CN102337530A - Silane composite material for surface treatment before metal coating - Google Patents
Silane composite material for surface treatment before metal coating Download PDFInfo
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- CN102337530A CN102337530A CN2011101925769A CN201110192576A CN102337530A CN 102337530 A CN102337530 A CN 102337530A CN 2011101925769 A CN2011101925769 A CN 2011101925769A CN 201110192576 A CN201110192576 A CN 201110192576A CN 102337530 A CN102337530 A CN 102337530A
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Abstract
The invention discloses a phosphorus-free silane composite material which is used for surface treatment before metal coating and can effectively replace the traditional phosphating agent, belonging to the technical field of new materials for metal surface treatment. Each liter of silane composite material contains 20-80 g of zirconium salt and/or titanium salt, 5-30 g of stabilizing agent, 5-100 g of silane coupling agent, 1-30 ml acid and the balance of water. A compact composite conversion film can be formed on the metal surface treated by the silane composite material. By comparing pitting tests for investigating the properties of the phosphating film, the time for the conversion film to resist the pitting of a CuSO4 solution can reach 5-15 min, substantially exceeding the standard time namely 1-5 min for the traditional phosphating conversion film to resist the pitting of the CuSO4 solution. Moreover, the adhesion force of the paint film after surface coating is equivalent to that of the traditional phosphating film. The composite material treatment liquid does not contain any phosphorus, zirconium and titanium salts in the composite material treatment liquid are non-toxic or harmless, and the composite material treatment liquid is a novel environmental-friendly treatment liquid and can totally substitute for the traditional phosphating solution.
Description
Technical field
The present invention relates to the metal finishing new material technology field, be specifically related to a kind of without phosphorus silane matrix material that can effectively substitute the conventional phosphatizing agent that the coated metal front surface is handled that is used for.
Background technology
Phosphatization is traditional metal material surface treatment technology.Metallic substance (mainly being steel part) can form the fine and close phosphatic double salt conversion film (being commonly called as phosphatize phosphate coat) of one deck on the surface through bonderizing.Phosphatize phosphate coat not only has good interim rustless property, and can improve bonding force and the whole solidity to corrosion of coating between ferrous materials and the top coat, is requisite operation in the steel material surface Coating Pretreatment.Mostly the phosphorization technology that uses in China's industry at present is the peracidity phosphate system under the medium and high temperature condition, shortcoming such as have that energy consumption is big, phosphatization corrosion property is strong, the acid corrosion of phosphatization workshop is serious, discharging of waste liquid difficult treatment, environmental pollution are serious.Since the nineties in 20th century, Low-Temperature Phosphate Liquid and multifunction phosphide liquid begin to be widely used, though reduced energy consumption, because a large amount of deleterious additives such as nitrite, dichromate, fluorine-containing promotor that use have further increased environmental protection harm.Along with the pay attention to day by day of the whole world, advance cleaner production to become the inevitable choice that economy, social sustainable development are realized in countries in the world to environment protection.Low cost, less energy-consumption, the pollution-free new developing direction of metal finishing that becomes.In order to eliminate the eutrophic pollution of phosphorus to water body, without phosphorus conversion film technology more and more receives the attention of national governments over past ten years, and wherein, the silane treatment technology is the without phosphorus conversion film technology that is expected to substitute conventional phosphatizing technology at present most.But polycondensation takes place easily in silane in the aqueous solution, less stable, and also simple silane treatment is difficult in production technique, reach the performance requriements of conventional phosphatizing technology, and it is used and still is difficult to large-scale promotion at present.Without phosphorus compound silane coupling agent of the present invention has overcome the shortcoming of simple silane coupling agent poor stability, and has environmental protection and the good advantage of solidity to corrosion.
