CN102719821B - 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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- CN102719821B CN102719821B CN201210120750.3A CN201210120750A CN102719821B CN 102719821 B CN102719821 B CN 102719821B CN 201210120750 A CN201210120750 A CN 201210120750A CN 102719821 B CN102719821 B CN 102719821B
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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 for cold-rolled steel and surface of galvanized steel rot-resistant composite Nano silane film and film thereof.
Two, background technology
Cold-rolled steel and galvanized steel have good mechanical property, and especially good processing characteristics is widely used in manufacturing the fields such as automobile, household electrical appliances, industrial equipments and various engineering machinery.At present, to the more employing chromating of the surface treatment of cold-rolled steel and galvanized steel or method for bonderizing, so that its surface has good solidity to corrosion better with the bonding force of coating.But chromating technology can produce harmful material to human body and environment, still there is subproblem in the corrosion resisting property of phosphatize phosphate coat and self-healing property, and the water resources that its waste water after treatment is depended on for existence to the mankind has a significant impact.Therefore seek green and efficiently process for treating surface seem particularly important.Adopting silane film to carry out pre-treatment to metallic surface is a kind of novel green environmental protection technique, is more and more subject to people's attention, and recent year has had relevant report.Had some researchs although galvanized steel is carried out to surface preparation with silane, the corrosion resistance nature that improves surface of galvanized steel by γ-aminopropyl methyldiethoxysilane report is at home little.Carry out surface anticorrosion processing and substitute phosphatize phosphate coat with composite Nano γ-aminopropyl methyldiethoxysilane film on cold-rolled steel and galvanized steel, at home and abroad also do not appear in the newspapers so far.
Three, summary of the invention
The present invention is directed to the antiseptic deficiency of existing cold-rolled steel and 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, after making γ-aminopropyl methyldiethoxysilane concentration expressed in percentage by volume reach 1-30%, adjust pH 8-13, add again the nano material of activation stir and at 10-70 DEG C, be hydrolyzed the silanol solution forming, then the metal of handling well is immersed to the appropriate time, can generate in metallic surface composite Nano silane film, in every liter of silane hydrolyzate solution, add 10-500 milligram activation nano material.
Described γ-aminopropyl methyldiethoxysilane is colourless transparent liquid, and boiling point 85-88 DEG C is of many uses, is universal tackifier, is again the even stick of good silane etc.Committed step in this film forms is the silane hydrolyzate technique 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 again the nano material of activation, nano material add-on is that every liter of silane hydrolyzate solution adds 10-500 milligram, and stirs.Then within 1-60 hour, obtain composite Nano silanol solution 10-70 DEG C of Water Under solution.
Described nano material is selected from nanometer SiO
2or/and nanometer Al
2o
3.
Described activation is by nanometer SiO
2put into sulfuric acid: water=1: the solution of 1 (volume ratio) soaks 5-10 minute (min), after taking out, water repetitive scrubbing is 7 left and right to pH, then 600 DEG C of roastings naturally cool to room temperature after (h) in 2 hours in retort furnace.
Nanometer Al
2o
3activation: 600 DEG C of roastings 2 hours in retort furnace, naturally cooling, takes out for subsequent use.
The film of this composite Nano silane film, described film forming refers in process rust cleaning, oil removing, cold rolling steel part after cleaning or the surface filming of galvanized steel parts, this film comprises the surface treatment of metalwork, hydrolysis, dipping and dry, 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%, make the concentration expressed in percentage by volume of γ-aminopropyl methyldiethoxysilane reach 1-30%, stir and adjust pH 8-13 after, add again the nano material of activation, nano material add-on is that every liter of silane hydrolyzate solution adds 10-500 milligram, and stir.Then within 1-60 hour, can obtain composite Nano silanol solution 10-70 DEG C of Water Under solution.Described dip-coating is in the cold rolling steel part after surface treatment or the above-mentioned solution of galvanized steel parts submergence, to be no less than 3 minutes, dip-coating finishes rear taking-up metal parts and is dried, described dry be the loft drier that the metal after dip-coating is placed in to certain temperature, constant temperature certain hour.Dry condition is: temperature 20-150 DEG C, 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 activate 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 temperature is low, the time is longer, and height is shorter.
