CN102719821A - Composite nanometer silane film for preventing corrosion on metal surface and film forming method thereof - Google Patents
Composite nanometer silane film for preventing corrosion on metal surface and film forming method thereof Download PDFInfo
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- CN102719821A CN102719821A CN2012101207503A CN201210120750A CN102719821A CN 102719821 A CN102719821 A CN 102719821A CN 2012101207503 A CN2012101207503 A CN 2012101207503A CN 201210120750 A CN201210120750 A CN 201210120750A CN 102719821 A CN102719821 A CN 102719821A
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Abstract
Disclosed is a composite nanometer silane film for preventing corrosion on metal surfaces. The composite nanometer silane film is prepared by the steps of: adding Gamma- aminopropyl methyl diethoxysilane in ethanol-water solution with a volume percentage concentration of 1-40% and mixing to enable the volume percentage concentration of silane to reach 1-30%; adjusting the pH value to 8-13, adding activated nanometer materials SiO2 or/and Al2O3, stirring evenly and carrying out hydrolysis at a temperature of 10-70 DEG C to form silanol solution; and then immersing the treated metal in the silanol solution for a proper amount of time to generate a composite nanometer silane film on the surface of the metal, wherein 10-500 milligrams of activated nanometer material are added in every liter of silane hydrolysis solution. The composite nanometer silane film has excellent performance on corrosion preventing, and corrosion current is almost zero when the overpotential of an anodizing curve reaches 700mV in 3.5% NaCl solution.
Description
One, technical field
The present invention relates to the corrosion prevention film of metallic surface, particularly be used for CRS and surface of galvanized steel rot-resistant composite Nano silane film and film thereof.
Two, background technology
CRS and galvanized steel have good mechanical property, and especially good processing properties is widely used in making fields such as automobile, household electrical appliances, industrial equipments and various engineering machinery.At present, to more employing chromating of the surface treatment of CRS and galvanized steel or method for bonderizing, so that its surface has good solidity to corrosion and better with coating's adhesion.But the chromating technology can produce deleterious material to human body and environment, and still there are subproblem in the corrosion resisting property of phosphatize phosphate coat and self-healing property, and the water resources that the waste water after it is handled is depended on for existence to the mankind has very big influence.Therefore seek green and efficiently process for treating surface seem particularly important.Adopting silane film that pre-treatment is carried out in the metallic surface is a kind of novel green environmental protection technique, more and more receives people's attention, and domestic in recent years had a relevant report.Though galvanized steel is carried out surface preparation some researchs have been arranged, used corrosion resistance nature report at home that γ-aminopropyl methyldiethoxysilane improves surface of galvanized steel seldom with silane.Carry out the surface anticorrosion processing and on CRS and galvanized steel, substitute phosphatize phosphate coat, at home and abroad also do not appear in the newspapers so far with composite Nano γ-aminopropyl methyldiethoxysilane film.
Three, summary of the invention
The present invention is directed to existing CRS and the antiseptic deficiency of surface of galvanized steel, the composite Nano silane film that aims to provide a kind of environment-friendly type carries out anticorrosion, and technical problem to be solved is to select suitable silane and film thereof.
The alleged composite Nano silane film of the present invention is to be added in the aqueous ethanolic solution of concentration expressed in percentage by volume 1-40% by γ-aminopropyl methyldiethoxysilane; γ-aminopropyl methyldiethoxysilane concentration expressed in percentage by volume is reached add again behind 1-30%, the adjust pH 8-13 silanol solution that the activatory nano material stirs and form in 10-70 ℃ of following hydrolysis; Then the metal of handling well is immersed the wherein an amount of time; Can generate the composite Nano silane film in the metallic surface, add 10-500 milligram activation nano material in every liter of silane hydrolyzate solution.
Described γ-aminopropyl methyldiethoxysilane is a colourless transparent liquid, boiling point 85-88 ℃, and of many uses, be universal tackifier, be again good silane idol stick etc.Committed step in this film forms is the silane hydrolyzate technology in early stage; γ-aminopropyl methyldiethoxysilane is added in the aqueous ethanolic solution of concentration expressed in percentage by volume 1-40%; Make the concentration expressed in percentage by volume of γ-aminopropyl methyldiethoxysilane reach 1-30%, stir and adjust pH 8-13 after, add the activatory nano material again; The nano material add-on is that every liter of silane hydrolyzate solution adds the 10-500 milligram, and stirs.Under 10-70 ℃ of condition, promptly got composite Nano silanol solution then in hydrolysis 1-60 hour.
