CN100552086C - Normal temperature fast filming fluid for aluminium alloy surface and using method thereof - Google Patents
Normal temperature fast filming fluid for aluminium alloy surface and using method thereof Download PDFInfo
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- CN100552086C CN100552086C CNB2007100175063A CN200710017506A CN100552086C CN 100552086 C CN100552086 C CN 100552086C CN B2007100175063 A CNB2007100175063 A CN B2007100175063A CN 200710017506 A CN200710017506 A CN 200710017506A CN 100552086 C CN100552086 C CN 100552086C
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
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Abstract
The invention discloses a kind of normal temperature fast filming fluid for aluminium alloy surface and using method thereof, contain in the prescription of described film forming liquid: the pH value of silicate, titanium salt, superoxide, fluorochemical, metal trivalent salt, solution is 1～9, and the temperature of solution is 1～40 ℃ scope.The present invention in use, temperature is controlled at 1～40 ℃, pH is 2～8, with duration of contact of aluminium alloy be 1～10 minute.Because of the present invention does not contain six chromium valency and potassium ferricyanates, so not only the pollution of environment is alleviated greatly; The present invention is because the adding of metal trivalent salt, easy precipitation character under their normal temperature conditions makes it be easy to become the crystal seed that needed heterogeneous nucleation takes place in follow-up conversion film precipitin reaction in aluminum alloy surface, thereby quicken the formation speed of conversion film, save the industrial production time and the energy, reduce production costs, satisfy the requirement of industrial large-scale continuous production.The present invention is solution-stabilized, be easy to film forming, and formed conversion film is corrosion-resistant and bond properties is superior.
Description
Technical field
The present invention relates to the method that aluminum alloy surface is handled, be a kind of not chromyl metallic surface chemical conversion solution of under normal temperature condition, giving the superior corrosion-resistant and bond properties of aluminum alloy surface fast specifically, and use this chemical conversion solution to handle the method for aluminum alloy surface.
Background technology
It is a kind of traditional complete processing that the metallic surface chromic salt is learned chemical conversion (passivation), a nearly century is widely used in functional coating and decorative coating field with the anticorrosion and bond properties of its brilliance, as space flight and aviation, electronics, automobile, pharmacy, printing, machinery, chemical industry, food-processing and other production.
In the past, the surface treatment method of aluminium and alloy thereof was to handle with chromate conversion liquid.The chemical conversion processing of the aluminium that uses and the chromic compound of alloy thereof has many, as A Luodingfa by the invention of american chemical pigment company, adopt the formed conversion film of chromate treating, has superior solidity to corrosion, but in this conversion fluid, contain deleterious potassium ferricyanate, the hexavalent chromium polluted environment of hypertoxic carcinogens, it is produced the environmental requirement height, and wastewater treatment is numerous and diverse, expensive.In addition, owing to contain sexavalent chrome in the protective membrane that forms, so consider from production environment, angle safe in utilization, countries in the world are all in cancellation chromate treating technology.In addition, resource and environment, the especially consumer's goods to the use problem of non-sustainable resource, have been subjected to the generally attention of countries in the world to the influence of environment and people.European Union's in February, 2003 promulgation that the world today is of greatest concern, RoHS (the The Restriction of the Use of CertainHazardous Substances in Electrical and Electric Equipment) instruction of " the using some objectionable impurities " of implementing on July 1st, 2006 about restriction in electronic and electrical equipment, stipulate to rise on July 1st, 2006, the new electric equipment products that enters European Union market should not contain six kinds of objectionable impuritiess such as comprising sexavalent chrome, and its purpose is to improve recovery and the recirculation rate of scrapping electric equipment products, reduce the secondary pollution that the electric equipment products waste material causes water source and soil, ensure the Sustainable development of society.Some states of the AAA and the U.S. are also being discussed and banning use of the sexavalent chrome conversion film on trolley parts, and are expected to the formal legislation in 2007.Cancel metallic surface chromic salt chemistry conversion processing, develop the important task that its substitute technology has become the countries in the world industry member.
