CN102503554B - Method for preparing oil-water-soaked light-operated reversible SiO2/TiO2 composite coating on silicon substrate surface - Google Patents
Method for preparing oil-water-soaked light-operated reversible SiO2/TiO2 composite coating on silicon substrate surface Download PDFInfo
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- CN102503554B CN102503554B CN 201110342473 CN201110342473A CN102503554B CN 102503554 B CN102503554 B CN 102503554B CN 201110342473 CN201110342473 CN 201110342473 CN 201110342473 A CN201110342473 A CN 201110342473A CN 102503554 B CN102503554 B CN 102503554B
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Abstract
The invention discloses a method for preparing an oil-water-soaked light-operated reversible SiO2/TiO2 composite coating on a silicon substrate surface. The method comprises the following steps of: soaking a silicon substrate sample cleaned with a sulfuric acid wash solution into SiO2 gel; pulling out of a liquid level at the uniform speed of 14 centimeters per minute; covering a uniform SiO2 coating on a glass surface; calcining the coating at the temperature of 220 DEG C; soaking an obtained sample which is covered with the SiO2 coating into TiO2 gel; pulling out of the liquid level at the uniform speed of 14 centimeters per minute; calcining the coating at the temperature of 500 DEG C; and soaking into a silicon fluoride solution and performing surface modification on the coating to obtain the light-operated reversible SiO2/TiO2 composite coating. Compared with the conventional method for preparing a hydrophilic/hydrophobic and oleophylic/oleophobic reversible transition material, the method has the advantages of easiness, convenience, low time consumption and no need of special instrument. The coating has a structure in which the lotus-like surface of a micro SiO2 microsphere is coated with a nano-TiO2 microsphere, and has a good application prospect in the engineering field.
Description
Technical field
The present invention relates to the chemical industry functional materials, especially coating material is made the field.
Background technology
Because TiO
2Physics, chemical property and Photoinitiation Property so that TiO
2With contain TiO
2Surfacing have important using value, wherein based on TiO
2The conversion of light-operated close and distant water significant for making up self-cleaning material, regulation and control microfluidic flow direction and improving sensor performance.From reporting out under ultraviolet lighting nano-TiO for the first time
2Plane of crystal can become hydrophilic, has transferred since postpone can hydrophobicity occur again again in dark, and the research of light-operated parent/hydrophobic conversion emerges in an endless stream.Along with TiO
2Light-operated parent/hydrophobic conversion performance research go deep into TiO
2In the life of reality and industry, use more and more extensive, to TiO
2Light-operated close and distant water conversion performance is had higher requirement, and investigators also are devoted to finding method always and strengthen TiO
2Light-operated parent/hydrophobic conversion.A kind of method is to change TiO
2Surface topography, another kind of method is at TiO
2The surface add organism.Also have in addition the investigator that two kinds of methods are combined, prepare coarse TiO with photoetching technique
2The surface, and connect from the teeth outwards compound, so that TiO
2The hydrophilic and hydrophobic on surface is converted to further enhancing.But obtain at present TiO
2The method of surface irregularity pattern all is to adopt plasma or photoetching technique that inorganic material surface is carried out etching, and making method is loaded down with trivial details, and running cost is expensive, and being subject to the Restricted requirement such as environmental unit can't field conduct.The coating research that possesses simultaneously at present light-operated close and distant water and close and distant oily reversible transformation yet there are no report, and the parent of material surface/oleophobic conversion characteristic has significant application value in fields such as petrochemical complex, material of construction, harmless conveying, biochips.
Based on above deficiency, if adopt simple sol-gel method, with SiO
2Microballoon and TiO
2Nano particle deposits to inorganic material surface successively, constructing the micron silicon ball is substrate, the nano-titanium ball is deposited on the surface recombination micro nano structure on the silicon ball, and then with silicon fluoride this kind composite micro-nano rice body structure surface is carried out modification, certainly will strengthen the reversible transformation of the light-operated close and distant water in surface and close and distant oil.But yet there are no SiO so far,
2/ TiO
2Composite micro-nano rice coating and silicon fluoride chemical modification combine the relevant report for preparing light-operated profit wetting property reversible transformation compound coating.
Summary of the invention
In view of the above deficiency of prior art, the present invention aims to provide a kind of SiO of light-operated profit wetting property reversible transformation
2/ TiO
2Compound coating and preparation method make it to overcome the above shortcoming of prior art.
Purpose of the present invention realizes by following means.
