CN103540917A - Metal surface treatment agent as well as preparation method thereof - Google Patents
Metal surface treatment agent as well as preparation method thereof Download PDFInfo
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- CN103540917A CN103540917A CN201310450910.5A CN201310450910A CN103540917A CN 103540917 A CN103540917 A CN 103540917A CN 201310450910 A CN201310450910 A CN 201310450910A CN 103540917 A CN103540917 A CN 103540917A
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- triethoxysilyl
- metal conditioner
- zirconium
- ethane
- hexane
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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
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- Chemical Treatment Of Metals (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to a metal surface treatment agent as well as a preparation method thereof. The metal surface treatment agent consists of titanium fluoride, zirconium nitrate, zirconium fluoride, amino silane, 1,2-di(triethoxy silyl) ethane and di(triethoxy silyl) hexane. The titanium fluoride, the zirconium nitrate and the zirconium fluoride account for 110ppm-140ppm or 550ppm-650ppm of the total amount of the treatment agent in terms of metal elements, wherein a ratio of metal element atoms of the titanium fluoride to metal element atoms of the zirconium nitrate and the zirconium fluoride is 1:1-1:3; a ratio of metal element atoms of the zirconium nitrate to the metal element atoms of the zirconium fluoride is 2:5; a molar ratio of the amino silane to the 1,2-di(triethoxy silyl) ethane and the di(triethoxy silyl) hexane is 17:3-9:1; a molar ratio of the 1,2-di(triethoxy silyl) ethane to the di(triethoxy silyl) hexane is 1:1.
Description
Technical field
The invention belongs to field of metal surface treatment, specifically refer to treatment agent and preparation method thereof for a kind of metal finishing.
Background technology
In order to improve the erosion resistance of metallic surface, conventionally can use chromic salt process metal surfaces or use phosphatizing metallic surface.But environment and laborer's health is had to serious infringement adopting chromic salt or phosphoric acid salt to carry out waste water in metal finishing process etc., along with the enhancing of the world to the protection consciousness of environment, the strict restriction of now using chromic salt or phosphoric acid salt to be subject to.
Although phosphoric acid salt carries out in metal finishing process, injury to laborer is less, but rich phosphatization problem is serious in the waste water of postorder, and also inevitably use containing chromic salts in using phosphatic technique, therefore, existing many countries all to ban use of chromic salt or phosphoric acid salt be metal conditioner.
Now can substitute chromium hydrochlorate or phosphatic chromium-free metal surface treatment agent uses substantially is all zirconium metalloid surface treatment agent, titanium metalloid surface treatment agent or zirconium-titanium class surface treatment agent.This class treatment agent is generally to substitute phosphate radical with halogen, wherein particularly relatively the most fastening with the combination of matrix after the film process of fluorion in chromium-free metal surface treatment agent or film forming.
But, all chromate-free metal finishing or phosphoric acid salt metal finishing in existing technology, still cannot use together the effect ratio of chromic salt or phosphoric acid salt metal finishing, and aspect erosion resistance, also have difference, and the coating adhesion of postorder also there is gap.
Summary of the invention
The object of this invention is to provide a kind of metal conditioner and preparation method thereof, by this metal conditioner, can on pending matrix, form overlay film, the performance of this overlay film approaches substantially by chromic salt or phosphoric acid salt the treatment effect to metallic surface, and to the coating adhesion of postorder also larger raising.
The present invention is achieved by the following technical solutions:
, by titanium fluoride, zirconium nitrate, Zirconium tetrafluoride, aminosilane, 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane form; Titanium fluoride, zirconium nitrate and Zirconium tetrafluoride convert and account for 110-140ppm or the 550-650ppm for the treatment of agent total amount with metallic element, wherein, titanium fluoride is 1:1-1:3 with the ratio of the metallic element atom of zirconium nitrate and Zirconium tetrafluoride, and the ratio of the metallic element atom of zirconium nitrate and Zirconium tetrafluoride is 2:5; Aminosilane and 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane be take mol ratio as 17:3-9:1, wherein, 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane be take mol ratio as 1:1.
Described aminosilane includes 3-TSL 8330, APTES, 3-aminopropyl methyldiethoxysilane, N-phenyl-3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330 or N-(2-amino-ethyl) one or more combinations of-APTES.
Described metal conditioner includes one or more of the metallic elements such as magnesium, zinc, aluminium, cerium, rare earth element, vanadium and molybdenum.
In metal conditioner, magnesium, aluminium convert and account for the 100-500ppm for the treatment of agent total amount with metallic element.
