200610046516.5, CN10218122A).Metal inorganic salt such as employing zirconium, titanium etc. is the main component of film forming liquid, can form thinner conversion film under special organism and other Additives on Al and Alalloy surface.But Al and Alalloy surface is after the process of zirconium titanium system, its corrosion resistance nature is lower than chromic salt, and a large amount of adding of fluorion still can cause very large harm to environment, and form film and do not have color to be difficult to directly judge that film forming is good and bad, produce to work and bring inconvenience.
Organosilane film adopts silane coupling agent to be main component, by adding of various additive, controls its hydrolytic polymerization, forms silane conversion film in aluminum alloy surface.The preparation of silane film generally takes sol-gel method.And this method also can such as, at the preparation of Al and Alalloy surface various ceramic coating, silicon-dioxide, aluminum oxide, zirconium white, cerium oxide and complex oxide film etc.After silane surface treatment, the group of outside has stronger hydrophobicity.Higher and its surface hydrophobicity of the physical strength of silane film hinders corrosive medium to be diffused into Al and Alalloy matrix, can effectively improve its antiseptic property.But pure silane film is more weak in silane film/metal interface bonding strength, and mainly with the complex construction silane coupling agent of various multi-functional group as starting material, expensive, cost performance is lower.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of for aluminum or aluminum alloy surface passivation without chromium-silicon system passivating solution, method of preparation and use.The preparation method of this passivating solution is simple, cost is low, Passivation Treatment can be carried out at normal temperatures and the treatment time short, the conversion film excellent anti-corrosion performance after passivation, passivating solution stability is high.
Summary of the invention
The present invention adopts silane coupling agent to be host, tetraethoxy (TEOS) is assistant agent, using cobalt, zirconium, Ti-inorganic salt or the organic alkoxide aqueous solution as hydrolytic accelerating agent, adds organic inhibitor, prepare without chromium-silicon system passivating solution, this passivating solution belongs to organic and inorganic passivating solution.This passivating solution is used for the process of aluminum or aluminum alloy surface impregnation, obtain the organic-inorganic conversion film that solidity to corrosion is good, performance is better than the conversion film that chromic salt process obtains, and is produced on a large scale.
Detailed Description Of The Invention
Technical solution of the present invention is as follows:
A kind of for aluminum or aluminum alloy surface passivation without chromium-silicon system passivating solution, this passivating solution take silane coupling agent as host, and TEOS is assistant agent, with the inorganic salt of cobalt, zirconium and/or titanium or the organic alkoxide aqueous solution for hydrolytic accelerating agent, add organic inhibitor, reaction prepares;
Described organic inhibitor is Sodium dodecylbenzene sulfonate or sodium laurylsulfonate.
According to the present invention, the above-mentioned preparation method without chromium-silicon system passivating solution, step is as follows:
(1) silane coupling agent and TEOS are joined in methanol aqueous solution or aqueous ethanolic solution, stir, obtain solution A; Silane coupling agent: TEOS: water: the volume ratio of (methyl alcohol or ethanol) is 1:(0.1-1): (1-100): (0.1-2);
(2) by the inorganic salt of cobalt, zirconium and/or titanium or organic alkoxide, Sodium dodecylbenzene sulfonate or sodium laurylsulfonate are added to the water, and stir, and obtain solution B;
Cobalt: zirconium: the mol ratio of titanium is 1:(0-1): (0-1), cobalt: water: the mol ratio of (Sodium dodecylbenzene sulfonate or sodium laurylsulfonate) is 1:(100-2000): (0.05-1);
(3) solution B is added drop-wise in solution A, makes cobalt: the mol ratio of silane coupling agent is 1:(5-20), stirring at normal temperature reaction 0.5-5h, to obtain final product.
According to the present invention, preferably, the silane coupling agent described in step (1) is that one or more in KH550, KH560, KH570, KH580, KH602, KH792 are composite;
Described silane coupling agent: TEOS: water: the volume ratio of (methyl alcohol or ethanol) is 1:(0.2-0.8): (2-80): (0.2-1.5).