Described nano material is selected from nanometer SiO
2Or/and nanometer Al
2O
3
Described activation is with nanometer SiO
2Put into sulfuric acid: the solution of water=1: 1 (volume ratio) soaks 5-10 minute (min), and taking out back water repetitive scrubbing is about 7 to pH, and 600 ℃ of roastings naturally cooled to room temperature after (h) in 2 hours in retort furnace again.
Nanometer Al
2O
3Activation: 600 ℃ of roastings are 2 hours in retort furnace, and naturally cooling takes out subsequent use.
The film of this composite Nano silane film; Described film forming is meant through the cold rolling steel part after the rust cleaning, oil removing, cleaning or the surface filming of galvanized steel parts; This film comprises surface treatment, hydrolysis, dipping and the drying of metalwork, and difference with the prior art is that described hydrolysis is that γ-aminopropyl methyldiethoxysilane is added in the aqueous ethanolic solution of concentration expressed in percentage by volume 1-40%, makes the concentration expressed in percentage by volume of γ-aminopropyl methyldiethoxysilane reach 1-30%; Stir and adjust pH 8-13 after; Add the activatory nano material again, the nano material add-on is that every liter of silane hydrolyzate solution adds the 10-500 milligram, and stirs.Under 10-70 ℃ of condition, can obtain composite Nano silanol solution in hydrolysis 1-60 hour then.Described dip-coating is with being no less than 3 minutes in cold rolling steel part after surface treatment or the above-mentioned solution of galvanized steel parts submergence; Dip-coating finishes back taking-up metal parts and carries out drying; Described drying is the loft drier that the metal after the dip-coating is placed certain temperature, the constant temperature certain hour.The exsiccant condition is: temperature 20-150 ℃, the time is 20-1200 minute.Just form the fine and close composite Nano silane film uniformly of one deck on the surface of metal works.
Described nano material and activation thereof are the same.
The time of silane hydrolyzate is relevant with pH value and temperature, when one timing of pH value, and hydrolysis time and temperature inverse correlation, when promptly temperature was low, the time was longer, and height is then short.
This composite Nano silane film antiseptic property is very excellent.Corrosion current was still almost nil when the anodic polarization curves overpotential reached 700mV in 3.5%NaCl solution.
Four, description of drawings
Fig. 1 provides the surface respectively to be had, the anodic polarization curves of CRS sample in 30 ℃ the 3.5%NaCl aqueous solution of no composite Nano silane film, and scanning speed is 1mv/s.
No. 0 curve is the polarized potential of the CRS sample of no composite Nano silane film and the relation of corrosion current;
The d curve is polarized potential and the relation of corrosion current that the CRS sample of composite Nano silane film is arranged.
Fig. 2 provides the surface respectively the CRS sample polarization corrosion of composite Nano silane film is arranged that (in 30 ℃ the 3.5%NaCl aqueous solution, scanning speed is 1mv/s, and the anodic polarization overpotential is 0.7V.) before and after electron scanning micrograph.
(a) figure is the SEM photo of CRS sample before corrosion that there is the composite Nano silane film on the surface;
(b) figure is the SEM photo of CRS sample after corrosion that there is the composite Nano silane film on the surface.
Fig. 3 provides the surface respectively to be had, the anodic polarization curves of galvanized steel sample in 30 ℃ the 3.5%NaCl aqueous solution of no composite Nano silane film, and scanning speed is 1mv/s.
No. 0 curve is the polarization overpotential of the galvanized steel sample of no composite Nano silane film and the relation of corrosion current;
The D curve is polarization overpotential and the relation of corrosion current that the galvanized steel sample of composite Nano silane film is arranged.
Fig. 4 provides the surface respectively the galvanized steel sample polarization corrosion of composite Nano silane film is arranged that (in 30 ℃ the 3.5%NaCl aqueous solution, scanning speed is 1mv/s, and the anodic polarization overpotential is 0.7V.) before and after electron scanning micrograph.
(A) figure is the SEM photo of galvanized steel sample before corrosion that there is the composite Nano silane film on the surface;
(B) figure is the SEM photo of galvanized steel sample after corrosion that there is the composite Nano silane film on the surface.
Five, embodiment
The non-limiting examples narration as follows.
(1) surface treatment of CRS and galvanized steel
The CRS surface treatment: polishing → cleaning → oil removing → cleaning → except that oxide compound → cleaning
Surface of galvanized steel is handled: oil removing → cleaning → and except that oxide compound → cleaning
(2) activation of nano material
1, nanometer SiO
2Activation: nano material is put into sulfuric acid: the solution of water=1: 1 (volume ratio) soaks 5-10 minute (min); Taking out back water repetitive scrubbing is about 7 until pH; Put into 600 ℃ of roastings of retort furnace again and naturally cooled to room temperature after (h) in 2 hours, take out subsequent use.
