CN101323965B - Middle temperature sealant and closing process for aluminum anodized film - Google Patents
Middle temperature sealant and closing process for aluminum anodized film Download PDFInfo
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- CN101323965B CN101323965B CN2008100484930A CN200810048493A CN101323965B CN 101323965 B CN101323965 B CN 101323965B CN 2008100484930 A CN2008100484930 A CN 2008100484930A CN 200810048493 A CN200810048493 A CN 200810048493A CN 101323965 B CN101323965 B CN 101323965B
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title abstract description 26
- 239000000565 sealant Substances 0.000 title description 2
- 238000007789 sealing Methods 0.000 claims abstract description 62
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 239000008139 complexing agent Chemical class 0.000 claims abstract description 12
- -1 alkaline earth metal salt Chemical class 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 239000007864 aqueous solution Chemical class 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract 2
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000006174 pH buffer Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims 1
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 23
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 9
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 150000001868 cobalt Chemical class 0.000 abstract description 4
- 150000002815 nickel Chemical class 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 239000006179 pH buffering agent Substances 0.000 abstract 2
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000008393 encapsulating agent Substances 0.000 description 24
- 239000004411 aluminium Substances 0.000 description 21
- 239000011575 calcium Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 8
- 229960004418 trolamine Drugs 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 229910000737 Duralumin Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052728 basic metal Inorganic materials 0.000 description 6
- 150000003818 basic metals Chemical class 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 6
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 5
- 229940078494 nickel acetate Drugs 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 229960004249 sodium acetate Drugs 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 4
- 239000005695 Ammonium acetate Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- 235000019257 ammonium acetate Nutrition 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YFHNDHXQDJQEEE-UHFFFAOYSA-N acetic acid;hydrazine Chemical compound NN.CC(O)=O YFHNDHXQDJQEEE-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910013594 LiOAc Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
本发明用于铝阳极氧化膜的中温封闭剂及封闭工艺，属铝及铝合金阳极氧化膜的封闭后处理技术领域，本发明封闭剂是由碱金属或碱土金属的盐类、络合剂、pH缓冲剂组成的水溶液，其中碱金属或碱土金属的盐类5-15g/L，络合剂10-20g/L，pH缓冲剂0-10g/L，余为量水，封闭剂水溶液pH值为5-6，按本封闭剂封闭处理铝氧化膜，其封闭剂水溶液温度为75-90℃，浸渍封闭时间为20-30min，本封闭剂采用资源广阔成本低廉碱金属盐或碱土金属盐取代现有技术重金属镍盐或钴盐；采用易于生物降解价格低的简单分子的有机物络合剂，取代大分子现有技术含苯环的表面活性剂，按本发明封闭处理的铝阳极氧化膜，获得了优良的抗粉霜特性，全面提高铝及铝合金阳极氧化膜的耐蚀性和抗污染性。The present invention is a medium-temperature sealing agent and sealing process for aluminum anodic oxidation film, which belongs to the technical field of sealing post-treatment of aluminum and aluminum alloy anodic oxidation film. The sealing agent of the present invention is composed of salts of alkali metals or alkaline earth metals, complexing agents, Aqueous solution composed of pH buffering agent, including 5-15g/L of alkali metal or alkaline earth metal salt, 10-20g/L of complexing agent, 0-10g/L of pH buffering agent, the rest is water, and the pH value of the sealing agent aqueous solution 5-6, the aluminum oxide film is sealed and treated according to this sealing agent. The temperature of the sealing agent aqueous solution is 75-90 ° C, and the sealing time is 20-30 minutes. This sealing agent is replaced by alkali metal salt or alkaline earth metal salt with extensive resources and low cost. Prior art heavy metal nickel salt or cobalt salt; adopt the organic compound complexing agent of the simple molecule that is easy to biodegradation price low, replace the surfactant of macromolecular prior art that contains benzene ring, the aluminum anodized film of sealing treatment according to the present invention, It has obtained excellent anti-powder and frost characteristics, and comprehensively improved the corrosion resistance and pollution resistance of aluminum and aluminum alloy anodic oxidation films.
Description
Technical field
The present invention is used for the warm encapsulant and the closing process of aluminum anodized film, belongs to the sealing post-processing technology field of aluminium and aluminium alloy anode oxide film, and is irrelevant with the sealing technique of aluminium hard anodized film or non-electrolytics conversion film.