This composite Nano silane film antiseptic property is very excellent.In the time that 3.5%NaCl solution Anodic polarization curve overpotential reaches 700mV, corrosion current is still almost nil.
Four, brief description of the drawings
Fig. 1 provides respectively surface to be had, anodic polarization curves without the cold-rolled steel sample of composite Nano silane film in the 3.5%NaCl aqueous solution of 30 DEG C, and scanning speed is 1mv/s.
No. 0 curve is the polarized potential of cold-rolled steel sample and the relation of corrosion current without composite Nano silane film;
D curve is the polarized potential of cold-rolled steel sample and the relation of corrosion current that has composite Nano silane film.
Fig. 2 provides respectively surface and has the cold-rolled steel sample polarization corrosion of composite Nano silane film that (in the 3.5%NaCl aqueous solution of 30 DEG C, scanning speed is 1mv/s, and anodic polarization overpotential is 0.7V.) before and after electron scanning micrograph.
(a) figure is the SEM photo of cold-rolled steel sample before corrosion that there is a composite Nano silane film on surface;
(b) figure is the SEM photo of cold-rolled steel sample after corrosion that there is a composite Nano silane film on surface.
Fig. 3 provides respectively surface to be had, anodic polarization curves without the galvanized steel sample of composite Nano silane film in the 3.5%NaCl aqueous solution of 30 DEG C, and scanning speed is 1mv/s.
No. 0 curve is the polarization overpotential of galvanized steel sample and the relation of corrosion current without composite Nano silane film;
D curve is the polarization overpotential of galvanized steel sample and the relation of corrosion current that has composite Nano silane film.
Fig. 4 provides respectively surface and has the galvanized steel sample polarization corrosion of composite Nano silane film that (in the 3.5%NaCl aqueous solution of 30 DEG C, scanning speed is 1mv/s, and 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 a composite Nano silane film on surface;
(B) figure is the SEM photo of galvanized steel sample after corrosion that there is a composite Nano silane film on surface.
Five, embodiment
Non-limiting examples is described below.
(1) surface treatment of cold-rolled steel and galvanized steel
Cold-rolled steel surface treatment: polishing → cleaning → oil removing → cleaning → except oxide compound → cleaning
Surface of galvanized steel processing: oil removing → cleaning → except oxide compound → cleaning
(2) activation of nano material
1, nanometer SiO
2activation: nano material is put into sulfuric acid: water=1: the solution of 1 (volume ratio) soaks 5-10 minute (min), after taking out, water repetitive scrubbing is until pH is 7 left and right, put into again 600 DEG C of roastings of retort furnace and after (h), naturally cool to room temperature in 2 hours, take out for subsequent use.
2, nanometer Al
2o
3activation: in retort furnace, 600 DEG C of roastings naturally cool to room temperature after (h) in 2 hours, take out for subsequent use.
(3) metalwork surface filming
Embodiment 1:
Get liquid γ-aminopropyl methyldiethoxysilane 5ml and join in the mixing solutions of dehydrated alcohol 20ml deionized water 175ml, stir, regulating pH value is 11, then adds 50 milligrams of nano materials after activated, is uniformly mixed.At 50 DEG C, constant temperature hydrolysis 20 hours, obtains composite Nano silanol solution, stand-by.The cold-rolled steel matrix handled well is immersed in the silanol solution after hydrolysis 20 minutes, in 120 DEG C of drying in oven 0.5 hour and get final product.
Embodiment 2:
Getting liquid γ-aminopropyl methyldiethoxysilane 10ml joins in the mixing solutions of dehydrated alcohol 10ml deionized water 180ml, stir, regulating pH is 12, add again 40 milligrams of activated nano materials, after stirring, at 40 DEG C, constant temperature hydrolysis 25 hours, obtains composite Nano silanol solution, stand-by.The galvanized steel matrix handled well is immersed in the silanol solution after hydrolysis 30 minutes, in 90 DEG C of drying in oven 2 hours and get final product.