Summary of the invention
To the deficiency that exists in the prior art, the object of the present invention is to provide a kind of silane matrix material that is used for the processing of coated metal front surface and preparation method thereof.Silane matrix material of the present invention is a major ingredient with silane coupling agent and inorganic zirconates, titanium salt, synthesizes to have prepared a kind of special composite treating agent, and through adding stablizer, controls the hydrolytie polycondensation time of silane coupling agent, guarantees the stability of its storage and use.Metallic surface after this silane matrix material treatment solution is handled can form the fine and close compound conversion film of organic-inorganic of one deck, compares the anti-CuSO of this conversion film according to the pittingtest of investigating the phosphatize phosphate coat performance
4The time of solution spot corrosion can reach 5-15min (changing to some extent with the variation in thickness of conversion film), substantially exceeds the anti-CuS0 of conventional phosphatizing conversion film
4The time of solution spot corrosion has only the standard of 1-5min; And the paint film adhesion behind the external coating is suitable with the conventional phosphatizing film.This matrix material treatment solution is without phosphorus fully, and wherein zirconates, titanium salt are nontoxic, is a kind of novel environmental protection treatment liquid, can substitute conventional phosphatizing solution fully.
In order to realize above-mentioned technical purpose, technical scheme of the present invention is following:
A kind ofly be used for the silane matrix material that the coated metal front surface is handled, it is characterized in that containing in every liter of described silane matrix material the water of 20～80g zirconates and/or titanium salt, 5～30g stablizer, 5～100g silane coupling agent, 1～30ml acid and surplus.
Wherein, described zirconates is a fluozirconate.
Wherein, described titanium salt is titanyl sulfate or fluotitanate.
Wherein, the mass ratio of described fluozirconate and titanium salt mixture is 3: 0～5.
Wherein, described stablizer is the polyvalent alcohol that contains two above hydroxyls, as: terepthaloyl moietie, glycerine, tetramethylolmethane etc.
Wherein, described stablizer is the mixture of terepthaloyl moietie or glycerine and tetramethylolmethane, and its weight ratio is 1: 0.5～1.
Wherein, described silane coupling agent comprises the disilane (like tetra-sulfurized pair triethoxyl silane, 1,2-diethoxy estersil base ethane) of aminopropyl silane, epoxy radicals silicone hydride, urea propyl silane, vinyl silanes and sulfur-bearing chain or alkyl.
Wherein, described acid is acetate, nitric acid or hydrochloric acid.
Table one: the best silane coupling agent that different metal is selected for use
The above-mentioned preparation method who is used for the silane matrix material that the coated metal front surface handles is following:
1, takes by weighing zirconates and/or titanium salt according to formula ratio, add water and be heated to 60-80 ℃ and make it dissolving, in solution, add the stablizer of formula ratio then, to 3-4, stir 1-2h with the pH value of acid adjustment solution;
2, the silane coupling agent with formula ratio under agitation is added drop-wise in the above-mentioned solution, dropwises continued and stirs 2-3h;
3, supply the water of surplus according to formula ratio, continue to stir 1-2h and promptly get silane matrix material of the present invention.
The method that the prepared silane matrix material of the inventive method is used for the processing of coated metal front surface is following:
1, the silane matrix material with gained uses deionized water to be diluted to the working fluid of solid content as 1-5wt%;
2, with after pending steel oil removing, rust cleaning, the washing totally, put into working fluid, the treatment time is 1-5min;
3, the workpiece dry 5-15min in 60-80 ℃ environment after will handling gets final product.
Compared with prior art, advantage of the inventive method and beneficial effect are following:
The silane matrix material of the present invention preparation has been eliminated phosphoric in the conventional phosphatizing liquid to the harm of environment, has reduced the strong acid corrosive nature of conventional phosphatizing liquid, is a kind of novel environment friendly safe handling liquid.Technology, the equipment of use technology, equipment and the conventional phosphatizing of the silane matrix material treatment solution that the present invention relates to are suitable.Its simple and reliable process of technological experiment proof, the etch resistant properties of the steel plate after this treatment solution is handled is superior to conventional phosphatizing technology.This silane matrix material treatment solution has also overcome the shortcoming of many silane treatment liquid stable upon storage property differences, and its package stability at room temperature was 6 months, therefore can substitute conventional phosphatizing liquid fully.