Technical background
Aluminium and duraluminum are one of metals the most frequently used in the current industry, and aluminium and duraluminum are not only in light weight, and quality is hard, and has good ductility, electroconductibility, thermal conductivity, thermotolerance and anti-radioprotective property, is the important foundation starting material of the national economic development.
Aluminium and duraluminum are very stable in the exsiccant atmosphere, but in humid atmosphere, particularly are easy to corrosion in the air of salt concentration.Adopt anodic oxidation in the industry widely, generate layer oxide film at aluminium and articles made of aluminium alloy surface, adopting sulfuric acid or oxalic acid usually is electrolytic solution; Carry out anode electrolysis with aluminium and duraluminum as anode and handle, the formed conversion film of anodic oxidation is cellular porous structure, has high porosity and adsorptivity; This high porosity and adsorptivity both be convenient to technology dyeing; But be easy to contaminatedly, especially in corrosive atmosphere, corrosive medium gets into the rete hole easily and causes corrosion.Therefore, in the industrial production,, before dyeing or after the dyeing, generally all need the antianode oxidation film layer to carry out sealing treatment in order to improve the quality of aluminum anodized film.
The enclosure method that aluminum anodized film the most often adopts is boiling water sealing and nickel acetate closing process.And the drawback of these two kinds of closing process commonly used be sull behind sealing treatment, its surface is easy to generate disgusting white or grey meal, industry is referred to as sealing " pollen " or " sealing China ".When " pollen " was slight, available rag was wiped gently, then was difficult to wipe when serious, need move back film and handle again, caused sull to be scrapped.Research shows that the plurality of impurity ions of sealing treatment liquid can promote the generation of " pollen ", wherein Ca
2+, Mg
2+, Al
3+Isoionic existence effect is the most obvious.This shows for traditional boiling water closing process and nickel acetate closing process, alkaline earth metal ion Ca
2+, Mg
2+Be deleterious, so let alone prepare sealing treatment liquid with them.
Should carry out sealing treatment after the sull dyeing, to increase the light permanency and the solidity to corrosion of color and luster.Sealing technique the earliest is to adopt pure water to boil to boil; Its principle is that hydration reaction takes place in hot water the aluminium sesquioxide of sull surface and hole wall, generates hydrated aluminum oxide, and the volume of original sull is increased; The expansion of sull volume is significantly dwindled fenestra, thereby reaches the purpose of sealing of hole.Be difficult to control in the boiling water sealing actual production, the evaporation of sealing tank liquor is very fast, and impurity run-up in the tank liquor causes the sealing quality deterioration, needs the frequent change pure water.
Interpolation nickel acetate or Cobaltous diacetate carry out sealing of hole to sull in pure water, and hydrolysis takes place in hot water for these nickel salts or cobalt salt, in the sull hole, produces precipitation of hydroxide, plays sealing process equally.Such closing process can carry out under low slightly temperature condition, as 71-88 ℃.The tank liquor life-span is longer than the boiling water sealing; Sealing quality is better, and this closing process is still very popular in industry so far, and nickel acetate or Cobaltous diacetate closing process have an environmental issue; Just contain a large amount of heavy metal nickels and cobalt in the waste water of sealing treatment; Heavy metal ion can cause serious harm to environment, in order to protect environmental safety, needs to use complicated and expensive wastewater treatment equipment.
Basic metal and earth alkali metal extensively are present in natural soil and the seawater, and be very little to the toxicity of biology, and the processing of its trade effluent is fairly simple and cheap.Proposed not contain the composition of heavy metal nickel (Ni) and cobalt (Co) encapsulant in the U.S. Pat 5362317, used alkaline earth salt: calcium acetate (Ca (0Ac)
2), or magnesium acetate (Mg (OAc)
2), with AS: korenyl ether sulfonate, pH value are 4.5-7.5.Temperature range at 71-82 ℃ is sealed, time 15min.Sealing quality is good, the no pollen in surface.
Proposed in the U.S. Pat 5411607 with the prescription of an alkali metal salt as encapsulant: Lithium Acetate (LiOAc), every liter contains (Li
+) ion 0.5g, AS: every liter contains korenyl ether sulfonate 1g, and the pH value is 5.5-6.5, at 88 ℃ temperature range sealing, time 10min.Sealing quality is good, the no pollen in surface.
