CN113122832A - Chromium-free passivator and preparation method thereof - Google Patents
Chromium-free passivator and preparation method thereof Download PDFInfo
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- CN113122832A CN113122832A CN201911393005.4A CN201911393005A CN113122832A CN 113122832 A CN113122832 A CN 113122832A CN 201911393005 A CN201911393005 A CN 201911393005A CN 113122832 A CN113122832 A CN 113122832A
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- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 37
- 238000002161 passivation Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 49
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 36
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 16
- 239000001509 sodium citrate Substances 0.000 claims description 15
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 15
- 235000010344 sodium nitrate Nutrition 0.000 claims description 15
- 239000004317 sodium nitrate Substances 0.000 claims description 15
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 15
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical group F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 claims description 12
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 claims description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 125000005375 organosiloxane group Chemical group 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052804 chromium Inorganic materials 0.000 abstract description 9
- 239000011651 chromium Substances 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 230000006378 damage Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 238000004512 die casting Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical class [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides a chromium-free passivator for aluminum alloy passivation, which comprises the following raw materials in parts by weight: 6.3-10.5 parts of film-forming agent, 3-5 parts of complexing agent, 1-3 parts of initiator, 1-2 parts of film-forming promoter, 1-2 parts of oxidant, 0.5-2 parts of organic film-forming agent, 1-1.5 parts of organic film-forming assistant, 0.5-1 part of neutralizer, 3-4.5 parts of organic acid and 70-80 parts of water. The chromium-free passivator has corrosion resistance close to that of a trivalent chromium passivator, has stronger adhesive force to the surface of die-cast aluminum alloy and a coating than the trivalent chromium passivator, is used at low concentration, greatly reduces pollution to the environment, and avoids the harm of volatile acid to workers.
Description
Technical Field
The invention relates to a chromium-free passivator, in particular to a chromium-free passivator for aluminum alloy.
Background
In the middle and late stages of the last century, hexavalent chromate is used for passivation of the surface of aluminum alloy in the aluminum alloy industry of China, although the corrosion resistance of the aluminum alloy is obviously improved by the hexavalent chromate passivation, the generated passivation film has a self-repairing effect and is low in price and very wide in use at that time, but the chromate passivation solution contains hexavalent chromium which is a highly toxic carcinogen, and the human health and the environment are seriously influenced. Currently, various countries around the world are beginning to restrict or prohibit the use of chromate treatment processes. In this century, the trivalent chromate passivation technology with much lower carcinogenic toxicity than the hexavalent chromate passivation technology is developed in the aluminum alloy industry of China, and the hexavalent chromate passivation technology is gradually replaced. Although the trivalent chromate passivating agent has a good treatment effect, trivalent chromium still has certain toxicity, and meanwhile, the wastewater treatment of trivalent chromium ions is difficult and the cost is high.
Therefore, the development of chromium-free passivators in the aluminum alloy surface treatment industry has been receiving more and more attention in the last decade. Currently, aluminum alloy chromium-free passivators are mainly used for passivation treatment of aluminum profiles and high-purity aluminum workpiece in the industry, but when the aluminum alloy chromium-free passivators are used for surface passivation treatment of die-cast aluminum alloy, the residual parting medium on the surface of the die-cast aluminum alloy mostly contains organic silicon which permeates into micropores among crystal grains of the die-cast aluminum alloy and is difficult to remove, so that the spray adhesion of the passivated surface can not meet the relevant requirements, and the corrosion resistance of the passivated film layer is also reduced.
Therefore, the environment-friendly passivator which can be simultaneously suitable for aluminum profiles, high-purity aluminum and die-casting aluminum alloys is developed, and is more favorable for widely replacing hexavalent chromate and trivalent chromate for passivation. The method is also an especially urgent requirement of the development of the current fine chemical industry towards green and environment-friendly products.
Disclosure of Invention
The invention aims to provide a passivator which is suitable for passivating the surfaces of aluminum alloy sections, high-purity aluminum and die-casting aluminum alloys and has no pollution to the environment.
