CN1844451A - Nano self-assembling granular membrane surface treatment liquid and method for preparing same - Google Patents
Nano self-assembling granular membrane surface treatment liquid and method for preparing same Download PDFInfo
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- CN1844451A CN1844451A CNA2005100462069A CN200510046206A CN1844451A CN 1844451 A CN1844451 A CN 1844451A CN A2005100462069 A CNA2005100462069 A CN A2005100462069A CN 200510046206 A CN200510046206 A CN 200510046206A CN 1844451 A CN1844451 A CN 1844451A
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
This invention relates to a nanometer self-assembly grain film surface disposal fluid and its preparation method. The disposal fluid is composed of 1-10% positive silicon acid formic esters, 3-20% organic silanes, 0.01-2% nanometer oxide, 50-1000ppm organic inhibitor and or 1-10% inorganic inhibitor, some pH regulator and curing agent, surplus water. The preparation steps as follows: adding the prepared nanometer oxide plasma by ratio under disturbing condition to the prepared nanometer self-assembly grain film foundation fluid, and adding thinner, inhibitor and curing agent, dispersing the mixture fully by high-speed dispersion machine or magnetic beater. The character of this invention is that its environment compatibility is well, the technology is simple, and it can be used in surface preprocessing of aluminum, aluminum alloy, magnesium, magnesium alloy, zinc, zinc alloy and so on.
Description
Technical field
The present invention relates to process for treating surface, be specially a kind of eco-friendly generation chromium technology-nano self-assembling granular membrane (SNAP) surface treatment liquid and preparation method thereof.
Background technology
The chromate conversion coating surface treatment is the most effectively process for treating surface of aluminium, magnesium and alloy thereof, and formed chemical conversion film has good self-reparing capability, good solidity to corrosion and coating performance.But, because of the toxicity and the carcinogenesis of hexavalent chromate stronger, aerosol that produces in the surface treatment process and waste water are very serious to the harm of environment and organism, and in recent years, more and more countries use and discharge of wastewater thereof to chromic salt in the environmental protection legislation done very strict restriction.Therefore, research and development technology is simple, environmental friendliness, Chrome-free process for treating surface and coating system with long-lasting protection ability, is a very urgent task, has important scientific meaning and very big actual application value.
The eighties in last century, that improves chromate treating technology, development environment close friend has just become a focus that receives much concern for the chromiumcoating system.But, up to now, still do not have a kind of surface conversion coating can reach the such performance of chromate conversion coating.In recent years, people attempt by the blended method design and prepare have simultaneously good shielding properties, self-repairability and coating performance for chromiumcoating.Some studies show that sol-gel technique is exactly a kind of method that application prospect is arranged, composite organic-inorganic material by this method preparation has necessary machinery of long-lived coating and physicals, its inorganic component is given the sticking power of coating weather resistance, resistance to marring, improvement and matrix, and organic constituent increase coating elasticity, density and with the consistency of organic coating film.But the wet sticking power of the composite organic-inorganic material that sol-gel method at room temperature prepares does not still reach the level of chromate conversion coating, needs to improve its wet sticking power through pyroprocessing.The eco-friendly process for treating surface that has good shielding properties, selfreparing and adhesive property does not simultaneously appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of nano self-assembling granular membrane surface treatment liquid and preparation method thereof with good shielding properties, self-repairability and coating performance.
Technical scheme of the present invention is:
A kind of nano self-assembling granular membrane surface treatment liquid and preparation method thereof is characterized in that: this treatment solution is made up of the water of the inorganic inhibitor of 1～10% tetramethoxysilance, 3～20% organosilanes, 0.01～2% nano-oxide, 50～1000ppm organic inhibitor and/or 1～10%, an amount of pH regulator agent and solidifying agent, surplus; Nano-oxide in the described nano self-assembling granular membrane surface treatment liquid is preferably 0.02～0.1%.
Nano-oxide refers to nano silicon and/or nano-cerium oxide or the nano titanium oxide of mean particle size below 100nm of primary particle.