2, nanometer Al
2O
3Activation: 600 ℃ of roastings naturally cooled to room temperature after (h) in 2 hours in retort furnace, took out subsequent use.
(3) metalwork surface filming
Embodiment 1:
Get liquid γ-aminopropyl methyldiethoxysilane 5ml and join in the mixing solutions of absolute ethyl alcohol 20ml deionized water 175ml, stir, regulating the pH value is 11, adds 50 milligrams of nano materials after activated again, mixes.50 ℃ of following constant temperature hydrolysis 20 hours, obtain composite Nano silanol solution, for use.The CRS matrix handled well was immersed in the silanol solution after the hydrolysis 20 minutes, promptly got in 0.5 hour in 120 ℃ of drying in oven.
Embodiment 2:
Getting liquid γ-aminopropyl methyldiethoxysilane 10ml joins in the mixing solutions of absolute ethyl alcohol 10ml deionized water 180ml; Stir, regulating pH is 12, adds 40 milligrams of activated nano materials again; After stirring; 40 ℃ of following constant temperature hydrolysis 25 hours, obtain composite Nano silanol solution, for use.The galvanized steel matrix handled well was immersed in the silanol solution after the hydrolysis 30 minutes, promptly got in 2 hours in 90 ℃ of drying in oven.
Embodiment 3:
Getting liquid γ-aminopropyl methyldiethoxysilane 2ml joins in the mixing solutions of absolute ethyl alcohol 15ml deionized water 183ml; Stir, it is about 9 to regulate the pH value, adds 100 milligrams of activated nano materials again; After stirring; 30 ℃ of following constant temperature hydrolysis 30 hours, obtain composite Nano silanol solution, for use.The galvanized steel matrix handled well was immersed in the composite Nano silanol solution after the hydrolysis 40 minutes, under 25 ℃ of room temperatures, promptly got in dry 20 hours.
Embodiment 4:
Get liquid γ-aminopropyl methyldiethoxysilane 25ml and join in the mixing solutions of absolute ethyl alcohol 60ml deionized water 115ml, stir, regulating the pH value is 8, adds 2 milligrams of nano materials after activated again, mixes.10 ℃ of following constant temperature hydrolysis 60 hours, obtain composite Nano silanol solution, for use.The CRS matrix handled well was immersed in the silanol solution after the hydrolysis 50 minutes, promptly got in 8 hours in 50 ℃ of drying in oven.
Embodiment 5:
Get liquid γ-aminopropyl methyldiethoxysilane 40ml and join in the mixing solutions of absolute ethyl alcohol 50ml deionized water 110ml, stir, regulating the pH value is 13, adds 10 milligrams of nano materials after activated again, mixes.20 ℃ of following constant temperature hydrolysis 48 hours, obtain composite Nano silanol solution, for use.The CRS matrix handled well was immersed in the silanol solution after the hydrolysis 15 minutes, promptly got in 4 hours in 80 ℃ of drying in oven.
Embodiment 6:
Get liquid γ-aminopropyl methyldiethoxysilane 60ml and join in the mixing solutions of absolute ethyl alcohol 56ml deionized water 84ml, stir, regulating the pH value is 10, adds 20 milligrams of nano materials after activated again, mixes.65 ℃ of following constant temperature hydrolysis 5 hours, obtain composite Nano silanol solution, for use.The CRS matrix handled well was immersed in the silanol solution after the hydrolysis 10 minutes, promptly got in 10 hours in 40 ℃ of drying in oven.
Claims (4)
1. one kind is used for metallic surface rot-resistant composite Nano silane film; It is characterized in that: γ-aminopropyl methyldiethoxysilane is added to mix in the concentration expressed in percentage by volume 1-40% aqueous ethanolic solution γ-aminopropyl methyldiethoxysilane concentration expressed in percentage by volume is reached add again behind 1-30%, the adjust pH 8-13 that the activatory nano material stirs and in the composite Nano silane film that the silanol solution that 10-70 ℃ of following hydrolysis forms generates in the metallic surface, add 10-500 milligram activation nano material in every liter of silane hydrolyzate solution.
2. composite Nano silane film according to claim 1 is characterized in that: described nano material is selected from nanometer SiO
2Or/and nanometer Al
2O
3
3. the film of a composite Nano silane film as claimed in claim 1; The surface treatment, hydrolysis, dipping and the drying that comprise metalwork; It is characterized in that: described hydrolysis is that γ-aminopropyl methyldiethoxysilane is added in the aqueous ethanolic solution of concentration expressed in percentage by volume 1-40%; Make the concentration expressed in percentage by volume of γ-aminopropyl methyldiethoxysilane reach 1-30%, stir and adjust pH 8-13, and then add the activatory nano material; The quality that adds nano material by every liter of silane hydrolyzate solution is the 10-500 milligram and need stirs, under 10-70 ℃ of condition hydrolysis 1-60 hour.