The invention provides a chromium-free passivator for aluminum alloy, which comprises the following raw materials in parts by weight: 6.3-10.5 parts of film-forming agent, 3-5 parts of complexing agent, 1-3 parts of initiator, 1-2 parts of film-forming promoter, 1-2 parts of oxidant, 0.5-2 parts of organic film-forming agent, 1-1.5 parts of organic film-forming assistant, 0.5-1 part of neutralizer, 3-4.5 parts of organic acid and 70-80 parts of water.
Preferably, the film forming agent comprises a main film forming agent and a complex film forming agent, wherein the weight part of the main film forming agent is 6-10 parts, and the weight part of the complex film forming agent is 0.3-0.5 part.
Preferably, the main film forming agent is potassium fluozirconate, and the complexing film forming agent is titanyl sulfate.
Preferably, the complexing agent is sodium citrate, the initiator is sodium persulfate, the film forming promoter is sodium hydrogen fluoride, and the oxidizer is sodium nitrate.
Preferably, the organic film former is an organosiloxane.
Preferably, the organic coalescent is ethanol.
Preferably, the neutralizing agent is ethylenediamine.
Preferably, the organic acid is malonic acid and dodecanedicarboxylic acid, the weight part of the malonic acid is 2-3 parts, and the weight part of the dodecanedicarboxylic acid is 1-1.5 parts.
The invention also provides a preparation method of the chromium-free passivator, which comprises the following steps:
s1: pouring potassium fluorozirconate, sodium citrate, sodium persulfate, sodium hydrogen fluoride, sodium nitrate, malonic acid, titanyl sulfate, ethylenediamine, dodecacarboxylic acid and water into a reaction kettle according to a first preset weight part, stirring for 15-25 minutes under the conditions that the temperature is 10-25 ℃ and the pressure is 0.05-0.1Mpa, the rotating speed of a stirrer is 25-50 revolutions per minute, then stirring for 35-50 minutes under the conditions that the rotating speed of the stirrer is 400-550 revolutions per minute, and adjusting the pH value to be 3-3.5 after the stirring is finished;
s2: stirring and uniformly mixing the organic siloxane and the ethanol according to a second preset weight part by using a container;
s3: adding the solution obtained in the step S2 into the solution obtained in the step S1, wherein the flow rate is 0.08-0.28m/S, the temperature in the reaction kettle is 15-25 ℃, the pressure is 0.07-0.1MPa, stirring is carried out while adding, and the rotating speed of a stirrer is 400-; after the solution obtained in step S2 is completely added to the solution obtained in step S1, the stirrer continues to stir for 15-25 minutes, and the pH is adjusted to 3-3.5 after the stirring is completed.
Preferably, the first predetermined parts by weight include: 6-10 parts of potassium fluorozirconate, 3-5 parts of sodium citrate, 1-3 parts of sodium persulfate, 1-2 parts of sodium hydrogen fluoride, 1-2 parts of sodium nitrate, 2-3 parts of malonic acid, 0.3-0.5 part of titanyl sulfate, 0.5-1 part of ethylenediamine, 1-1.5 parts of dodecanedicarboxylic acid and 70-80 parts of water; the second preset weight part comprises: 0.5-2 parts of organic siloxane and 1-1.5 parts of ethanol.
The aluminum alloy chromium-free passivator and the preparation method thereof have the following technical effects:
firstly, the corrosion resistance of the aluminum alloy chromium-free passivator prepared by the invention is close to that of a trivalent chromium passivator;
secondly, the adhesive force of the aluminum alloy chromium-free passivator prepared by the invention to the surface and the coating of the die-casting aluminum alloy is stronger than that of a trivalent chromium passivator:
thirdly, the passivator obtained by the invention is used in low concentration, thus greatly reducing the pollution to the environment;
fourthly, the preparation method of the aluminum alloy chromium-free passivator avoids the harm of volatile acid to workers.