Organosilane of the present invention is γ-glycidyl ether propyl trimethoxy silicane and/or β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane.
Organic inhibitor of the present invention is one or more of benzotriazole, mercaptobenzothiazole, aminobenzothiazole, amino benzoglyoxaline, amino piperidine, mercaptobenzimidazole, aminopiperazine, tetramethyl-diethyl phosphoric acid ester, dextrin.
Organic inhibitor is mercaptobenzothiazole, aminobenzothiazole, amino benzoglyoxaline, amino piperidine, mercaptobenzimidazole, dextrin preferably.
Inorganic inhibitor of the present invention is one or more of molybdate, phosphoric acid salt, phosphomolybdate, Lin Wusuanyan, metaborate, vanadate, tungstate, silicate, rare-earth salts.
Inorganic inhibitor is molybdate, phosphoric acid salt and rare-earth salts preferably.
Solidifying agent of the present invention is N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, N-aminoethyl-γ-An Bingjisanjiayangjiguiwan, aminopropyl trimethoxysilane.Solidifying agent is an aminopropyl trimethoxysilane preferably.
The present invention also provides the preparation method of above-mentioned nano self-assembling granular membrane, comprises the steps:
1) at first, the pH regulator agent is added in the entry, then under stirring condition, the mixture that dropwise adds tetramethoxysilance and organosilane, dropwise, add nano-oxide again, continue to stir 24～72h, the gained slurry grinds 1～2h in sand mill or ball mill, the nano-oxide of making is in 100% weight, by nano silicon and/or nano-cerium oxide or nano titanium oxide 30～50%, tetramethoxysilance 2～18%, organosilane 5～28%, the water of surplus is formed.
2) the pH regulator agent is added in the entry, then under stirring condition, the mixture that dropwise adds tetramethoxysilance and organosilane, dropwise, continue to stir 24～72h, the basal liquid of the nano self-assembling granular membrane of making is in 100% weight, by tetramethoxysilance 5～25%, organosilane 10～40%, the water of surplus is formed.
3) in proportion the nano-oxide slurry for preparing is joined under stirring condition in the nano self-assembling granular membrane basal liquid for preparing, add remaining diluent water, inhibiter and solidifying agent respectively in described ratio then, fully disperse this mixture with high speed dispersor or magnetic stirring apparatus, time is 10～60 minutes, is coated in alloy surface and gets final product.
The invention has the beneficial effects as follows:
1, the present invention's method of having proposed prefabricated nano-oxide slurry and prefabricated nano self-assembling granular membrane basal liquid first prepares nano self-assembling granular membrane surface treatment liquid, this preparation method has improved the handiness of nano self-assembling granular membrane preparation greatly, simplify production technique greatly, improved production efficiency; Only need prepare the basal liquid of nano-oxide slurry and nano self-assembling granular membrane in advance, just can adjust the consumption of nano-oxide in nano self-assembling granular membrane surface treatment liquid and the kind and the consumption of inhibiter and solidifying agent at any time according to actual needs.
2, nano self-assembling granular membrane surface treatment liquid of the present invention can be used for the surface preparation of aluminium, aluminium alloy, magnesium, magnesium alloy, zinc, zinc alloy etc.Nano self-assembling granular membrane 2～3 μ m of the present invention are thick, and its Corrosion Protection reaches the level of chromate conversion coating.
Embodiment
Embodiment 1
In the 600ml beaker, take by weighing distilled water 54g, adjust pH value to 4～5 with acetate, under stirring condition, dropwise add 22.83g tetramethoxysilance and 11.82g β-(3, the 4-epoxycyclohexyl) mixture of ethyl trimethoxy silane, dropwise, add the 59.1g nano-cerium oxide again, continue to stir 24h, grind 2h with sand mill then.Make the nano-cerium oxide weight ratio and be 40% nano-cerium oxide slurry.