More than two patents all adopted macromole and contained the tensio-active agent of phenyl ring, this type organic cpds is slow at natural degradation speed, life-time service is accumulated in environment easily, and ecology is damaged.
Summary of the invention
The purpose of this invention is to provide a kind of warm encapsulant and closing process that is used for aluminum anodized film; Replace heavy metal nickel salt or the cobalt salt that costs an arm and a leg and environment had pollution with wide an alkali metal salt with low cost of resource or alkaline earth salt; To be easy to the organism complexing agent of the low simple molecules of biological degradation price, replace the tensio-active agent that macromole contains phenyl ring, make aluminium and the aluminium alloy anode oxide film handled through this encapsulant; Not only has good anti-pollen characteristic; Improve the solidity to corrosion and the resistance to crocking of aluminium and aluminium alloy anode oxide film comprehensively, and help reducing cost, help ecology and environment protection.
The aqueous solution that encapsulant of the present invention is made up of salt, complexing agent, the pH buffer reagent of basic metal or earth alkali metal, wherein
The salt 5-15g/L of basic metal or earth alkali metal.
Complexing agent 10-20g/L
PH buffer reagent 0-10g/L
Excess water
PH value 5-6
An alkali metal salt that the present invention adopts or alkaline earth salt are alkali metal lithium or earth alkali metal magnesium, the acetate of calcium, formate, lactic acid salt, and wherein acetate, formate best results are considered cost factor, generally use their acetate.Under the condition of the acetate that is difficult for obtaining them, also can use their oxyhydroxide or carbonate to prepare with corresponding acid-respons temporarily.Because the sealing of sulfate radical, nitrate radical, cl ions antianode sull is deleterious, do not adopt vitriol, nitrate salt, muriate so do not advocate;
The complexing agent that the present invention adopts is nitrogenous organic acid or organic bases; The organism that belongs to simple molecules; Be easy to biological degradation, can not damage, like trolamine, nitrilotriacetic acid(NTA), YD 30 ecology; Acetic acid hydrazine, sulfamate, wherein trolamine, nitrilotriacetic acid(NTA) effect are best;
PH buffer reagent of the present invention is selected sodium-acetate and ammonium acetate for use, adds the rangeability that the pH buffer reagent can reduce encapsulant pH value of solution value, keeps the stable of encapsulant solution, makes the longer service life of encapsulant solution.According to the acid-basicity of institute's obtain solution, can adopt acetic acid or ammoniacal liquor, sodium hydroxide solution, adjustment pH value is to the regulation numerical value of 5-6.
Closing process by encapsulant of the present invention is:
75-90 ℃ of aqueous sealant solution temperature
Dipping 20-30min off-period
Adopt encapsulant sealing treatment aluminium of the present invention and duraluminum through the technology of anode oxide film to be: aluminium and duraluminum through thoroughly washing, immerse immediately and carry out sealing treatment in the confining liquid of the present invention after the anodize film forming; The centre can not stop, and the encapsulant solution temperature is 75-90 ℃, and the dipping close process time depends on the thickness of sull; Encapsulant antianode sull speed in a closed circuit of the present invention is about 0.5 μ m/min, so, be the sull of 10-15 μ m for thickness; Its sealing dip treating time is 20-30min, after dip treating is accomplished, with the washing from the beginning of flowing; Through dry air, promptly obtain the sull of satisfied sealing effect again, the no pollen in surface.
The present invention realizes that successfully substituting the hole sealing agent that nickel acetate, Cobaltous diacetate be used for aluminium and aluminium alloy anode oxide film with basic metal or alkaline earth salt carries out sealing treatment, and its key is that science selects complexing agent, on the one hand this complex compound should with Li
+, Ca
2+, Mg
2+Ion has enough complexation strengths, makes free Li
+, Ca
2+, Mg
2+The ionic concn appropriateness is low, is not enough in electrolytic solution or the generation precipitation of hydroxide of anode oxide film surface, thereby avoids basic metal Li
+Ion, alkaline earth metal ion Ca
2+, Mg
2+Form the problem of " pollen " on the sull surface.This complex compound and Al on the other hand
3+The ionic complexation constant should greater than with Ca
2+, Mg
2+The ion complexation constant is reflected at sealing of hole and is able in the sull hole carry out.