Detailed Description
In order to solve the technical problem, the invention provides a chromium-free passivator for aluminum alloy, which comprises the following raw materials in parts by weight: 6.3-10.5 parts of film-forming agent, 3-5 parts of complexing agent, 1-3 parts of initiator, 1-2 parts of film-forming promoter, 1-2 parts of oxidant, 0.5-2 parts of organic film-forming agent, 1-1.5 parts of organic film-forming assistant, 0.5-1 part of neutralizer, 3-4.5 parts of organic acid and 70-80 parts of water.
In the prior art, the chromium-free passivator mainly uses fluorozirconate as a film forming agent, but the film forming material of the passivator is single and has limited effect. As both titanium and zirconium are transition metals, the inventor finds that the passivator with better film forming effect can be obtained by adopting the composite film forming agent of the two elements through experimental research. In order to obtain a passivation system with performance close to that of a trivalent chromium passivator, the invention verifies for many times that when 6-10 parts by weight of potassium fluozirconate is used as a main film forming agent and 0.3-0.5 part by weight of titanyl sulfate is used as a complexing film forming agent, the corrosion resistance of a passivation film layer is close to that of the trivalent chromium passivator. Furthermore, in order to ensure that the passivation film layer on the surface of the aluminum alloy, especially the die-casting aluminum alloy has stable corrosion resistance and the adhesion force with the coating is stronger than that of the trivalent chromium passivation agent, the inventor tries to combine inorganic passivation reaction and organic passivation reaction to improve the performance of the passivation agent, experiments prove that the inventor introduces organic siloxane into the passivation agent system, and finds that the organic siloxane with 0.5-2 parts by weight is used as an organic film forming agent and can be used at low concentration, and the adhesion force of the obtained oxide film on the surface of the die-casting aluminum alloy and the coating is stronger than that of the trivalent chromium passivation agent.
Through selection and combination tests of other components, when the complexing agent is sodium citrate, the initiator is sodium persulfate, the film forming promoter is sodium hydrogen fluoride, the oxidant is sodium nitrate, the organic film forming assistant is ethanol, the neutralizer is ethylenediamine, and the organic acid is malonic acid and dodecanedicarboxylic acid, the passivating agent effect is obvious. The inventor finds that the reason is that the dodecacarboxylic acid can fill intercrystalline pores among the passivation films in time when the passivation film layer is formed on the surfaces of zirconium, titanium ion salts and aluminum alloys, particularly die-casting aluminum alloys, so as to enhance the compactness of the films. Furthermore, experiments prove that the compactness of the oxide film is higher when the weight parts of the malonic acid is 2-3 parts and the weight parts of the dodecanedicarboxylic acid is 1-1.5 parts.
In order to avoid the injury of volatile acid to workers, the passivator is prepared by the following steps:
s1: pouring 6-10 parts by weight of potassium fluorozirconate, 3-5 parts by weight of sodium citrate, 1-3 parts by weight of sodium persulfate, 1-2 parts by weight of sodium fluoride, 1-2 parts by weight of sodium nitrate, 2-3 parts by weight of malonic acid, 0.3-0.5 part by weight of titanyl sulfate, 0.5-1 part by weight of ethylenediamine, 1-1.5 parts by weight of dodecane polycarboxylic acid and 70-80 parts by weight of water into a reaction kettle, stirring for 15-25 minutes under the conditions that the temperature is 10-25 ℃ and the pressure is 0.05-0.1Mpa, the rotating speed of a stirrer is 25-50 revolutions per minute, then stirring for 35-50 minutes under the conditions that the rotating speed of the stirrer is 400-550 revolutions per minute, and adjusting the pH to be 3-3.5 after the stirring is finished;
s2: 0.5-2 parts by weight of organic siloxane and 1-1.5 parts by weight of ethanol are stirred and mixed uniformly by using a container.