4. film according to claim 3 is characterized in that: described nano material is selected from nanometer SiO
2Or/and nanometer Al
2O
3
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Cited By (11)
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| CN103468205A (en) * | 2013-09-23 | 2013-12-25 | 无锡阳工机械制造有限公司 | Polishing anticorrosion slurry for metal tools |
| CN103484866A (en) * | 2013-09-23 | 2014-01-01 | 无锡阳工机械制造有限公司 | Polishing anti-corrosion slurry |
| CN103484865A (en) * | 2013-09-23 | 2014-01-01 | 无锡阳工机械制造有限公司 | Metal polishing and corrosion-resistant slurry |
| CN105039954A (en) * | 2015-06-04 | 2015-11-11 | 芜湖金龙模具锻造有限责任公司 | Preparation method for steel surface treatment agent |
| CN106756968A (en) * | 2016-12-22 | 2017-05-31 | 山东宝龙达新材料有限公司 | Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film |
| CN107475706A (en) * | 2017-06-26 | 2017-12-15 | 安徽雷萨重工机械有限公司 | A kind of surface treatment method for lifting aluminium alloy and using characteristic |
| CN107829086A (en) * | 2017-11-08 | 2018-03-23 | 安徽腾龙泵阀制造有限公司 | A kind of anticorrosion treatment technology of pump aluminium alloy part |
| CN111054605A (en) * | 2019-12-31 | 2020-04-24 | 天长市飞龙金属制品有限公司 | Metal material surface treatment method |
| CN111893486A (en) * | 2020-07-15 | 2020-11-06 | 浙江华电器材检测研究所有限公司 | Method for preparing silane conversion coating with cathodic protection effect on aluminum alloy surface |
| CN113088188A (en) * | 2021-03-31 | 2021-07-09 | 上海应用技术大学 | Hydrophobic nanoparticle-based super-hydrophobic silane membrane and preparation and application thereof |
| CN114000133A (en) * | 2021-10-22 | 2022-02-01 | 江西卓美金属制品有限公司 | Zinc steel fence and preparation method thereof |
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| CN103484866B (en) * | 2013-09-23 | 2016-05-18 | 无锡阳工机械制造有限公司 | A kind of polishing anti-corrosive pulp |
| CN103468205A (en) * | 2013-09-23 | 2013-12-25 | 无锡阳工机械制造有限公司 | Polishing anticorrosion slurry for metal tools |
| CN103484865A (en) * | 2013-09-23 | 2014-01-01 | 无锡阳工机械制造有限公司 | Metal polishing and corrosion-resistant slurry |
| CN103468205B (en) * | 2013-09-23 | 2015-09-09 | 无锡阳工机械制造有限公司 | A kind of polishing anti-corrosive pulp for iron tool |
| CN103484865B (en) * | 2013-09-23 | 2016-04-13 | 无锡阳工机械制造有限公司 | A kind of medal polish anti-corrosive pulp |
| CN103484866A (en) * | 2013-09-23 | 2014-01-01 | 无锡阳工机械制造有限公司 | Polishing anti-corrosion slurry |
| CN105039954A (en) * | 2015-06-04 | 2015-11-11 | 芜湖金龙模具锻造有限责任公司 | Preparation method for steel surface treatment agent |
| CN106756968A (en) * | 2016-12-22 | 2017-05-31 | 山东宝龙达新材料有限公司 | Protective treatment method of aluminum alloy surface is carried out with nano modification silicon systems composite passivation film |
| CN107475706A (en) * | 2017-06-26 | 2017-12-15 | 安徽雷萨重工机械有限公司 | A kind of surface treatment method for lifting aluminium alloy and using characteristic |
| CN107829086A (en) * | 2017-11-08 | 2018-03-23 | 安徽腾龙泵阀制造有限公司 | A kind of anticorrosion treatment technology of pump aluminium alloy part |
| CN111054605A (en) * | 2019-12-31 | 2020-04-24 | 天长市飞龙金属制品有限公司 | Metal material surface treatment method |
| CN111054605B (en) * | 2019-12-31 | 2023-01-10 | 天长市飞龙金属制品有限公司 | Metal material surface treatment method |
| CN111893486A (en) * | 2020-07-15 | 2020-11-06 | 浙江华电器材检测研究所有限公司 | Method for preparing silane conversion coating with cathodic protection effect on aluminum alloy surface |
| CN113088188A (en) * | 2021-03-31 | 2021-07-09 | 上海应用技术大学 | Hydrophobic nanoparticle-based super-hydrophobic silane membrane and preparation and application thereof |
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