In metal conditioner, vanadium, molybdenum convert and account for the 20-30ppm for the treatment of agent total amount with metallic element.
In described metal conditioner, include water-soluble or water dispersible organic resin, in solid components and concentration 50-1000ppm.
In described metal conditioner, further include and be selected from nitric acid, sulfuric acid, phosphoric acid and their salt, it take solid components and concentration metering is 50-10000ppm.
The pH value of described metal conditioner is 3.2-4.5.
A preparation method for metal conditioner,
First, by aminosilane, 1, the hydrolysis of 2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane makes condenses I;
Secondly, the titanium fluoride measuring, zirconium nitrate, Zirconium tetrafluoride are mixed with condenses I;
Finally, add one or more of the metallic elements such as magnesium, zinc, aluminium, cerium, rare earth element, vanadium and molybdenum; Add water-soluble or water dispersible organic resin; Add to contain and be selected from nitric acid, sulfuric acid, phosphoric acid and their salt; Add tensio-active agent; It is 3.2-4.5 that solution is adjusted into pH value with acid.
The invention has the beneficial effects as follows:
Technical scheme of the present invention is by the usage ratio to titanium-containing compound and zirconium-containing compound, improved at the overlay film effect of pending metallic surface and the coating adhesion of rear operation, and pass through aminosilane and 1, the ratio of components of 2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane, has improved the corrosion resistance nature of overlay film.
Embodiment
Describe by the following examples technical scheme of the present invention in detail, should be understood that, following embodiment is only exemplary, only can be used for explaining and technical scheme of the present invention being described, and can not to be interpreted as is the restriction to technical solution of the present invention.
In the present invention, titaniferous compound and zirconium compound are for form the material of the chemical transformation overlay film that contains titanium and zirconium on metal material surface, although this two compounds belongs to common used material in metal finishing, but cannot reach best effect always, and, the composition of this two compounds or the difference of proportioning are all not identical in performance and the characteristic of the overlay film of metallic surface yet.In the present invention, what select is titanium fluoride, zirconium nitrate and three kinds of compounds of Zirconium tetrafluoride, titanium fluoride, zirconium nitrate and Zirconium tetrafluoride convert and account for 110-140ppm or the 550-650ppm for the treatment of agent total amount with metallic element, wherein, titanium fluoride is 1:1-1:3 with the ratio of the metallic element atom of zirconium nitrate and Zirconium tetrafluoride, and the ratio of the metallic element atom of zirconium nitrate and Zirconium tetrafluoride is 2:5.
In technical scheme of the present invention, when the ratio of titanium fluoride and the metallic element atom of zirconium nitrate and Zirconium tetrafluoride is 1:1, it is preferred version of the present invention that titanium fluoride, zirconium nitrate and Zirconium tetrafluoride be take the metallic element 550-650ppm that accounts for treatment agent total amount that converts; When the ratio of titanium fluoride and the metallic element atom of zirconium nitrate and Zirconium tetrafluoride is 1:3, it is preferred version of the present invention that titanium fluoride, zirconium nitrate and Zirconium tetrafluoride be take the metallic element 110-140ppm that accounts for treatment agent total amount that converts.
In technical scheme of the present invention, aminosilane, 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane generation condensation reaction, reactant in the overlay film of metallic surface for improving the erosion resistance of overlay film, and improve the tack that aftertreatment is filmed, its preparation method is for making aminosilane, 1, and 2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane are hydrolyzed and make in water, alcohol or acidic aqueous solution.
In technical scheme of the present invention, aminosilane includes 3-TSL 8330, APTES, 3-aminopropyl methyldiethoxysilane, N-phenyl-3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330 or N-(2-amino-ethyl) one or more combinations of-APTES.
Aminosilane and 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane be take mol ratio as 17:3-9:1, wherein, 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane be take mol ratio as 1:1.
At aminosilane of the present invention, 1, the final condenses solid components and concentration of 2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane accounts for the 220-280ppm for the treatment of agent total amount.
In order to improve the erosion resistance for the treatment of agent overlay film and to improve the tack of filming, can in treatment agent, add one or more of the metallic elements such as magnesium, zinc, aluminium, cerium, rare earth element, vanadium and molybdenum, wherein add magnesium, zinc, aluminium can improve the tack of filming, add the metallic elements such as cerium, rare earth element, vanadium and molybdenum can improve the corrosion resistance nature of overlay film.