Embodiment
Below in conjunction with concrete embodiment the inventive method is done further detailed description:
Embodiment 1
Take by weighing the 20g potassium fluozirconate and join in the water of 500ml, be heated to 80 ℃ of stirring and dissolving, add 30g tetramethylolmethane stablizer again; Drip an amount of nitric acid adjustment pH value between 3-4; Stir 1h, under agitation drip 100g aminopropyl three ethoxy silane then, drip complete continued and stirred hydrolysis reaction 2 hours; Add water to 1L at last, continuation stirring 2h makes a kind of light yellow transparent liquid and is product.
The method that obtained product is used for the processing of coated metal front surface is following:
1, the silane matrix material with gained uses deionized water to be diluted to the working fluid of solid content as 1-5wt%.
2, with after pending steel oil removing, rust cleaning, the washing totally, put into working fluid, treatment time 1-5min.
3, the workpiece dry 5-15min in 60-80 ℃ environment after will handling.
Performance such as following table with metallic surface after this product treatment:
| Project | Performance |
| ?5％CuSO 4Pittingtest | ?14min |
| Handling the surface, back carries out quiet | Sticking power: 0 grade (cross cut test) |
| The electro-powder spray test | Anti-neutral salt spray test: intersect behind stroke fork, put into salt fog cabinet 800h corrosion and spread < 1mm |
Testing used powder coating is polyester-triglycidyl isocyanurate (TGIC) powder coating, and the salt-fog test method is undertaken by the GB/T10125-1997 standard.
In order to compare the treatment effect of silane matrix material and conventional phosphatizing agent, get identical steel plate and in different treatment solutions, handle, carry out the surface spraying after the drying, the etched width of testing test piece 600h in salt fog cabinet then.Its etching width such as following table:
| Treatment process before the spraying | Etching width (mm) |
| Iron is phosphatization | 25±2 |
| Zinc phosphating | 19±2 |
| Iron is phosphatization+chromating | 12±2 |
| This product | 1±0.5 |
This product is at room temperature placed and was not become turbid in 6 months.
Embodiment 2
Take by weighing the 20g potassium fluozirconate and the 30g titanyl sulfate joins in the water of 700ml, be heated to 65 ℃ of stirring and dissolving, add 20g glycerine stablizer again; Drip an amount of nitric acid adjustment pH value between 3-4; Stir 1.5h, under agitation drip 60g epoxypropyl Trimethoxy silane then, drip complete continued and stirred hydrolysis reaction 2 hours; Add water to 1L at last, continuation stirring 1h makes a kind of light yellow transparent liquid and is product.
Method by among the embodiment 1 experimentizes, its effect such as following table:
This product is at room temperature placed and was not become turbid in 6 months.
Embodiment 3
Take by weighing the 30g potassium fluozirconate and the 20g titanyl sulfate joins in the water of 700ml, be heated to 70 ℃ of stirring and dissolving, add 10g glycerine and 5g tetramethylolmethane again; Drip an amount of nitric acid adjustment pH value between 3-4; Stir 1.5h, under agitation drip 60g urea propyl-triethoxysilicane then, drip complete continued and stirred hydrolysis reaction 2 hours; Add water to 1L at last, continuation stirring 1.5h makes a kind of light yellow transparent liquid and is product.
Method by among the embodiment 1 experimentizes, its effect such as following table:
This product is at room temperature placed and was not become turbid in 6 months.
Embodiment 4
Take by weighing the 40g potassium fluozirconate and the 30g titanyl sulfate joins in the water of 800ml, be heated to 60 ℃ of stirring and dissolving, add 25g tetramethylolmethane stablizer again; Drip an amount of nitric acid adjustment pH value between 3-4; Stir 1.5h, under agitation drip 70g aminopropyl three ethoxy silane then, drip complete continued and stirred hydrolysis reaction 2 hours; Add water to 1L at last, continuation stirring 2h makes a kind of light yellow transparent liquid and is product.
Method by among the embodiment 1 experimentizes, its effect such as following table:
This product is at room temperature placed and was not become turbid in 6 months.