S3: adding the solution obtained in the step S2 into the solution obtained in the step S1, wherein the flow rate is 0.08-0.28m/S, the temperature in the reaction kettle is 15-25 ℃, the pressure is 0.07-0.1MPa, stirring is carried out while adding, and the rotating speed of a stirrer is 400-; after the solution obtained in step S2 was completely added to the solution obtained in step S1, the stirrer continued stirring for 15 to 25 minutes. After stirring, the pH value is adjusted to 3-3.5, and the chromium-free passivator is obtained.
In the step S1, after water, potassium fluorozirconate, sodium citrate, sodium persulfate, sodium hydrogen fluoride, sodium nitrate, malonic acid, titanyl sulfate, ethylenediamine, dodecane polycarboxylic acid, and water are poured into a reaction kettle, the mixture is stirred for 15 to 25 minutes at a temperature of 10 to 25 ℃ and a pressure of 0.05 to 0.1MPa with a stirrer rotating speed of 25 to 50 revolutions per minute, which is a slow stirring process, in order to uniformly mix and preliminarily dissolve the added materials. Then stirring for 35-50 minutes under the conditions that the temperature is 10-25 ℃, the pressure is 0.05-0.1MPa and the rotating speed of a stirrer is 400-550 revolutions per minute, which is the process of completely dissolving the added materials. After stirring, the pH value is adjusted to 3-3.5, which is a suitable pH value range of the aluminum alloy chromium-free passivator, and is beneficial to adding the mixed solution obtained in the step S2 into the step S1, wherein the operation flow rate is 0.08-0.28m/S, the temperature in the reaction kettle is 15-25 ℃, the pressure is 0.07-0.1MPa, stirring is carried out while adding, and the rotating speed of a stirrer is 400-550 revolutions per minute; after the solution obtained in step S2 was completely added to the solution obtained in step S1, the stirrer continued stirring for 15 to 25 minutes. After the stirring is completed, the pH is adjusted to between 3 and 3.5.
After the stirring is completed, the pH is adjusted to 3 to 3.5 by using 30 mass percent of potassium hydroxide or 15 mass percent of sulfuric acid. If the pH is greater than 3.5, the chromium-free passivator is susceptible to precipitation of a hydrolyzable zirconium salt and precipitation of a hydrolyzable titanium salt during storage. If the pH value is less than 3 after the stirring is finished, the film forming accelerant sodium persulfate in the chromium-free passivator is easy to decompose and gradually reduces the effect in the storage process.
The performance comparison test of the coating matching of the chromium-free passivation film of the aluminum alloy of the invention and the conventional chromate passivation film is carried out according to the national standard, and the results are as follows:
the invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
Example one
The aluminum alloy chromium-free passivator is prepared from the following raw materials in parts by weight:
8 parts of potassium fluorozirconate, 3.5 parts of sodium citrate, 2.5 parts of sodium persulfate, 1 part of sodium hydrogen fluoride, 1 part of sodium nitrate, 2 parts of malonic acid, 0.5 part of titanyl sulfate, 0.6 part of ethylenediamine, 1 part of organosiloxane, 1.5 parts of ethanol, 1.5 parts of dodecanedioic acid and 76.9 parts of water.
The preparation method of the chromium-free passivator for the aluminum alloy comprises the following steps:
(1) pouring water, potassium fluorozirconate, sodium citrate, sodium persulfate, sodium hydrogen fluoride, sodium nitrate, malonic acid, titanyl sulfate, ethylenediamine, dodecacarboxylic acid and water into a reaction kettle, stirring for 15-25 minutes under the conditions that the temperature is 10-25 ℃ and the pressure is 0.05-0.1MPa, the rotating speed of a stirrer is 25-50 revolutions per minute, then stirring for 35-50 minutes under the conditions that the rotating speed of the stirrer is 400-550 revolutions per minute, and adjusting the pH value to be 3-3.5 after the stirring is finished;
(2) the organic siloxane and the ethanol are mixed evenly by a container under the condition of stirring.