At present, in order to cancel the hexavalent chromium chemistry conversion treatment process, people have proposed the chemical conversion processing method of various non-hexavalent chromiums.As at United States Patent (USP) 6,638, in 369 " the Chrome-free conversion films " announced, use and contain sodium titanate or potassium titanate, the solution of potassium ferricyanate and fluorochemical and nitric acid, the pH of solution is 1 to 6, and temperature is 60 to 80 ℃ scope.
For United States Patent (USP) 6,638, in 369 " the Chrome-free conversion films " announced, its treatment solution has not chromyl advantage, and has added fluorochemical with existing sexavalent chrome conversion process same range as amount at treatment solution, but because sodium titanate or the solubleness of potassium titanate in water used in this technology are extremely low, so it is low effectively to dissolve titanium ion concentration, can not guarantee the quality of film in the continuous flow procedure, can't realize industrial continuous production requirement, and contain virulent potassium ferricyanate.More, will expend a large amount of energy owing to the scope of the conversion fluid temperature of using in this technology at 60 to 80 ℃.
For aldural, owing to dissolve many metal ions in the conversion reaction process, as Cu
2+, Zn
2+Deng, the treatment solution of this patent does not contain the composition of removing these ion interference, therefore, is difficult to obtain the uniform protective membrane of color and luster for this method of this type of aluminium alloy.
Summary of the invention
The object of the present invention is to provide a kind of aluminum alloy chemically film forming liquid that does not contain sexavalent chrome and under normal temperature condition, be easy to fast filming, make its surface be easy to form to have good anticorrosion and bond properties, the uniform conversion film of color and luster.
For achieving the above object, the technical solution used in the present invention is: the prescription of described film forming liquid is to contain in every liter of solution:
Silicate: the concentration of silicate is at 0.1mg/L～2000mg/L;
Titanium salt: titanium ion concentration is at 0.1mg/L～10000mg/L;
Superoxide: the concentration of hydrogen peroxide is at 0.1mg/L～10000mg/L;
Fluorochemical: the concentration of fluorion is at 1000mg/L～4000mg/L;
Metal trivalent salt: the concentration of metal trivalent ion is at 0.1mg/L～100000mg/L;
The pH value of solution: the pH of solution is in 1～9 scope;
The temperature of solution: the temperature of solution is 1～40 ℃ scope.
The prescription of described film forming liquid be preferred version in every liter of solution for containing:
Silicate: the concentration of silicate is at 0.1mg/L～500mg/L;
Titanium salt: titanium ion concentration is at 0.5mg/L～5000mg/L;
Superoxide: the concentration of hydrogen peroxide is at 0.1mg/L～5000mg/L;
Fluorochemical: fluorinion concentration is at 1500mg/L～3000mg/L;
Metal trivalent salt: the concentration of metal trivalent ion is at 0.5mg/L～50000mg/L;
The pH value of solution: the pH of solution is in 2～8 scope;
The temperature of solution: the temperature of solution is 5～30 ℃ scope.
Described silicate adopts at least a in silicic acid, water glass, the potassium silicate.
Described titanium salt adopts at least a in titanium chloride, titanium sulfate, titanyl sulfate, titanyl nitrate, sodium titanate, potassium titanate, the titanium dioxide.
Described superoxide adopts at least a in sodium peroxide, Potassium peroxide, the hydrogen peroxide.
Described fluorochemical adopts at least a in Neutral ammonium fluoride, ammonium acid fluoride, Sodium Fluoride, Potassium monofluoride, the sodium hydrogen fluoride.
At least a in the trivalent aluminium that described metal trivalent salt adopts, ferric iron, trivalent cerium, the chromic salt.
Described hydrogen ion comes from least a in hydrochloric acid, phosphoric acid, sulfuric acid or the nitric acid.