For improve treatment agent the wear resisting property of metallic surface and with the tack of filming, can add water-soluble or water dispersible organic resin, in the present invention, such as, epoxy resin, acrylic resin etc., wherein, the weathering resistance of epoxy resin is poor, does not select epoxy resin during to metal finishing for outdoor; The good weatherability of acrylic resin, and be applicable to low temperature, can be for extremely frigid zones, but the hardness of this resin is larger, and fragility is large, and time and overlay film thickness that when processing, the time is less than other resin also should reduce.When the resin using has acrylic resin, in solid composition, should not surpass 1000ppm, best with 50-300ppm.
In order to promote the formation of overlay film, improve the erosion resistance of overlay film, in treatment agent, can select nitric acid, sulfuric acid, phosphoric acid etc. and their salt, can also adjust on the one hand the pH value for the treatment of agent, the pH value of the treatment agent of this programme is optimum 3.2-4.5.
In order to improve the stability for the treatment of agent and the property separated out, can add tensio-active agent, mainly add anionic species tensio-active agent and/or nonionic class tensio-active agent.
Embodiment mono-
, by titanium fluoride, zirconium nitrate, Zirconium tetrafluoride, aminosilane, 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane form; Titanium fluoride, zirconium nitrate and Zirconium tetrafluoride convert and account for the 110-140ppm for the treatment of agent total amount with metallic element, and wherein, titanium fluoride is 1:3 with the ratio of the metallic element atom of zirconium nitrate and Zirconium tetrafluoride, and the ratio of the metallic element atom of zirconium nitrate and Zirconium tetrafluoride is 2:5; Aminosilane and 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane be take mol ratio as 17:3, wherein, 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane be take mol ratio as 1:1.
Embodiment bis-
, by titanium fluoride, zirconium nitrate, Zirconium tetrafluoride, aminosilane, 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane form; Titanium fluoride, zirconium nitrate and Zirconium tetrafluoride convert and account for the 550-650ppm for the treatment of agent total amount with metallic element, and wherein, titanium fluoride is 1:1 with the ratio of the metallic element atom of zirconium nitrate and Zirconium tetrafluoride, and the ratio of the metallic element atom of zirconium nitrate and Zirconium tetrafluoride is 2:5; Aminosilane and 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane be take mol ratio as 9:1, wherein, 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane be take mol ratio as 1:1.
The preparation method of metal conditioner,
First, by aminosilane, 1, the hydrolysis of 2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane makes condenses I;
Secondly, the titanium fluoride measuring, zirconium nitrate, Zirconium tetrafluoride are mixed with condenses I;
Finally, add one or more of the metallic elements such as magnesium, zinc, aluminium, cerium, rare earth element, vanadium and molybdenum; Add water-soluble or water dispersible organic resin; Add to contain and be selected from nitric acid, sulfuric acid, phosphoric acid and their salt; Add tensio-active agent; It is 3.2-4.5 that solution is adjusted into pH value with acid.
In technical scheme of the present invention, the preparation method of all embodiment is identical, and distinguishing is only that each forms difference to some extent.
Claims (9)
1. a metal conditioner, is characterized in that: by titanium fluoride, zirconium nitrate, Zirconium tetrafluoride, aminosilane, 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane form; Titanium fluoride, zirconium nitrate and Zirconium tetrafluoride convert and account for 110-140ppm or the 550-650ppm for the treatment of agent total amount with metallic element, wherein, titanium fluoride is 1:1-1:3 with the ratio of the metallic element atom of zirconium nitrate and Zirconium tetrafluoride, and the ratio of the metallic element atom of zirconium nitrate and Zirconium tetrafluoride is 2:5; Aminosilane and 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane be take mol ratio as 17:3-9:1, wherein, 1,2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane be take mol ratio as 1:1.
2. metal conditioner according to claim 1, is characterized in that: described aminosilane includes 3-TSL 8330, APTES, 3-aminopropyl methyldiethoxysilane, N-phenyl-3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330 or N-(2-amino-ethyl) one or more combinations of-APTES.
3. metal conditioner according to claim 1, is characterized in that: described metal conditioner includes one or more of the metallic elements such as magnesium, zinc, aluminium, cerium, rare earth element, vanadium and molybdenum.
4. metal conditioner according to claim 3, is characterized in that: in metal conditioner, magnesium, aluminium convert and account for the 100-500ppm for the treatment of agent total amount with metallic element.
5. metal conditioner according to claim 3, is characterized in that: in metal conditioner, vanadium, molybdenum convert and account for the 20-30ppm for the treatment of agent total amount with metallic element.
6. metal conditioner according to claim 1, is characterized in that: in described metal conditioner, include water-soluble or water dispersible organic resin, in solid components and concentration 50-1000ppm.