According to the present invention, preferably, the cobalt described in step (2): zirconium: the mol ratio of titanium is 1:(0.2-0.8): (0.2-0.8);
The inorganic salt of described cobalt, zirconium and/or titanium are the nitrate of cobalt, zirconium and/or titanium, vitriol or chlorate;
Described cobalt: water: the mol ratio of (Sodium dodecylbenzene sulfonate or sodium laurylsulfonate) is 1:(150-450): (0.2-0.8).
According to the present invention, preferably, the cobalt described in step (3): the mol ratio of silane coupling agent is 1:(8-18);
Described drop rate is 0.1-1mL/s, more preferably 0.2-0.8mL/s, and the reaction times is 1-4h.
According to the present invention, utilize above-mentioned without the method for chromium-silicon system passivating solution to aluminum or aluminum alloy surface passivation, step is as follows:
I () washes
By deionized water cleaning showers 2-3 time of aluminum or aluminum alloy surface, each 2-5min; Or aluminum or aluminum alloy is soaked 5-20min in deionized water;
(ii) degreasing and alkaline etching
Aluminum or aluminum alloy after washing is soaked 1-20min in alkaline etching dosing, carries out degreasing and alkaline etching, then use washed with de-ionized water 2-3 time;
Alkaline etching dosing composition is, sodium hydroxide: sodium carbonate: sodium phosphate or tripoly phosphate sodium STPP: water glass: Sodium dodecylbenzene sulfonate or sodium laurylsulfonate: water=(5-30): (0.5-2): (0.1-2): (0.1-2): (0.1-1): 100, mass ratio.
(iii) neutralization and washing
Aluminum or aluminum alloy after degreasing and alkaline etching is directly used deionized water wash 2-3 time; Or be immersed in neutralizer and flood 1-10min, neutralizer consists of nitric acid or the aqueous sulfuric acid of 10-40wt%, then uses deionized water wash 2-3 time;
(iv) passivation
Aluminum or aluminum alloy after neutralization and washing process be impregnated in 0.5-10min in passivating solution; Clean with deionized water, then dry in 25-150 DEG C of baking oven or warm air drying, namely completes Passivation Treatment.
According to the present invention, preferably, in step (i), each deionized water cleaning showers 3-5min, or soak 8-15min in deionized water.
According to the present invention, preferably, in step (ii), alkaline etching dosing composition is, sodium hydroxide: sodium carbonate: sodium phosphate or tripoly phosphate sodium STPP: water glass: Sodium dodecylbenzene sulfonate or sodium laurylsulfonate: water=(10-25): (0.6-1.5): (0.2-1.5): (0.1-0.8): (0.1-0.8): 100, mass ratio;
In alkaline etching dosing, soak time is 2-18min.
According to the present invention, preferably, in step (iii), neutralizer consists of nitric acid or the aqueous sulfuric acid of 15-35wt%, and soak time is 1-8min.
According to the present invention, preferably, in step (iv), aluminum or aluminum alloy impregnated in 1-9min in passivating solution, and drying temperature is 35-120 DEG C.
The present invention compared with prior art, has the following advantages:
1, the present invention adopts cheap silane coupling agent and TEOS as silicon source, prepared using cobalt, zirconium, Ti-inorganic salt or the organic alkoxide aqueous solution as hydrolytic accelerating agent organic inorganic hybridization without chromium-silicon system passivating solution.Stronger protective membrane can be formed on Al and Alalloy surface, effectively prevent the shortcoming of simple organic or inorganic treatment agent.
2, the present invention is simple without the preparation technology of chromium-silicon system passivating solution, and cost is low, and treatment temp is low, and the time is short, is suitable for large-scale industrial production, and application prospect is good.