Another object of the present invention is to provide a kind of using method of normal temperature fast filming fluid for aluminium alloy surface, and its step is as follows:
(1), earlier the aluminum alloy surface grease is removed;
(2), again with aluminum alloy surface alkali cleaning, deoxidation activation;
(3), use normal temperature fast filming fluid for aluminium alloy surface, carry out conversion processing, this molten night, temperature was controlled at 1～40 ℃ in use, pH is 2～8, with duration of contact of aluminium alloy be 1～10 minute;
(4), again after the aluminium alloy water being cleaned, seasoning gets final product.
Described step (2) comprised for two steps:
(1), alkali cleaning, adopt 1～10% sodium hydroxide solution, after handling 1～5 minute under 30～60 ℃ of temperature by rinsed with deionized water;
(2), deoxidation activation, adopt 1～10% nitric acid at room temperature to handle after 1～10 minute by rinsed with deionized water.
The invention has the beneficial effects as follows:
Conversion fluid of the present invention does not contain hypertoxic potassium ferricyanate owing to do not contain carcinogens six chromium valencys (chromic salt), and not only the pollution to environment alleviates greatly, and cost reduces significantly.
The present invention is because the adding of metal trivalent salt, easy precipitation character under their normal temperature conditions makes it be easy to become the crystal seed that needed heterogeneous nucleation takes place in follow-up conversion film precipitin reaction in aluminum alloy surface, thereby quicken the formation speed of conversion film, save the industrial production time and the energy, reduce production costs, satisfy the requirement of industrial large-scale continuous production.
The superoxide that conversion fluid of the present invention contains can change into the titanic ion-oxygen in the solution sexivalent titanium oxide ion (Ti
2O
5 2+).This high price titanium oxide ion can be generated quaternary titanium dioxide conversion film by aluminium reducing when aluminum alloy surface generation redox reaction.
The superoxide that conversion fluid of the present invention contains can promote titanium salt, dissolving as titanium chloride, titanium sulfate, titanyl sulfate, titanyl nitrate, sodium titanate, potassium titanate, titanium dioxide etc., so the titanium ion concentration in the conversion fluid greatly increases, can satisfy the requirement that realizes industrial continuous production.
Conversion fluid of the present invention is owing to contain silicate, and in certain concentration range, silicate ion can not only be removed the interference of metal ion, and is easy to film forming.
The protective membrane that the present invention generated has been owing to utilized the advantage of silicate, titanium salt and superoxide, thereby is easy to form conversion film, and the conversion film of generation not only corrosion resisting property is superior, and because color and luster is even, combines strong adhesion with organic coating.
Embodiment
Normal temperature fast filming fluid for aluminium alloy surface of the present invention is made by containing silicate, titanium salt, superoxide, fluorochemical, metal trivalent salt and aqueous acid.
1, silicate
Adopt silicic acid or potassium silicate, concentration is at 0.1mg/L to 2000mg/L.Be preferably 0.5mg/L to 500mg/L.Silicate concentration is too high, can make the aluminum alloy surface conversion reaction be difficult to take place; And silicate concentration is too low, the silicon-dioxide (SiO that produces under reaction conditions
2) concentration is too low, it is electrical to be difficult to change aluminum alloy surface.Under reaction conditions, aluminium surface positively charged, and the electronegative property of silicon dioxide granule, because the electrostatic attraction effect, coated with silica makes the electronegative property of aluminum alloy surface in aluminum alloy surface, makes the titanium oxide ion (Ti of positively charged
2O
5 2+) easily at aluminum alloy surface generation film formation reaction.
2, titanium salt
As titanium salt, for example can enumerate titanium oxide (TiCl
4), titanium sulfate (Ti (SO
4)
2), titanyl sulfate (TiOSO
4), titanyl nitrate (TiO (NO
3)
2), sodium titanate (Na
2TiO
3), potassium titanate (K
2TiO
3), titanium dioxide (TiO
2) wait at least a.The concentration of pressing metal titanium conversion titanium ion is preferably in 0.5mg/L～5000mg/L at 0.1mg/L～10000mg/L.When the concentration of titanium salt titanium ion in treatment solution is too low, almost can not be formed with the conversion film of imitating antiseptic property.On the other hand, in treatment solution, even add titanium, effect does not increase, and therefore, calculates titanium concentration by metal titanium concentration and is advisable with interior at 10000mg/L.