Embodiment 2
The preparation method is with embodiment 1, adjust nano-cerium oxide and tetramethoxysilance and β-(3, the 4-epoxycyclohexyl) add-on of ethyl trimethoxy silane, wherein tetramethoxysilance and β-(3, the 4-epoxycyclohexyl) ratio between the ethyl trimethoxy silane is with embodiment 1, and the weight ratio that makes the nano-cerium oxide of preparing is 50%.
Embodiment 3
In the 600ml beaker, take by weighing distilled water 54g, adjust pH value to 4～5 with acetate, under stirring condition, dropwise add the mixture of 22.83g tetramethoxysilance and 11.82g β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, dropwise, continue to stir 24h.Make the SNAP basal liquid of the nano-cerium oxide slurry coupling use that makes with embodiment 1 and embodiment 2.
Embodiment 4
In the 600ml beaker, take by weighing distilled water 135g, adjust pH value to 4～5 with acetate, under stirring condition, dropwise add 19.03g tetramethoxysilance and 88.65g β-(3, the 4-epoxycyclohexyl) mixture of ethyl trimethoxy silane, dropwise, add the 161.8g nano silicon again, continue to stir 72h, grind 1h with sand mill then.Make the nano silicon weight ratio and be 40% nano silicon slurry.
Embodiment 5
The preparation method is with embodiment 4, adjust the add-on of nano silicon and tetramethoxysilance and γ-glycidyl ether propyl trimethoxy silicane, wherein the ratio between tetramethoxysilance and γ-glycidyl ether propyl trimethoxy silicane is with embodiment 4, and the weight ratio that makes the nano silicon of preparing is 30%.
Embodiment 6
In the 600ml beaker, take by weighing distilled water 135g, adjust pH value to 4～5, under stirring condition, dropwise add the mixture of 19.03g tetramethoxysilance and 88.65g γ-glycidyl ether propyl trimethoxy silicane, dropwise, continue to stir 72h with acetate.Make the SNAP basal liquid of the nano silicon slurry coupling use that makes with embodiment 4 and embodiment 5.
Embodiment 7
In the 600ml beaker, take by weighing distilled water 54g, adjust pH value to 4～5 with acetate, the mixture that under stirring condition, dropwise adds 7.61g tetramethoxysilance and 35.46g γ-glycidyl ether propyl trimethoxy silicane, dropwise, add the 97.07g nano titanium oxide again, continue to stir 48h, grind 2h with sand mill then.Make the nano titanium oxide weight ratio and be 50% nano titanium dioxide paste.
Embodiment 8
The preparation method is with embodiment 7, adjust the add-on of nano titanium oxide and tetramethoxysilance and γ-glycidyl ether propyl trimethoxy silicane, wherein the ratio between tetramethoxysilance and γ-glycidyl ether propyl trimethoxy silicane is with embodiment 7, and the weight ratio that makes the nano titanium oxide of preparing is 30%.
Embodiment 9
In the 600ml beaker, take by weighing distilled water 54g, adjust pH value to 4～5, under stirring condition, dropwise add the mixture of 7.61g tetramethoxysilance and 35.46g γ-glycidyl ether propyl trimethoxy silicane, dropwise, continue to stir 48h with acetate.Make the SNAP basal liquid of the nano silicon slurry coupling use that makes with embodiment 7 and embodiment 8.
Embodiment 10
In the 300ml beaker, take by weighing the SNAP basal liquid 64g that embodiment 3 methods are made, add the 0.46g 40% nano-cerium oxide slurry that embodiment 1 method is made, add diluent water 112.59g again, solidifying agent diethyl three ammonia 1.59g, inhibiter amino piperidine 17.8mg, dispersed with stirring is even.Be coated with this treatment solution then on the aluminium alloy plate of 50 * 50 * 3mm, the sample behind the coating treatment solution is made the nano self-assembling granular membrane that thickness is 2～3 μ m in one week of drying at room temperature.