3, the conversion film tool dense uniform that obtains of passivating method of the present invention, has excellent corrosion resistance nature.
Accompanying drawing explanation
Fig. 1 is the dynamic potential polarization curve of the embodiment of the present invention 2 naked aluminium used.
Fig. 2 is the dynamic potential polarization curve of gained conversion film after the embodiment of the present invention 2 passivation.
Fig. 3 is the SEM figure on naked aluminium surface in the embodiment of the present invention 2.
Fig. 4 is the SEM figure of gained aluminium surface conversion coating after the embodiment of the present invention 2 passivation.
Embodiment:
Below in conjunction with specific embodiment, also the present invention will be further described by reference to the accompanying drawings, but be not limited thereto.
Raw materials usedly in embodiment be convenient source, commercial products.
Embodiment 1
A kind of for aluminum or aluminum alloy surface passivation without chromium-silicon system passivating solution, this passivating solution take silane coupling agent as host, and TEOS is assistant agent, with the inorganic salt solution of cobalt, zirconium and titanium for hydrolytic accelerating agent, add Sodium dodecylbenzene sulfonate as organic inhibitor, reaction prepares;
Preparation process is as follows:
(1) by 7mL KH560,3mL TEOS, 7mL water and 5mL methanol mixed, stir, obtain solution A;
(2) 0.1g (0.344mmol) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 0.05g zirconium nitrate (0.147mmol), 0.05g titanium sulfate (0.208mmol) and 0.01g (0.029mmol) Sodium dodecylbenzene sulfonate are joined in 10mL water, stir, obtain solution B;
(3) be added drop-wise in solution A by solution B with the speed of 0.1mL/s, stirring at normal temperature reaction 3h, obtains without chromium-silicon system passivating solution.
Embodiment 2
Utilize embodiment 1 obtained without the method for chromium-silicon system passivating solution to aluminium surface passivation, step is as follows:
I () washes
By deionized water cleaning showers used for aluminum surface 2 times, each 5min;
(ii) degreasing and alkaline etching
Aluminium after washing is soaked 8min in alkaline etching dosing, carries out degreasing and alkaline etching, then use washed with de-ionized water 2 times;
Alkaline etching dosing composition is 10g sodium hydroxide, 1g sodium carbonate, 0.3g sodium phosphate, 0.3g water glass, 0.2g sodium laurylsulfonate and 100g deionized water;
(iii) neutralization and washing
Aluminium after degreasing and alkaline etching is flooded 1min in the salpeter solution of 15wt%, then uses deionized water wash 2 times;
(iv) passivation
Aluminium after neutralization and washing process be impregnated in 2min in passivating solution; Clean 2 times with deionized water after taking-up, then dry in 80 DEG C of baking ovens, namely complete Passivation Treatment.
Fig. 1 is the dynamic potential polarization curve of naked aluminium used before the present embodiment is washed, and as shown in Figure 1, the corrosion potential of naked aluminium is-1.269V, and corrosion current is 1.004 × 10
-4a.
Fig. 2 is the dynamic potential polarization curve of the present embodiment after passivating solution process, and as shown in Figure 2, the corrosion potential in 3.5wt% sodium chloride solution is-1.06V, and corrosion current is 2.08 × 10
-9a, protection ratio is 99.99%.
Fig. 3 is the SEM figure of naked aluminium used before the present embodiment is washed, and as shown in Figure 3, naked aluminium surface is not fine and close, and there is the existence of large slight crack on surface, is very easily corroded.
Fig. 4 is the SEM figure of the aluminium of the present embodiment after passivating solution process, and as shown in Figure 4, after passivating solution process, aluminium surface is made up of the organic-inorganic hybrid films of densification, do not have crackled appearance.
Embodiment 3
As described in Example 1 for aluminum or aluminum alloy surface passivation without chromium-silicon system passivating solution, difference adds 4mL KH560 and 3mL KH570 in preparation process (1).