3, superoxide
As superoxide, for example can enumerate at least a in sodium peroxide, Potassium peroxide, the hydrogen peroxide.Added concentration of hydrogen peroxide is at 0.1mg/L～10000mg/L in the treatment solution, preferably 0.5mg/L～5000mg/L.In the solution concentration of hydrogen peroxide can not be too low can not be too high.Too low can not guarantee certain oxidisability that solution has and make titanium with the high price--sexivalent titanium oxide ion (Ti
2O
5 2+) exist, this ionic concn is too low, is not enough to form effective protective membrane; The concentration of hydrogen peroxide is too high to be unfavorable for making film formation reaction to take place on passivation aluminum metal surface.
4, fluorochemical
As fluorochemical, for example can enumerate Neutral ammonium fluoride (NH
4F), ammonium acid fluoride (NH
4HF
2), Sodium Fluoride (NaF), Potassium monofluoride (KF), sodium hydrogen fluoride (NaHF
2) etc.In the treatment solution of this way of example, the fluorine of adding is wherein a kind of of above-mentioned fluorochemical, and the amount of adding is preferably 1500mg/L to 3000mg/L for to change 1000mg/L to 4000mg/L by fluorine.Fluorine concentration is lower than 1000mg/L or is higher than 3000mg/L, and the aluminum metal surface conversion coating all is difficult to form.
5. metal trivalent salt
As metal trivalent salt, for example can enumerate and adopt at least a in trivalent aluminium, ferric iron, trivalent cerium, the chromic salt.Added trivalent chromium concentration is at 0.1mg/L～100000mg/L in the treatment solution, preferably 0.5mg/L～50000mg/L.GOLD FROM PLATING SOLUTION belong to the concentration of trivalent salt can not be too low also should not be too high.Too lowly be not enough to help film forming; On the other hand, in treatment solution, add metal trivalent salt dissolving difficulty and help film forming effect not increase, therefore, calculate metal trivalent salt concn by the metal chromium ion concentration and be advisable with interior at 50000mg/L.
6, acid
Adopt the pH value of a kind of regulator solution in hydrochloric acid, phosphoric acid, sulfuric acid or the nitric acid, the pH that makes solution is preferably in 2～8 scope 1～9.
Below, will use the step of the process metal surfaces method of this chemical conversion solution to be listed below:
(1), earlier the aluminum alloy surface grease is removed;
(2), again with aluminum alloy surface alkali cleaning, deoxidation activation; Alkali cleaning is for adopting 1～10% sodium hydroxide solution, after handling 1～5 minute under 30～60 ℃ of temperature by rinsed with deionized water; The deoxidation activation is at room temperature handled after 1～10 minute by rinsed with deionized water for adopting 1～10% nitric acid;
(3), use Aluminum Alloy Room Temperature fast filming hexavalent chromium chemistry to transform replacement liquid, carry out conversion processing, this molten night, temperature was controlled at 1～40 ℃ in use, pH is 2～8, with duration of contact of aluminium alloy be 1～10 minute;
(4), again after Al alloy parts being washed with water, seasoning gets final product.
Specific embodiment 1: aluminium alloy 3A21 surface is cleaned with gasoline, immerse temperature then and carried out skimming treatment in 3 minutes at 30～60 ℃ 3% sodium hydroxide solution, after the washing this alloy at room temperature immersed in 5% the salpeter solution 5 minutes, and after rinsed with deionized water, immersed aluminum alloy surface normal temperature fast filming hexavalent chromium chemistry again and transform replacement liquid and handle.The chemical conversion solution composition is water glass 0.10g/L, titanyl sulfate 0.5g/L, hydrogen peroxidase 10 .5g/L, Tai-Ace S 150 1g/L, Sodium Fluoride 5g/L.It is 2-8 that sulfuric acid is regulated conversion fluid pH, and temperature is 15～20 ℃, reacts and after 10 minutes aluminium alloy is taken out the after washing drying.Formed film has passed through 336 hours neutral salt spray test (ASTM B117) test, and adopting hundred lattice cuttves to draw the lattice experiment test, to show that conversion film and colored paint or varnish combine sticking power good.