Embodiment 11
In the 300ml beaker, take by weighing the SNAP basal liquid 64.1g that embodiment 3 methods are made, add the 0.37g 50% nano-cerium oxide slurry that embodiment 2 methods are made, add diluent water 112.59g again, solidifying agent diethyl three ammonia 1.59g, inhibiter amino piperidine 17.8mg, dispersed with stirring is even.Be coated with this treatment solution then on the aluminium alloy plate of 50 * 50 * 3mm, the sample behind the coating treatment solution is made the nano self-assembling granular membrane that thickness is 2～3 μ m in one week of drying at room temperature.
Embodiment 12
In the 300ml beaker, take by weighing the SNAP basal liquid 95.5g that embodiment 6 methods are made, add the 1.38g 40% nano silicon slurry that embodiment 4 methods are made, add diluent water 168.88g again, solidifying agent diethyl three ammonia 2.38g, inhibiter mercaptobenzothiazole 45mg, dispersed with stirring is even.Be coated with this treatment solution then on the aluminium alloy plate of 50 * 50 * 3mm, the sample behind the coating treatment solution is made the nano self-assembling granular membrane that thickness is 2～3 μ m in one week of drying at room temperature.
Embodiment 13
In the 300ml beaker, take by weighing the SNAP basal liquid 96g that embodiment 6 methods are made, add the 0.92g 30% nano silicon slurry that embodiment 5 methods are made, add diluent water 168.88g again, solidifying agent diethyl three ammonia 2.38g, inhibiter mercaptobenzothiazole 45mg, dispersed with stirring is even.Be coated with this treatment solution then on the aluminium alloy plate of 50 * 50 * 3mm, the sample behind the coating treatment solution is made the nano self-assembling granular membrane that thickness is 2～3 μ m in one week of drying at room temperature.
Embodiment 14
In the 300ml beaker, take by weighing the SNAP basal liquid 48g that embodiment 9 methods are made, add 1.1g 50% nano titanium dioxide paste that embodiment 7 methods are made, add diluent water 84.44g again, solidifying agent aminopropyl trimethoxysilane 5.2g, inhibiter Sodium orthomolybdate 6.7g, dispersed with stirring is even.Be coated with this treatment solution then on the aluminium alloy plate of 50 * 50 * 3mm, the sample behind the coating treatment solution is made the nano self-assembling granular membrane that thickness is 2～3 μ m in one week of drying at room temperature.
Embodiment 15
In the 300ml beaker, take by weighing the SNAP basal liquid 48g that embodiment 9 methods are made, add 0.73g 30% nano titanium dioxide paste that embodiment 8 methods are made, add diluent water 84.44g again, aminopropyl trimethoxysilane 5.2g, inhibiter Sodium orthomolybdate 6.7g, dispersed with stirring is even.Be coated with this treatment solution then on the aluminium alloy plate of 50 * 50 * 3mm, the sample behind the coating treatment solution is made the nano self-assembling granular membrane that thickness is 2～3 μ m in one week of drying at room temperature.
The aluminium alloy plate of nano self-assembling granular membrane surface treatment liquid application of the present invention and the aluminium alloy plate after the A Luoding processing are carried out the solidity to corrosion comparative evaluation in same corrosive medium, what evaluation method adopted is morphology observation and electrochemical impedance spectroscopy EIS bonded method.The extent of corrosion that two class samples soak in the 3.5wt% sodium chloride solution behind the 240h is approaching, and is all light than the corrosion of blank aluminium alloy plate.
Claims (10)
1, a kind of nano self-assembling granular membrane surface treatment liquid, it is characterized in that by weight percentage, it basic composition is: 1～10% tetramethoxysilance, 3～20% organosilanes, 0.01～2% nano-oxide, 50～100ppm organic inhibitor and/or 1～10% inorganic inhibitor and 0.2～1% solidifying agent, all the other are water.