Utilize the present embodiment to obtain without the method for chromium-silicon system passivating solution to aluminium surface passivation, step is with embodiment 2.
Result: the corrosion potential in 3.5wt% sodium chloride solution is-0.98V, corrosion current is 4 × 10
-9a, protection ratio is 99.99%.
Embodiment 4
As described in Example 1 for aluminum or aluminum alloy surface passivation without chromium-silicon system passivating solution, difference does not add zirconium nitrate and titanium sulfate in preparation process (2).
Utilize the present embodiment to obtain without the method for chromium-silicon system passivating solution to aluminium surface passivation, step is with embodiment 2.
Result: the corrosion potential in 3.5wt% sodium chloride solution is-1.01V, corrosion current is 2.51 × 10
-8a, protection ratio is 99.99%.
Embodiment 5
As described in Example 1 for aluminum or aluminum alloy surface passivation without chromium-silicon system passivating solution, difference adds 0.1g (0.258mmol) zirconium iso-propoxide in preparation process (2), 0.1g (0.294mmol) tetrabutyl titanate, and regulate pH=4 with acetic acid.
Utilize the present embodiment to obtain without the method for chromium-silicon system passivating solution to aluminium surface passivation, step is with embodiment 2.
Result: the corrosion potential in 3.5wt% sodium chloride solution is-0.539V, corrosion current is 9.72 × 10
-7a, protection ratio is 99.03%.
Embodiment 6
As described in Example 1 for aluminum or aluminum alloy surface passivation without chromium-silicon system passivating solution, difference is preparation process (3) the middle reaction times is 4.5h.
Utilize the present embodiment to obtain without the method for chromium-silicon system passivating solution to aluminium surface passivation, step is with embodiment 2.
Result: the corrosion potential in 3.5wt% sodium chloride solution is-1.1v, corrosion current is 6.31 × 10
-8a, protection ratio is 99.93%.
Embodiment 7
Utilize as described in Example 2 embodiment 1 obtained without the method for chromium-silicon system passivating solution to aluminium surface passivation, unlike in step (iv) in passivating solution dipping time be 9min.
Corrosion potential in 3.5wt% sodium chloride solution is-1.18V, and corrosion current is 1.259 × 10
-7a, protection ratio is 99.87%.
Embodiment 8
Utilize as described in Example 2 embodiment 1 obtained without the method for chromium-silicon system passivating solution to aluminium surface passivation, unlike in step (iv) by the drying in 120 DEG C of baking ovens of the aluminium after dipping in passivating solution.
Corrosion potential in 3.5wt% sodium chloride solution is-1.07V, and corrosion current is 1.0 × 10
-8a, protection ratio is 99.99%.
Embodiment 9
Utilize as described in Example 2 embodiment 1 obtained without the method for chromium-silicon system passivating solution to aluminium surface passivation, unlike in step (iv) by the aluminium employing warm air drying after dipping in passivating solution.
Corrosion potential in 3.5wt% sodium chloride solution is-1.1V, and corrosion current is 6.31 × 10
-8a, protection ratio is 99.4%.
Embodiment 10
A kind of for aluminum or aluminum alloy surface passivation without chromium-silicon system passivating solution, this passivating solution take silane coupling agent as host, and TEOS is assistant agent, with the inorganic salt solution of cobalt, zirconium and titanium for hydrolytic accelerating agent, add Sodium dodecylbenzene sulfonate as organic inhibitor, reaction prepares;
Preparation process is as follows:
(1) by 7mL KH580,0.7mL TEOS, 7mL water and 0.7mL methanol mixed, stir, obtain solution A;
(2) 0.1g (0.344mmol) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 0.0148g (0.044mmol) zirconium nitrate, 0.0138g (0.057mmol) titanium sulfate and 0.012g (0.034mmol) Sodium dodecylbenzene sulfonate are joined in 2mL water, stir, obtain solution B;
(3) be added drop-wise in solution A by solution B with the speed of 0.5mL/s, stirring at normal temperature reaction 1h, obtains without chromium-silicon system passivating solution.