Specific embodiment 2: aluminium alloy LD2CS immerses this alloy and contains 0.05g/L water glass, the titanyl sulfate of 2g/L after the pre-treatment identical with embodiment 1, hydrogen peroxidase 10 .5g/L, Cerium II Chloride 2g/L, in the conversion fluid of Sodium Fluoride 4g/L, the pH value of sulfuric acid regulation solution.Reaction conditions is with embodiment 1.The rete that has formed one deck white through the aluminium alloy LD2CS surface of above-mentioned processing is tested still non-corrosive through 336 hours neutral salt spray (ASTM B117), and hundred lattice cuttves are drawn lattice experiment test result and shown that conversion film and colored paint, the bonding labor of varnish are solid.
Claims (10)
1, a kind of normal temperature fast filming fluid for aluminium alloy surface is characterized in that, the prescription of this film forming liquid that makes is to contain in every liter of solution:
Silicate: the concentration of silicate is at 0.1mg/L～2000mg/L;
Titanium salt: titanium ion concentration is at 0.1mg/L～10000mg/L;
Superoxide: the concentration of hydrogen peroxide is at 0.1mg/L～10000mg/L;
Fluorochemical: the concentration of fluorion is at 1000mg/L～4000mg/L;
Metal trivalent salt: the concentration of metal trivalent ion is at 0.1mg/L～100000mg/L;
The pH value of solution is 1～9, and the temperature of solution is 1 ℃～40 ℃.
2, normal temperature fast filming fluid for aluminium alloy surface as claimed in claim 1 is characterized in that, the prescription of described film forming liquid is to contain in every liter of solution:
Silicate: the concentration of silicate is at 0.1mg/L～500mg/L;
Titanium salt: titanium ion concentration is at 0.5mg/L～5000mg/L;
Superoxide: the concentration of hydrogen peroxide is at 0.1mg/L～5000mg/L;
Fluorochemical: fluorinion concentration is at 1500mg/L～3000mg/L;
Metal trivalent salt: the concentration of metal trivalent ion is at 0.5mg/L～50000mg/L;
The pH value of solution is 2～8, and the temperature of solution is 5 ℃～30 ℃.
3, normal temperature fast filming fluid for aluminium alloy surface as claimed in claim 1 or 2 is characterized in that, described silicate adopts water glass or potassium silicate.
4, normal temperature fast filming fluid for aluminium alloy surface as claimed in claim 1 or 2 is characterized in that, described titanium salt adopts at least a in titanium chloride, titanium sulfate, titanyl sulfate, the titanyl nitrate.
5, normal temperature fast filming fluid for aluminium alloy surface as claimed in claim 1 or 2 is characterized in that, described superoxide adopts sodium peroxide, Potassium peroxide, hydrogen peroxide wherein at least a.
6, normal temperature fast filming fluid for aluminium alloy surface as claimed in claim 1 or 2 is characterized in that, described fluorochemical adopts at least a in Neutral ammonium fluoride, ammonium acid fluoride, Sodium Fluoride, Potassium monofluoride, the sodium hydrogen fluoride.
7, normal temperature fast filming fluid for aluminium alloy surface as claimed in claim 1 or 2 is characterized in that, described metal trivalent salt adopts at least a in trivalent aluminium, ferric iron, trivalent cerium, the chromic salt.
8, normal temperature fast filming fluid for aluminium alloy surface as claimed in claim 1 or 2 is characterized in that, the pH value of described solution adopts at least a adjusting the in hydrochloric acid, phosphoric acid, sulfuric acid or the nitric acid.