Embodiment 5
Take by weighing the 50g potassium fluozirconate and the 30g titanyl sulfate joins in the water of 800ml, be heated to 60 ℃ of stirring and dissolving, add 30g tetramethylolmethane stablizer again; Drip an amount of acetate adjustment pH value between 3-4; Stir 2h, under agitation drip 20g aminopropyl three ethoxy silane and 60g four sulfuration triethoxy disilane then, drip complete continued and stirred hydrolysis reaction 2 hours; Add water to 1L at last, continuation stirring 1.5h makes a kind of light yellow transparent liquid and is product.
Method by among the embodiment 1 experimentizes, its effect such as following table:
| Project | Performance |
| 5％CuSO 4Pittingtest | ?5min |
| Handling the surface, back carries out quiet | Sticking power: 0 grade (cross cut test) |
| The electro-powder spray test | Anti-neutral salt spray test: intersect behind stroke fork, put into salt fog cabinet 800h corrosion and spread＜1mm |
| The etching width | ?1±0.5mm |
This product is at room temperature placed and was not become turbid in 6 months.
Embodiment 6
Take by weighing the 80g titanyl sulfate and join in the water of 800ml, be heated to 65 ℃ of stirring and dissolving, add 10g glycerine and 10g terepthaloyl moietie again; Drip appropriate hydrochloric acid adjustment pH value between 3-4; Stir 1.5h, under agitation drip 60g ethyl triethoxy disilane and 30g mercaptopropyltriethoxysilane then, drip complete continued and stirred hydrolysis reaction 2 hours; Add water to 1L at last, continuation stirring 1h makes a kind of light yellow transparent liquid and is product.
Method by among the embodiment 1 experimentizes, its effect such as following table:
This product is at room temperature placed and was not become turbid in 6 months.
Embodiment 7
Take by weighing the 40g potassium fluozirconate and the 40g titanyl sulfate joins in the water of 800ml, be heated to 65 ℃ of stirring and dissolving, add the 5g tetramethylolmethane again; Drip appropriate hydrochloric acid adjustment pH value between 3-4; Stir 1.5h, Dropwise 5 g aminopropyl three ethoxy silane under agitation drip a complete continued and stirred hydrolysis reaction 2 hours then; Add water to 1L at last, continuation stirring 1h makes a kind of light yellow transparent liquid and is product.
Method by among the embodiment 1 experimentizes, its effect such as following table:
This product is at room temperature placed and was not become turbid in 6 months.
Claims (6)
1. one kind is used for the silane matrix material that the coated metal front surface is handled, and it is characterized in that containing in every liter of described silane matrix material the water of 20-80g zirconates and/or titanium salt, 5-30g stablizer, 5-100g silane coupling agent, 1-30ml acid and surplus;
Described zirconates is a fluozirconate;
Described titanium salt is titanyl sulfate or fluotitanate;
Described stablizer is the polyvalent alcohol that contains two above hydroxyls;
Described silane coupling agent comprises the disilane of aminopropyl silane, epoxy radicals silicone hydride, urea propyl silane, vinyl silanes and sulfur-bearing chain or alkyl;
Described acid is acetate, nitric acid or hydrochloric acid.
2. silane matrix material according to claim 1 is characterized in that: contain fluozirconate and titanium salt in the described silane matrix material, its mass ratio is 3:0-5.
3. silane matrix material according to claim 1 is characterized in that: described stablizer is terepthaloyl moietie, glycerine or tetramethylolmethane.
4. silane matrix material according to claim 1 is characterized in that: described stablizer is the mixture of terepthaloyl moietie or glycerine and tetramethylolmethane, and its weight ratio is 1:0.5-1.
5. silane matrix material according to claim 1 is characterized in that: the disilane of described sulfur-bearing chain or alkyl is tetra-sulfurized pair triethoxyl silane, 1,2-diethoxy estersil base ethane.
6. preparation method like arbitrary described silane matrix material among the claim 1-5, step is following:
(1) takes by weighing zirconates and/or titanium salt according to formula ratio, add water and be heated to 60-80oC and make it dissolving, in solution, add the stablizer of formula ratio then, to 3-4, stir 1-2h with the pH value of acid adjustment solution;
(2) silane coupling agent with formula ratio under agitation is added drop-wise in the above-mentioned solution, dropwises continued and stirs 2-3h;
(3) supply the water of surplus according to formula ratio, continue to stir 1-2h and promptly get silane matrix material of the present invention.