Embodiment 11
A kind of for aluminum or aluminum alloy surface passivation without chromium-silicon system passivating solution, this passivating solution take silane coupling agent as host, and TEOS is assistant agent, with the inorganic salt solution of cobalt, zirconium and titanium for hydrolytic accelerating agent, add Sodium dodecylbenzene sulfonate as organic inhibitor, reaction prepares;
Preparation process is as follows:
(1) 7mL KH602,7mL TEOS, 700mL water are mixed with 14mL ethanol, stir, obtain solution A;
(2) 0.1g (0.344mmol) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 0.148g (0.44mmol) zirconium nitrate, 0.138g (0.57mmol) titanium sulfate and 0.12g (0.34mmol) Sodium dodecylbenzene sulfonate are joined in 5mL water, stir, obtain solution B;
(3) be added drop-wise in solution A by solution B with the speed of 0.3mL/s, stirring at normal temperature reaction 5h, obtains without chromium-silicon system passivating solution.
Embodiment 12
Utilize embodiment 10 obtained without the method for chromium-silicon system passivating solution to aluminum alloy surface passivation, step is as follows:
I () washes
By deionized water cleaning showers used for aluminum surface 3 times, every 2min;
(ii) degreasing and alkaline etching
Aluminium alloy after washing is soaked 10min in alkaline etching dosing, carries out degreasing and alkaline etching, then use washed with de-ionized water 3 times;
Alkaline etching dosing composition is 30g sodium hydroxide, 2g sodium carbonate, 2g sodium phosphate, 2g water glass, 1g sodium laurylsulfonate and 100g deionized water;
(iii) neutralization and washing
Aluminium alloy after degreasing and alkaline etching is flooded 10min in the salpeter solution of 10wt%, then uses deionized water wash 3 times;
(iv) passivation
By the aluminium alloy dipping 5min in passivating solution after neutralization and washing process; Clean 2 times with deionized water after taking-up, then dry in 100 DEG C of baking ovens, namely complete Passivation Treatment.
Corrosion potential in 3.5wt% sodium chloride solution is-1.01V, and corrosion current is 2.9 × 10
-9a, protection ratio is 99.99%.
Embodiment 13
Utilize embodiment 11 obtained without the method for chromium-silicon system passivating solution to aluminum alloy surface passivation, step is as follows:
I () washes
By deionized water cleaning showers used for aluminum surface 3 times, every 2min;
(ii) degreasing and alkaline etching
Aluminium alloy after washing is soaked 20min in alkaline etching dosing, carries out degreasing and alkaline etching, then use washed with de-ionized water 3 times;
Alkaline etching dosing composition is 5g sodium hydroxide, 0.5g sodium carbonate, 0.1g sodium phosphate, 0.1g water glass, 0.1g sodium laurylsulfonate and 100g deionized water;
(iii) neutralization and washing
Aluminium alloy after degreasing and alkaline etching is flooded 5min in the salpeter solution of 20wt%, then uses deionized water wash 3 times;
(iv) passivation
By the aluminium alloy dipping 5min in passivating solution after neutralization and washing process; Clean 2 times with deionized water after taking-up, then dry in 120 DEG C of baking ovens, namely complete Passivation Treatment.
Corrosion potential in 3.5wt% sodium chloride solution is-0.99V, and corrosion current is 3.5 × 10
-9a, protection ratio is 99.99%.
Claims (10)
1. for aluminum or aluminum alloy surface passivation without a chromium-silicon system passivating solution, it is characterized in that, this passivating solution take silane coupling agent as host, TEOS is assistant agent, with the inorganic salt of cobalt, zirconium and/or titanium or the organic alkoxide aqueous solution for hydrolytic accelerating agent, add organic inhibitor, reaction prepares;
Described organic inhibitor is Sodium dodecylbenzene sulfonate or sodium laurylsulfonate.