7. metal conditioner according to claim 1, is characterized in that: in described metal conditioner, further include and be selected from nitric acid, sulfuric acid, phosphoric acid and their salt, it take the metering of solid components and concentration is 50-10000ppm.
8. metal conditioner according to claim 1, is characterized in that: the pH value of described metal conditioner is 3.2-4.5.
9. according to the preparation method of the metal conditioner described in claim 1 to 8, it is characterized in that:
First, by aminosilane, 1, the hydrolysis of 2-bis-(triethoxysilyl) ethane and two (triethoxysilyl) hexane makes condenses I;
Secondly, the titanium fluoride measuring, zirconium nitrate, Zirconium tetrafluoride are mixed with condenses I;
Finally, add one or more of the metallic elements such as magnesium, zinc, aluminium, cerium, rare earth element, vanadium and molybdenum; Add water-soluble or water dispersible organic resin; Add to contain and be selected from nitric acid, sulfuric acid, phosphoric acid and their salt; Add tensio-active agent; It is 3.2-4.5 that solution is adjusted into pH value with acid.
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Cited By (10)
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| CN103602971A (en) * | 2013-09-27 | 2014-02-26 | 宁波英科特精工机械股份有限公司 | Metal surface treating agent |
| CN103898593A (en) * | 2014-03-26 | 2014-07-02 | 北京大学深圳研究院 | Metal zirconium-treatment coating pretreatment agent with high electrophoretic rate |
| CN104099020A (en) * | 2014-06-19 | 2014-10-15 | 锐展(铜陵)科技有限公司 | Multi-silane aluminum alloy surface treating agent |
| CN106835098A (en) * | 2016-12-01 | 2017-06-13 | 三达奥克化学股份有限公司 | Environmentally friendly vitrification inorganic agent and production method before iron and steel parts electrophoretic painting |
| CN106892582A (en) * | 2017-03-06 | 2017-06-27 | 浙江大学 | A kind of composite coating based on silane coupler being modified for steel fiber surface |
| CN107473624A (en) * | 2017-06-26 | 2017-12-15 | 浙江大学 | A kind of cement-base composite material based on steel fibre after silane surface treatment |
| CN108165967A (en) * | 2017-12-25 | 2018-06-15 | 宁波市新光货架有限公司 | A kind of metal conditioner |
| CN108165968A (en) * | 2017-12-25 | 2018-06-15 | 宁波市新光货架有限公司 | A kind of metal surface treatment process and metal conditioner |
| CN108330478A (en) * | 2018-03-06 | 2018-07-27 | 上海耀岩化学品有限公司 | A kind of aqueous metal surface inorganic agent |
| CN109402621A (en) * | 2017-08-17 | 2019-03-01 | 中国科学院金属研究所 | A kind of film forming solution and film layer preparation method of magnesium alloy chromium-free flawless conversion film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103602971A (en) * | 2013-09-27 | 2014-02-26 | 宁波英科特精工机械股份有限公司 | Metal surface treating agent |
| CN103898593A (en) * | 2014-03-26 | 2014-07-02 | 北京大学深圳研究院 | Metal zirconium-treatment coating pretreatment agent with high electrophoretic rate |
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| CN106835098A (en) * | 2016-12-01 | 2017-06-13 | 三达奥克化学股份有限公司 | Environmentally friendly vitrification inorganic agent and production method before iron and steel parts electrophoretic painting |
| CN106892582A (en) * | 2017-03-06 | 2017-06-27 | 浙江大学 | A kind of composite coating based on silane coupler being modified for steel fiber surface |
| CN107473624A (en) * | 2017-06-26 | 2017-12-15 | 浙江大学 | A kind of cement-base composite material based on steel fibre after silane surface treatment |
| CN109402621A (en) * | 2017-08-17 | 2019-03-01 | 中国科学院金属研究所 | A kind of film forming solution and film layer preparation method of magnesium alloy chromium-free flawless conversion film |
| CN108165967A (en) * | 2017-12-25 | 2018-06-15 | 宁波市新光货架有限公司 | A kind of metal conditioner |
| CN108165968A (en) * | 2017-12-25 | 2018-06-15 | 宁波市新光货架有限公司 | A kind of metal surface treatment process and metal conditioner |
| CN108165967B (en) * | 2017-12-25 | 2019-11-22 | 宁波市新光货架有限公司 | A kind of metal conditioner |
| CN108165968B (en) * | 2017-12-25 | 2019-11-22 | 宁波市新光货架有限公司 | A kind of metal surface treatment process |
| CN108330478A (en) * | 2018-03-06 | 2018-07-27 | 上海耀岩化学品有限公司 | A kind of aqueous metal surface inorganic agent |
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