It is following that capping takes place in the sull hole:
MY+Al(OH)
3＝AlY
++M
2++3OH
-
M
2++2OH
-＝M(OH)
2↓
M representation metal ion Ca in the top formula
2+, Mg
2+Ion or Li
+Ion is because free Li in the sealing treatment agent
+, Ca
2+, Mg
2+The ionic concn appropriateness is low, and its concentration is not enough in electrolytic solution or anode oxide film surface produces precipitation of hydroxide, and the Li of appropriate concentration in the sull hole only
+, Ca
2+, Mg
2+Ion is able to generate Ca, Mg or Li precipitation of hydroxide, and makes hole obtain filling, has reached the purpose of sealing.
The complexing agent that the present invention selects is nitrogenous organic acid or organic bases, is selected from trolamine, nitrilotriacetic acid(NTA), YD 30, and acetic acid hydrazine, sulfamate be as complex compound, and wherein trolamine, nitrilotriacetic acid(NTA) effect are best.Trolamine be alkalescence to its pH value be neutralized to 5-6 with acetic acid, the acetic acid hydrazine also is with in the acetic acid and hydrazine hydrate acquisition.
Metal-salt can be selected their acetate, formate, lactic acid salt for use, and wherein acetate, formate best results are considered cost factor, generally use their acetate.Because the sealing of sulfate radical, nitrate radical, cl ions antianode sull is harmful, does not recommend to use vitriol, nitrate salt, muriate.Can't directly obtain under the condition of acetate, can use their oxyhydroxide or carbonate to prepare temporarily with corresponding acid-respons.
The present invention selects for use sodium-acetate and ammonium acetate as the pH buffer reagent, can reduce the pH value rangeability of encapsulant solution, keeps the stable of encapsulant solution, prolongs the work-ing life of encapsulant solution.Under certain conditions, when after anodic oxidation, cleaning very thoroughly, also can not add buffer reagent like workpiece.
The present invention adopts CNS GB/T14952.1 evaluation sealing quality, and the anode oxide film after just will sealing is in the solution of following prescription and temperature:
CrO
3 20g/L
H
3PO
4(85％) 35mL/L
38 ℃ of temperature
Dipping 15min detects its corrosion weight loss, and is weightless less than 30mg/dm
2For the sealing qualified.
The present invention adopts an alkali metal salt or alkaline earth salt to replace heavy metal nickel salt or the cobalt salt that prior art is used; Sealing treatment aluminium and aluminium alloy anode oxide film have obtained the anode oxide film of anti-pollen characteristic, improve the solidity to corrosion and the resistance to crocking of aluminium and aluminium alloy anode oxide film comprehensively; Not only basic metal or earth alkali metal resource are wide with low cost; And avoided to handling the expensive treatment device that the contaminated wastewater institute that contains heavy metal nickel and cobalt must employing, in addition, the complexing agent of the present invention's employing is the organism of simple molecules; Be easy to biological degradation, ecotope is had no adverse effects.These complexing agents all are industrial chemicals commonly used, are widely used in clean-out system industry like trolamine, and material obtains easily, and cost is low.
Embodiment
Combine specific examples explanation the present invention how to implement at present:
One, aluminium and aluminium alloy anode oxide film forming are handled
Sample adopts 6063 duraluminums, and technical process is following:
1. acid degreasing: AC-98 acid degreasing agent 15g/L, sulfuric acid 150g/L, room temperature dipping 5min.
2. secondary flow is washed from the beginning.
3. caustic corrosion: ALC-2001 caustic corrosion agent 20g/L, sodium hydroxide 50g/L, 65 ℃ of dipping 5min.
4. secondary flow is washed from the beginning.
5. bright dipping: nitric acid 250g/L, room temperature dipping 3min.
6. secondary flow is washed from the beginning.
7. anodic oxidation: sulfuric acid 186g/L, Al
3+≤25g/L, 20 ℃, current density 1.2A/dm
2, electrolysis time 35min, thickness of oxidation film 15 μ m.
8. secondary flow is washed from the beginning.
Two, adopt encapsulant of the present invention and treatment process that above-mentioned anode oxide film is carried out sealing treatment.
Instance 1
1, after 1.-8. aluminium and aluminum alloy specimen carry out the anode oxidation film-forming processing by above-mentioned steps, immediately sull is carried out following sealing treatment.