9, the using method of normal temperature fast filming fluid for aluminium alloy surface as claimed in claim 8 is characterized in that, comprises the steps:
(1), earlier the aluminum alloy surface grease is removed;
(2), again with aluminum alloy surface alkali cleaning, deoxidation activation;
(3), use normal temperature fast filming fluid for aluminium alloy surface to carry out conversion processing, this molten night, temperature was controlled at 1～40 ℃ in use, pH is 2～8, with duration of contact of aluminium alloy be 1～10 minute;
(4), again after the aluminium alloy water being cleaned, seasoning gets final product.
10, the using method of normal temperature fast filming fluid for aluminium alloy surface as claimed in claim 9 is characterized in that, described step (2) comprised for two steps:
(1), alkali cleaning, adopt 1～10% sodium hydroxide solution, after handling 1～5 minute under 30～60 ℃ of temperature by rinsed with deionized water;
(2), deoxidation activation, adopt 1～10% nitric acid at room temperature to handle after 1～10 minute by rinsed with deionized water.
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| CNB2007100175063A CN100552086C (en) | 2007-03-15 | 2007-03-15 | Normal temperature fast filming fluid for aluminium alloy surface and using method thereof |
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| CN100552086C true CN100552086C (en) | 2009-10-21 |
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| CN101519776B (en) * | 2009-04-17 | 2011-03-30 | 昆明理工大学 | Preparation method of clean rare-earth salt passivation liquid |
| CN101525747B (en) * | 2009-04-17 | 2011-04-20 | 昆明理工大学 | Clean rare-earth salt passivation solution |
| CN102041496B (en) * | 2009-10-13 | 2015-07-01 | 北京中科三环高技术股份有限公司 | Chromium-free passivating agent for permanent magnet material and passivating method thereof |
| CN103540924A (en) * | 2012-07-15 | 2014-01-29 | 吴启龙 | Chrome-free chemical conversion liquid for magnesium alloy and use method thereof |
| CN103924229B (en) * | 2014-04-29 | 2017-05-24 | 无锡铱美特科技有限公司 | Aluminum alloy surface titanium dioxide conversion coating solution and using method thereof |
| CN106283019A (en) * | 2015-06-03 | 2017-01-04 | 天津市航宇金属加工有限公司 | A kind of alloy product surface style keeping liquid and using method thereof |
| CN104878374A (en) * | 2015-06-25 | 2015-09-02 | 潘应生 | Aluminum alloy low chromium passivation solution and preparation method of passivation solution |
| CN104878376A (en) * | 2015-06-25 | 2015-09-02 | 潘应生 | Aluminum alloy low chromium passivation solution and preparation method of passivation solution |
| CN107012458B (en) * | 2017-04-27 | 2019-06-25 | 江苏乐嘉华创建筑科技有限公司 | Aluminium alloy pretreatment liquid and its application method |
| BR112020022626A2 (en) * | 2018-05-11 | 2021-02-02 | Mineração Floresta S/A | process for the production of titanium dioxide pigment by digesting raw materials containing titanium in hydrochloric acid in the presence of a fluorine-based substance |
| US20200032411A1 (en) * | 2018-07-25 | 2020-01-30 | The Boeing Company | Compositions and Methods for Activating Titanium Substrates |
| CN110129781B (en) * | 2019-06-28 | 2020-12-15 | 东北大学秦皇岛分校 | Preparation method of aluminum alloy conversion solution and colored chemical conversion film |
| CN112899670B (en) * | 2019-11-19 | 2023-04-18 | 佛山市顺德区美的电热电器制造有限公司 | Chromium-free passivator and application thereof |
| CN112064007A (en) * | 2020-09-24 | 2020-12-11 | 嵊州市浙江工业大学创新研究院 | Passivation treatment process method of cast aluminum alloy for integrated stove gas valve |
| CN115305464B (en) * | 2022-08-23 | 2024-02-06 | 江门市安诺特炊具制造有限公司 | Surface treatment method of aluminum alloy cooker and aluminum alloy cooker |
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