2. the preparation method without chromium-silicon system passivating solution according to claim 1, step is as follows:
(1) silane coupling agent and TEOS are joined in methanol aqueous solution or aqueous ethanolic solution, stir, obtain solution A; Silane coupling agent: TEOS: water: the volume ratio of (methyl alcohol or ethanol) is 1:(0.1-1): (1-100): (0.1-2);
(2) by the inorganic salt of cobalt, zirconium and/or titanium or organic alkoxide, Sodium dodecylbenzene sulfonate or sodium laurylsulfonate are added to the water, and stir, and obtain solution B;
Cobalt: zirconium: the mol ratio of titanium is 1:(0-1): (0-1), cobalt: water: the mol ratio of (Sodium dodecylbenzene sulfonate or sodium laurylsulfonate) is 1:(100-2000): (0.05-1);
(3) solution B is added drop-wise in solution A, makes cobalt: the mol ratio of silane coupling agent is 1:(5-20), stirring at normal temperature reaction 0.5-5h, to obtain final product.
3. the preparation method without chromium-silicon system passivating solution according to claim 2, is characterized in that, the silane coupling agent described in step (1) is that one or more in KH550, KH560, KH570, KH580, KH602, KH792 are composite;
Described silane coupling agent: TEOS: water: the volume ratio of (methyl alcohol or ethanol) is 1:(0.2-0.8): (2-80): (0.2-1.5).
4. the technology of preparing without chromium-silicon system passivating solution according to claim 2, is characterized in that, the cobalt described in step (2): zirconium: the mol ratio of titanium is 1:(0.2-0.8): (0.2-0.8).
5. the technology of preparing without chromium-silicon system passivating solution according to claim 2, is characterized in that, described in step (2) the inorganic salt of cobalt, zirconium and/or titanium be the nitrate of cobalt, zirconium and/or titanium, vitriol or chlorate;
Described cobalt: water: the mol ratio of (Sodium dodecylbenzene sulfonate or sodium laurylsulfonate) is 1:(150-450): (0.2-0.8).
6. the technology of preparing without chromium-silicon system passivating solution according to claim 2, is characterized in that, the cobalt described in step (3): the mol ratio of silane coupling agent is 1:(8-18).
7. the technology of preparing without chromium-silicon system passivating solution according to claim 2, is characterized in that, the drop rate described in step (3) is 0.1-1mL/s, and the reaction times is 1-4h.
8. utilize described in claim 1 without the method for chromium-silicon system passivating solution to aluminum or aluminum alloy surface passivation, step is as follows:
I () washes
By deionized water cleaning showers 2-3 time of aluminum or aluminum alloy surface, each 2-5min; Or aluminum or aluminum alloy is soaked 5-20min in deionized water;
(ii) degreasing and alkaline etching
Aluminum or aluminum alloy after washing is soaked 1-20min in alkaline etching dosing, carries out degreasing and alkaline etching, then use washed with de-ionized water 2-3 time;
Alkaline etching dosing composition is, sodium hydroxide: sodium carbonate: sodium phosphate or tripoly phosphate sodium STPP: water glass: Sodium dodecylbenzene sulfonate or sodium laurylsulfonate: water=(5-30): (0.5-2): (0.1-2): (0.1-2): (0.1-1): 100, mass ratio.
(iii) neutralization and washing
Aluminum or aluminum alloy after degreasing and alkaline etching is directly used deionized water wash 2-3 time; Or be immersed in neutralizer and flood 1-10min, neutralizer consists of nitric acid or the aqueous sulfuric acid of 10-40wt%, then uses deionized water wash 2-3 time;
(iv) passivation
Aluminum or aluminum alloy after neutralization and washing process be impregnated in 0.5-10min in passivating solution; Clean with deionized water, then dry in 25-150 DEG C of baking oven or warm air drying, namely completes Passivation Treatment.