Embodiment 3:
Getting liquid γ-aminopropyl methyldiethoxysilane 2ml joins in the mixing solutions of dehydrated alcohol 15ml deionized water 183ml, stir, regulate pH value approximately 9, add again 100 milligrams of activated nano materials, after stirring, at 30 DEG C, constant temperature hydrolysis 30 hours, obtains composite Nano silanol solution, stand-by.The galvanized steel matrix handled well is immersed in the composite Nano silanol solution after hydrolysis 40 minutes under 25 DEG C of room temperatures dry 20 hours and get final product.
Embodiment 4:
Get liquid γ-aminopropyl methyldiethoxysilane 25ml and join in the mixing solutions of dehydrated alcohol 60ml deionized water 115ml, stir, regulating pH value is 8, then adds 2 milligrams of nano materials after activated, is uniformly mixed.At 10 DEG C, constant temperature hydrolysis 60 hours, obtains composite Nano silanol solution, stand-by.The cold-rolled steel matrix handled well is immersed in the silanol solution after hydrolysis 50 minutes, in 50 DEG C of drying in oven 8 hours and get final product.
Embodiment 5:
Get liquid γ-aminopropyl methyldiethoxysilane 40ml and join in the mixing solutions of dehydrated alcohol 50ml deionized water 110ml, stir, regulating pH value is 13, then adds 10 milligrams of nano materials after activated, is uniformly mixed.At 20 DEG C, constant temperature hydrolysis 48 hours, obtains composite Nano silanol solution, stand-by.The cold-rolled steel matrix handled well is immersed in the silanol solution after hydrolysis 15 minutes, in 80 DEG C of drying in oven 4 hours and get final product.
Embodiment 6:
Get liquid γ-aminopropyl methyldiethoxysilane 60ml and join in the mixing solutions of dehydrated alcohol 56ml deionized water 84ml, stir, regulating pH value is 10, then adds 20 milligrams of nano materials after activated, is uniformly mixed.At 65 DEG C, constant temperature hydrolysis 5 hours, obtains composite Nano silanol solution, stand-by.The cold-rolled steel matrix handled well is immersed in the silanol solution after hydrolysis 10 minutes, in 40 DEG C of drying in oven 10 hours and get final product.
Claims (1)
1. the film for metallic surface rot-resistant composite Nano silane film, comprise the surface treatment of metalwork, hydrolysis, dipping and dry, it is characterized in that: described hydrolysis is that γ-aminopropyl methyldiethoxysilane 10ml is joined to dehydrated alcohol 10ml, in the mixing solutions of deionized water 180ml, stir, regulating pH is 12, add again 40 milligrams of activated nano materials, after stirring, constant temperature hydrolysis 25 hours at 40 DEG C, obtain composite Nano silanol solution, the galvanized steel matrix handled well is immersed in the silanol solution after hydrolysis 30 minutes, after taking-up in 90 DEG C of drying in oven 2 hours,
Described nano material is selected from nanometer SiO
2or/and nanometer Al
2o
3; Described nanometer SiO
2activation be to put it into sulfuric acid: water volume ratio is: in the solution of 1:1, soak 5-10 minute, after taking out, water repetitive scrubbing is 7 to pH, then 600 DEG C of roastings naturally cooled to room temperature after 2 hours in retort furnace; Described nanometer Al
2o
3activation be that its 600 DEG C of roastings in retort furnace were naturally cooled to room temperature after 2 hours.
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| CN201210120750.3A CN102719821B (en) | 2012-04-23 | 2012-04-23 | Composite nanometer silane film for preventing corrosion on metal surface and film forming method thereof |
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| CN102719821B true CN102719821B (en) | 2014-12-03 |
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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 |
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| 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 |
| 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 |
| CN107829086B (en) * | 2017-11-08 | 2019-11-26 | 安徽腾龙泵阀制造有限公司 | A kind of pump anticorrosion treatment technology of aluminium alloy part |
| 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 |
| 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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