2, nano self-assembling granular membrane surface treatment liquid according to claim 1, it is characterized in that: one or more of the nano silicon of the median size that nano-oxide refers to primary particle below 100nm, nano-cerium oxide, nano-titanium oxide, nano-oxide is to add with the form of starching, the nano-oxide slurry is one or more that nano silicon slurry, nano-cerium oxide are starched, nano-titanium oxide is starched, the nano-oxide slurry is by nano-oxide 30～50%, tetramethoxysilance 2～18%, organosilane 5～28%, the water of surplus is formed.
3, nano self-assembling granular membrane surface treatment liquid according to claim 1 is characterized in that: described organosilane is γ-glycidyl ether propyl trimethoxy silicane and/or β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane; Described organic inhibitor is one or more of benzotriazole, mercaptobenzothiazole, aminobenzothiazole, amino benzoglyoxaline, amino piperidine, mercaptobenzimidazole, aminopiperazine, tetramethyl-diethyl phosphoric acid ester, dextrin; Described inorganic inhibitor is one or more of molybdate, phosphoric acid salt, phosphomolybdate, Lin Wusuanyan, metaborate, vanadate, tungstate, silicate, rare-earth salts.
4, nano self-assembling granular membrane surface treatment liquid according to claim 1 is characterized in that: the content of described nano-oxide is preferably 0.02～0.1%.
5, nano self-assembling granular membrane surface treatment liquid according to claim 1 is characterized in that: also comprise the pH regulator agent, described pH regulator agent is an acetic acid; The consumption of described pH regulator agent guarantees that the pH value of basal liquid is between 4～5.
6, nano self-assembling granular membrane surface treatment liquid according to claim 1 is characterized in that: described solidifying agent is diethyl three ammonia and/or aminosilane.
7, nano self-assembling granular membrane surface treatment liquid according to claim 6, it is characterized in that: described aminosilane is N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, N-aminoethyl-γ-An Bingjisanjiayangjiguiwan, one or more of aminopropyl trimethoxysilane.
8, the preparation method of the described nano self-assembling granular membrane surface treatment liquid of one of a kind of claim 1～7 is characterized in that preparation process is as follows:
1) at first, the pH regulator agent is added in the entry, adjust pH value to 4～5, under stirring condition, dropwise add the mixture of tetramethoxysilance and organosilane then, dropwise, add nano-oxide again, continue to stir 24～72h, the gained slurry grinds 1～2h in sand mill or ball mill, and the nano-oxide slurry of making by weight percentage, by nano-oxide 30～50%, tetramethoxysilance 2～18%, organosilane 5～28%, the water of surplus is formed;
2) the pH regulator agent is added in the entry, adjust pH value to 4～5, then under stirring condition, dropwise add the mixture of tetramethoxysilance and organosilane, dropwise, continue to stir 24～72h, the basal liquid of the nano self-assembling granular membrane of making by weight percentage, by tetramethoxysilance 5～25%, organosilane 10～40%, the water of surplus is formed;
3) in described ratio the nano-oxide slurry for preparing is joined under stirring condition in the nano self-assembling granular membrane basal liquid for preparing, add diluent water, inhibiter and solidifying agent respectively in described ratio then, dispersed with stirring evenly gets final product.
9, the preparation method of nano self-assembling granular membrane surface treatment liquid according to claim 8 is characterized in that: the first step prepares the used organosilane of nano-oxide slurry and second step, and to prepare the used organosilane of nano self-assembling granular membrane basal liquid identical.
10, the preparation method of nano self-assembling granular membrane surface treatment liquid according to claim 8 is characterized in that: in the described step 3), adopt high speed dispersor or magnetic stirring apparatus fully to disperse this mixture, the time is 10～60 minutes.