9. the method to aluminum or aluminum alloy surface passivation according to claim 8, it is characterized in that, in step (ii), alkaline etching dosing composition is, sodium hydroxide: sodium carbonate: sodium phosphate or tripoly phosphate sodium STPP: water glass: Sodium dodecylbenzene sulfonate or sodium laurylsulfonate: water=(10-25): (0.6-1.5): (0.2-1.5): (0.1-0.8): (0.1-0.8): 100, mass ratio;
In alkaline etching dosing, soak time is 2-18min.
10. the method to aluminum or aluminum alloy surface passivation according to claim 8, is characterized in that, in step (iv), aluminum or aluminum alloy impregnated in 1-9min in passivating solution, and drying temperature is 35-120 DEG C.
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| CN109312468A (en) * | 2016-05-30 | 2019-02-05 | 赛峰直升机发动机公司 | Chromating method and the component obtained by this method |
| CN109487259A (en) * | 2018-12-28 | 2019-03-19 | 浙江五源科技股份有限公司 | The preparation method of Chrome-free silane film before a kind of aluminium coil painting |
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| CN115613022A (en) * | 2022-09-28 | 2023-01-17 | 湖南金裕环保科技有限公司 | Chromium-free natural color passivating agent for aluminum and aluminum alloy and preparation method thereof |
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| CN105177561A (en) * | 2015-08-21 | 2015-12-23 | 山东大学 | Aluminum or aluminum alloy protection chromium-free passivation solution, preparation method and aluminum or aluminum alloy surface protection method thereof |
| CN105483718A (en) * | 2016-01-19 | 2016-04-13 | 博罗县东明化工有限公司 | Wash-whitening and descaling liquid and die-casting aluminum alloy pretreatment method |
| CN109312468A (en) * | 2016-05-30 | 2019-02-05 | 赛峰直升机发动机公司 | Chromating method and the component obtained by this method |
| CN106480443A (en) * | 2016-12-02 | 2017-03-08 | 兰州理工大学 | A kind of processing method enabling aluminum alloy to the golden yellow passivating film of surface acquisition |
| CN106480443B (en) * | 2016-12-02 | 2018-10-12 | 兰州理工大学 | A kind of processing method for enabling aluminum alloy to surface and obtaining golden yellow passivating film |
| CN106756968A (en) * | 2016-12-22 | 2017-05-31 | 山东宝龙达新材料有限公司 | Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film |
| US10947635B2 (en) * | 2018-12-10 | 2021-03-16 | Hyundai Motor Company | Surface treatment method for aluminum exterior part of vehicle |
| CN109487259A (en) * | 2018-12-28 | 2019-03-19 | 浙江五源科技股份有限公司 | The preparation method of Chrome-free silane film before a kind of aluminium coil painting |
| CN110560344A (en) * | 2019-07-25 | 2019-12-13 | 广东省建筑科学研究院集团股份有限公司 | aluminum alloy surface ATS composite membrane compatible with FEVE fluorocarbon powder coating and preparation method thereof |
| CN110560344B (en) * | 2019-07-25 | 2022-02-22 | 广东省建筑科学研究院集团股份有限公司 | Aluminum alloy surface ATS composite membrane compatible with FEVE fluorocarbon powder coating and preparation method thereof |
| CN110923685A (en) * | 2019-12-10 | 2020-03-27 | 湖州织里宝丰铝业有限公司 | Surface passivation treatment process for aluminum alloy profile |
| CN113621956A (en) * | 2021-07-15 | 2021-11-09 | 深圳市豪龙新材料技术有限公司 | Chromium-free die-casting aluminum sealant, preparation method and application thereof |
| CN115613022A (en) * | 2022-09-28 | 2023-01-17 | 湖南金裕环保科技有限公司 | Chromium-free natural color passivating agent for aluminum and aluminum alloy and preparation method thereof |
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