1, sull sealing treatment:
(1), encapsulant forms: four water acetic acid magnesium 6.7g/L, trolamine 10mL/L, ammonium acetate 0.5g/L transfers to 5.6 with acetic acid with the pH value.
(2), closing process: 80 ℃, flood 30min.
(3), secondary flow is washed from the beginning.
(4), dry in air at room temperature.
(5), check
Specimen surface is clean, does not have " pollen " the weightless 25.7mg/dm of phosphoric acid-chromic acid corrosion
2, it is qualified to seal.
Instance 2
1, after 1.-8. aluminium and aluminum alloy specimen carry out the anode oxidation film-forming processing by above-mentioned steps, immediately sull is carried out following sealing treatment.
2, sull sealing treatment:
(1), encapsulant forms: four water acetic acid magnesium 6.7g/L, hydrazine hydrate (85%), ammonium acetate 1g/L transfers to 5.85 with acetic acid with the pH value.
(2), closing process: 80 ℃, flood 30min.
(3), secondary flow is washed from the beginning.
(4), dry in air at room temperature.
(5), check
Specimen surface does not totally have " pollen ", the weightless 24.1mg/dm of phosphoric acid-chromic acid corrosion
2, it is qualified to seal.
Instance 3
1, after 1.-8. aluminium and aluminum alloy specimen carry out the anode oxidation film-forming processing by above-mentioned steps, immediately sull is carried out following sealing treatment.
2, sull sealing treatment:
(1), encapsulant forms: Lithium Hydroxide MonoHydrate 10g/L, trolamine 10mL/L, sodium-acetate 0.5g/L transfers to 6.6 with acetic acid with the pH value.
(2), closing process: 85 ℃, flood 30min.
(3), secondary flow is washed from the beginning.
(4), dry in air at room temperature.
(5), check
Specimen surface is clean, does not have " pollen " the weightless 22.4mg/dm of phosphoric acid-chromic acid corrosion
2, it is qualified to seal.
Instance 4
1, after 1.-8. aluminium and aluminum alloy specimen carry out the anode oxidation film-forming processing by above-mentioned steps, by following sull is carried out sealing treatment immediately.
2, sull sealing treatment:
(1), encapsulant forms: Lithium Hydroxide MonoHydrate 10g/L, nitrilotriacetic acid(NTA) 10g/L, sodium-acetate 1g/L adds acetic acid and solids is dissolved fully and the pH value is transferred to 6.6.
(2), closing process: 85 ℃, flood 30min.
(3), secondary flow is washed from the beginning.
(4), dry in air at room temperature.
(5), check
Specimen surface is clean, does not have " pollen " the weightless 21.8mg/dm of phosphoric acid-chromic acid corrosion
2, it is qualified to seal.
Instance 5
1, after 1.-8. aluminium and aluminum alloy specimen carry out the anode oxidation film-forming processing by above-mentioned steps, immediately sull is carried out following sealing treatment.
2, sull sealing treatment:
(1), encapsulant forms: lime carbonate 5.5g/L, nitrilotriacetic acid(NTA) 10g/L, sodium-acetate 0.5g/L adds acetic acid and solids is dissolved fully and the pH value is transferred to 6.8.
(2), closing process: 85 ℃, flood 30min.
(3), secondary flow is washed from the beginning.
(4), dry in air at room temperature.
(5), check
Specimen surface is clean, does not have " pollen " the weightless 26.4mg/dm of phosphoric acid-chromic acid corrosion
2, it is qualified to seal.
Instance 6
1, after 1.-8. aluminium and aluminum alloy specimen carry out the anode oxidation film-forming processing by above-mentioned steps, immediately sull is carried out following sealing treatment.
2, sull sealing treatment:
(1), encapsulant forms: lime carbonate 10g/L, solids dissolved fully and transfer to 6.6 to the pH value with thionamic acid.
(2), closing process: 85 ℃, flood 30min.
(3), secondary flow is washed from the beginning.
(4), dry in air at room temperature.
(5), check
Specimen surface does not totally have " pollen ", the weightless 25.9mg/dm of phosphoric acid-chromic acid corrosion
2,
It is qualified to seal.
Remarks: AC-98 and ALC-2001 handle series additive for Wuhan Inst. of Material Protection's aluminum alloy surface.
Claims (1)
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| CN101323965B true CN101323965B (en) | 2012-03-14 |
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