(3) Adding the solution obtained in the step (2) into the solution obtained in the step (1), wherein the flow rate is 0.08-0.28m/s, the temperature in the reaction kettle is 15-25 ℃, the pressure is 0.07-0.1MPa, stirring is carried out while adding, and the rotating speed of a stirrer is 400-; and (3) after the solution obtained in the step (2) is completely added into the solution obtained in the step (1), continuing stirring by the stirrer for 15-25 minutes. After stirring, adjusting the pH value to 3-3.5;
example two
The aluminum alloy chromium-free passivator is prepared from the following raw materials in parts by weight:
10 parts of potassium fluorozirconate, 2.5 parts of sodium citrate, 2.5 parts of sodium persulfate, 1 part of sodium hydrogen fluoride, 1 part of sodium nitrate, 2 parts of malonic acid, 0.5 part of titanyl sulfate, 0.6 part of ethylenediamine, 0.5 part of organosiloxane, 1.5 parts of ethanol, 2.0 parts of dodecanedioic acid and 73.4 parts of water.
The preparation method of the chromium-free passivator for the aluminum alloy comprises the following steps:
(1) pouring water, potassium fluorozirconate, sodium citrate, sodium persulfate, sodium hydrogen fluoride, sodium nitrate, malonic acid, titanyl sulfate, ethylenediamine, dodecacarboxylic acid and water into a reaction kettle, stirring for 15-25 minutes under the conditions that the temperature is 10-25 ℃ and the pressure is 0.05-0.1MPa, the rotating speed of a stirrer is 25-50 revolutions per minute, then stirring for 35-50 minutes under the conditions that the rotating speed of the stirrer is 400-550 revolutions per minute, and adjusting the pH value to be 3-3.5 after the stirring is finished;
(2) the organic siloxane and the ethanol are mixed evenly by a container under the condition of stirring.
(3) Adding the solution obtained in the step (2) into the solution obtained in the step (1), wherein the flow rate is 0.08-0.28m/s, the temperature in the reaction kettle is 15-25 ℃, the pressure is 0.07-0.1MPa, stirring is carried out while adding, and the rotating speed of a stirrer is 400-; and (3) after the solution obtained in the step (2) is completely added into the solution obtained in the step (1), continuing stirring by the stirrer for 15-25 minutes. After stirring, adjusting the pH value to 3-3.5;
EXAMPLE III
The aluminum alloy chromium-free passivator is prepared from the following raw materials in parts by weight:
6 parts of potassium fluorozirconate, 3.5 parts of sodium citrate, 2.5 parts of sodium persulfate, 1 part of sodium hydrogen fluoride, 1 part of sodium nitrate, 2 parts of malonic acid, 0.5 part of titanyl sulfate, 0.6 part of ethylenediamine, 1.5 parts of organosiloxane, 1.5 parts of ethanol, 1.5 parts of dodecanedicarboxylic acid and 78.4 parts of water.
The preparation method of the chromium-free passivator for the aluminum alloy comprises the following steps:
(1) pouring water, potassium fluorozirconate, sodium citrate, sodium persulfate, sodium hydrogen fluoride, sodium nitrate, malonic acid, titanyl sulfate, ethylenediamine, dodecanedicarboxylic acid and water into a reaction kettle, stirring for 15-25 minutes under the conditions that the temperature is 10-25 ℃ and the pressure is 0.05-0.1MPa, the rotating speed of a stirrer is 25-50 revolutions per minute, then stirring for 35-50 minutes under the conditions that the rotating speed of the stirrer is 400-550 revolutions per minute, and adjusting the pH value to be 3-3.5 after the stirring is finished;
(2) the organic siloxane and the ethanol are mixed evenly by a container under the condition of stirring.