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| CN101845634A (en) * | 2010-06-21 | 2010-09-29 | 华中科技大学 | Corrosion inhibitor for inhibiting corrosion of magnesium alloy in automobile cooling liquid |
| CN101613543B (en) * | 2009-07-20 | 2012-05-23 | 北京科技大学 | Method for preparing coating with metal surface corrosion inhibition and self-repair functions |
| CN102534598A (en) * | 2012-03-16 | 2012-07-04 | 广西民族大学 | Preparation method and film-forming liquid for aluminum alloy high-performance trivalent chromium hybrid conversion film |
| CN102618861A (en) * | 2012-03-16 | 2012-08-01 | 广西民族大学 | Method for preparing trivalent chromium and phosphomolybdiumtungstic acid hybrid film on surface of aluminum alloy and film forming solution for method |
| CN102703893A (en) * | 2012-05-28 | 2012-10-03 | 武汉永正科技发展有限公司 | Environmental protection passivation solution for galvanized part and preparation method thereof |
| CN103086743A (en) * | 2011-11-04 | 2013-05-08 | 中国科学院金属研究所 | Nano self-assembly penetrant for magnesium alloy service and preparation method and application thereof |
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| CN1178994C (en) * | 2001-10-12 | 2004-12-08 | 中国科学院金属研究所 | Nano zinc oxide slurry composition and its preparation method |
| MXPA05000879A (en) * | 2002-07-24 | 2005-10-19 | Univ Cincinnati | Superprimer. |
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| CN101613543B (en) * | 2009-07-20 | 2012-05-23 | 北京科技大学 | Method for preparing coating with metal surface corrosion inhibition and self-repair functions |
| CN101845634A (en) * | 2010-06-21 | 2010-09-29 | 华中科技大学 | Corrosion inhibitor for inhibiting corrosion of magnesium alloy in automobile cooling liquid |
| CN103086743A (en) * | 2011-11-04 | 2013-05-08 | 中国科学院金属研究所 | Nano self-assembly penetrant for magnesium alloy service and preparation method and application thereof |
| CN103086743B (en) * | 2011-11-04 | 2014-09-03 | 中国科学院金属研究所 | Nano self-assembly penetrant for magnesium alloy service and preparation method and application thereof |
| CN102534598B (en) * | 2012-03-16 | 2013-12-18 | 广西民族大学 | Preparation method and film-forming liquid for aluminum alloy high-performance trivalent chromium hybrid conversion film |
| CN102618861A (en) * | 2012-03-16 | 2012-08-01 | 广西民族大学 | Method for preparing trivalent chromium and phosphomolybdiumtungstic acid hybrid film on surface of aluminum alloy and film forming solution for method |
| CN102618861B (en) * | 2012-03-16 | 2014-03-26 | 广西民族大学 | Method for preparing trivalent chromium and phosphomolybdiumtungstic acid hybrid film on surface of aluminum alloy and film forming solution for method |
| CN102534598A (en) * | 2012-03-16 | 2012-07-04 | 广西民族大学 | Preparation method and film-forming liquid for aluminum alloy high-performance trivalent chromium hybrid conversion film |
| CN102703893A (en) * | 2012-05-28 | 2012-10-03 | 武汉永正科技发展有限公司 | Environmental protection passivation solution for galvanized part and preparation method thereof |
| CN105802508A (en) * | 2014-12-29 | 2016-07-27 | 安集微电子（上海）有限公司 | Application of azole compound in improvement of stability of chemico-mechanical polishing solution |
| CN105802508B (en) * | 2014-12-29 | 2020-03-13 | 安集微电子（上海）有限公司 | Application of azole compound in improving stability of chemical mechanical polishing solution |
| CN108774597A (en) * | 2018-07-31 | 2018-11-09 | 广东利尔化学有限公司 | A kind of wiring board acidic cleaner and preparation method thereof |
| CN110205617A (en) * | 2019-06-24 | 2019-09-06 | 界首万昌新材料技术有限公司 | A kind of automobile axle shaft phosphorization treatment process |
| CN112064001A (en) * | 2020-09-24 | 2020-12-11 | 蚌埠学院 | Blackening-resistant chromium-free passivation solution for batch hot dip galvanized workpieces and preparation method thereof |
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