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| CN102653861A (en) * | 2012-05-14 | 2012-09-05 | 合肥华清金属表面处理有限责任公司 | Surface treating agent specially used for offshore drilling drill conductor and preparation method thereof |
| CN103074621A (en) * | 2012-08-29 | 2013-05-01 | 华南理工大学 | Environmental-protection cold-rolled steel surface coating pretreatment agent and preparation method thereof |
| CN104046973A (en) * | 2014-06-18 | 2014-09-17 | 上海大学 | Method for preparing alloy passivation film in inorganic and composite manner |
| CN104372323A (en) * | 2014-11-13 | 2015-02-25 | 无锡伊佩克科技有限公司 | Aluminum alloy chromium-free water-based passivator and preparation method thereof |
| CN104988563A (en) * | 2015-07-30 | 2015-10-21 | 南京科润工业介质股份有限公司 | Silane-nanoceramic composite surface conditioning agent |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239908A (en) * | 1996-11-05 | 1999-12-29 | 辛辛那提大学 | Method of preventing corrosion of metal sheet using vinyl silanes |
| CN101701336A (en) * | 2009-11-26 | 2010-05-05 | 芜湖市瑞杰环保材料科技有限公司 | Environment-friendly metal surface treating agent and using method thereof |
-
2011
- 2011-07-11 CN CN2011101925769A patent/CN102337530A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239908A (en) * | 1996-11-05 | 1999-12-29 | 辛辛那提大学 | Method of preventing corrosion of metal sheet using vinyl silanes |
| CN101701336A (en) * | 2009-11-26 | 2010-05-05 | 芜湖市瑞杰环保材料科技有限公司 | Environment-friendly metal surface treating agent and using method thereof |
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| CN102653861A (en) * | 2012-05-14 | 2012-09-05 | 合肥华清金属表面处理有限责任公司 | Surface treating agent specially used for offshore drilling drill conductor and preparation method thereof |
| CN103074621A (en) * | 2012-08-29 | 2013-05-01 | 华南理工大学 | Environmental-protection cold-rolled steel surface coating pretreatment agent and preparation method thereof |
| CN104046973A (en) * | 2014-06-18 | 2014-09-17 | 上海大学 | Method for preparing alloy passivation film in inorganic and composite manner |
| CN104372323A (en) * | 2014-11-13 | 2015-02-25 | 无锡伊佩克科技有限公司 | Aluminum alloy chromium-free water-based passivator and preparation method thereof |
| CN106148930A (en) * | 2015-03-24 | 2016-11-23 | 成都祥瑞化工厂 | A kind of nano-silicon pottery Combined Processing liquid and preparation method thereof |
| CN104988563A (en) * | 2015-07-30 | 2015-10-21 | 南京科润工业介质股份有限公司 | Silane-nanoceramic composite surface conditioning agent |
| CN106119724A (en) * | 2016-06-27 | 2016-11-16 | 滁州帝邦科技有限公司 | A kind of preparation method of the corrosion resisting steel for water-cooled nozzle |
| CN106221565A (en) * | 2016-08-27 | 2016-12-14 | 合肥普庆新材料科技有限公司 | A kind of preparation method of the reinforcing agent for strengthening chromium-free fingerprint-resistant plate powder coating adhesive force |
| CN106835093A (en) * | 2017-02-24 | 2017-06-13 | 武汉大学 | A kind of Q types POSS modified metal surface pretreating reagent and preparation method thereof, application |
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| CN113718240A (en) * | 2021-08-18 | 2021-11-30 | 东风商用车有限公司 | Surface treatment method for magnesium alloy before painting |
| CN115094405A (en) * | 2022-07-13 | 2022-09-23 | 德清县康祺化学品有限公司 | Novel metal coating pretreatment material |
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Application publication date: 20120201 |