(3) Adding the solution obtained in the step (2) into the solution obtained in the step (1), wherein the flow rate is 0.08-0.28m/s, the temperature in the reaction kettle is 15-25 ℃, the pressure is 0.07-0.1MPa, stirring is carried out while adding, and the rotating speed of a stirrer is 400-; and (3) after the solution obtained in the step (2) is completely added into the solution obtained in the step (1), continuing stirring by the stirrer for 15-25 minutes. After stirring was complete the pH was adjusted to between 3 and 3.5.
Claims (10)
1. A chromium-free passivator for aluminum alloy passivation is characterized by comprising the following raw materials in parts by weight: 6.3-10.5 parts of film-forming agent, 3-5 parts of complexing agent, 1-3 parts of initiator, 1-2 parts of film-forming promoter, 1-2 parts of oxidant, 0.5-2 parts of organic film-forming agent, 1-1.5 parts of organic film-forming assistant, 0.5-1 part of neutralizer, 3-4.5 parts of organic acid and 70-80 parts of water.
2. The chromium-free passivator according to claim 1, wherein the film forming agent comprises a main film forming agent and a complex film forming agent, the weight portion of the main film forming agent is 6-10, and the weight portion of the complex film forming agent is 0.3-0.5.
3. The chromium-free passivator according to claim 2, wherein the main film former is potassium fluozirconate and the complexing film former is titanyl sulfate.
4. The chromium-free passivating agent according to claim 1, wherein the complexing agent is sodium citrate, the initiator is sodium persulfate, the film forming promoter is sodium hydrogen fluoride, and the oxidizer is sodium nitrate.
5. The chromium-free passivating agent according to claim 1, wherein the organic film-forming agent is an organosiloxane.
6. The chromium-free passivating agent according to claim 1, wherein the organic film forming aid is ethanol.
7. The chromium-free passivating agent according to claim 1, wherein the neutralizing agent is ethylenediamine.
8. The chromium-free passivator according to claim 1, wherein the organic acid is malonic acid and dodecanedicarboxylic acid, the weight part of the malonic acid is 2-3 parts, and the weight part of the dodecanedicarboxylic acid is 1-1.5 parts.
9. The preparation method of the chromium-free passivator is characterized by comprising the following steps:
s1: pouring potassium fluorozirconate, sodium citrate, sodium persulfate, sodium hydrogen fluoride, sodium nitrate, malonic acid, titanyl sulfate, ethylenediamine, dodecacarboxylic acid and water into a reaction kettle according to a first preset weight part, stirring for 15-25 minutes under the conditions that the temperature is 10-25 ℃ and the pressure is 0.05-0.1Mpa, the rotating speed of a stirrer is 25-50 revolutions per minute, then stirring for 35-50 minutes under the conditions that the rotating speed of the stirrer is 400-550 revolutions per minute, and adjusting the pH value to be 3-3.5 after the stirring is finished;
s2: stirring and uniformly mixing the organic siloxane and the ethanol according to a second preset weight part by using a container;
s3: adding the solution obtained in the step S2 into the solution obtained in the step S1, wherein the flow rate is 0.08-0.28m/S, the temperature in the reaction kettle is 15-25 ℃, the pressure is 0.07-0.1MPa, stirring is carried out while adding, and the rotating speed of a stirrer is 400-; after the solution obtained in step S2 is completely added to the solution obtained in step S1, the stirrer continues to stir for 15-25 minutes, and the pH is adjusted to 3-3.5 after the stirring is completed.
10. The method for preparing a chromium-free passivator according to claim 9, characterized in that: the first preset weight part comprises: 6-10 parts of potassium fluorozirconate, 3-5 parts of sodium citrate, 1-3 parts of sodium persulfate, 1-2 parts of sodium hydrogen fluoride, 1-2 parts of sodium nitrate, 2-3 parts of malonic acid, 0.3-0.5 part of titanyl sulfate, 0.5-1 part of ethylenediamine, 1-1.5 parts of dodecanedicarboxylic acid and 70-80 parts of water; the second preset weight part comprises: 0.5-2 parts of organic siloxane and 1-1.5 parts of ethanol.
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