A kind of at silicon matrix surface preparation profit wetting property light-operated reversible SiO
2/ TiO
2The method of compound coating, adopt following step:
(a) the silicon matrix device covers SiO
2Coating: each component volume ratio is ammoniacal liquor in the reaction solution: ethanol: tetraethoxy=30: 50: 3; Be first that 25% ammoniacal liquor is added drop-wise in the dehydrated alcohol of 60 ℃ of constant temperature with mass ratio, slowly drip again tetraethoxy, continue to keep 60 ℃ of constant temperature to stir and obtained SiO in 90 minutes
2Gel; The silicon matrix sample of the cleaning that sulfuric acid lotion was cleaned immerses described SiO
2In the gelating soln 2 minutes, lift out liquid level with the speed of 5～14 cm per minute, afterwards 200～220 ℃ of bakings 20 seconds, 220 ℃ of calcinings are 2 hours again, take out after the cooling and clean, and obtain being covered with SiO
2The silicon matrix sample of coating.
(b) SiO
2/ TiO
2The preparation of compound coating: each component volume ratio is butyl (tetra) titanate in the reaction solution: ethanol: water: Glacial acetic acid=9: 36: 12: 40; It is in 95% the ethanolic soln that butyl (tetra) titanate reagent is added volume percent, after mixing, be added drop-wise in the deionized water and Glacial acetic acid mixing solutions under the whipped state, in room temperature, continue to stir, until mixed solution is by muddy bleach, after leave standstill and obtained TiO in 30 hours
2Gel; Get the described SiO of being covered with that (a) obtains
2The silicon matrix sample of coating immerses TiO
2In the gel 2 minutes, lift out liquid level with the speed of 5～14 cm per minute, after drying up with cold wind, 220 ℃ of bakings 20 seconds, sample was taken out in 450～500 ℃ of calcinings in 30 minutes again.
(c) SiO
2/ TiO
2The modification of compound coating: get the sample that (b) step obtains, be immersed in an amount of silicon fluoride solution, place dark place to take out after 30～40 minutes, placed 15～20 minutes in the dark place, after surperficial seasoning, namely get target product.
Adopt the inventive method to obtain the SiOX/TiO of light-operated profit wetting property reversible transformation
2The invention product of compound coating, have the light-operated close and distant water of good ultraviolet and close and distant oily reversible transformation ability, faint ultraviolet luminous energy causes the conversion of 140 °/30 ° of coatingsurface and water contact angles, with the conversion of 100 °/30 ° of kerosene contact angles, and the conversion of above-mentioned light-operated wetting property is through repeatedly repeatedly still unattenuated after ultraviolet/dark cycle.The method that in the past prepared the close and distant oily reversible transformation material of close and distant water is compared, and the preparation method of this coating is easier, and it is few to expend time in, and does not need specific apparatus, also is applicable to the preparation of other inorganic material coating.Coating presents nano-TiO
2Microballoon parcel micron SiO
2The class lotus leaf surface structure of microballoon has a good application prospect in engineering field.This kind coated material mainly is hydroxyl and the SiO that relies on material surface
2, TiO
2Be combined micron order SiO by chemical bonded refractory
2Microballoon arrived substrate surface, then TiO by electroless plating before this
2Nano particle is wrapped in SiO again
2Microsphere surface is so coating has composite micro-nano rice structure, as shown in drawings.After the silicon fluoride modification, the significant part of material hydrophobic oleophobic is the F element, and this group has stronger hydrophobic oleophobic performance; That on the other hand, play wetting property switch transition function is TiO
2, UV-irradiation makes it produce both hole and electron, brings out near the H of coating
2O becomes hydroxyl; Moreover the constructed class lotus leaf composite micro-nano rice structure of coating so that surface oil water logging lubricant nature transfer capability further strengthen.
Description of drawings is as follows:
Accompanying drawing is the field emission electromicroscopic photograph of product of the present invention.
Embodiment
Below in conjunction with accompanying drawing enforcement of the present invention is further described.But should be emphasized that following embodiment is exemplary, rather than in order to limit the scope of the invention and to use.Related chemical feedstocks and reagent are conventional commercially available technical pure in the processing step.
Embodiment 1
(a) SiO
2The preparation of coating: the ammoniacal liquor of the commercially available mass ratio 25% of 30ml is added drop-wise in the 50ml dehydrated alcohol, and 60 ℃ of constant temperature stirred 30 minutes, and the tetraethoxy that slowly drips 3ml again continues to keep 60 ℃ of constant temperature to stir and can get SiO in 90 minutes in mentioned solution
2Gel.The sulfuric acid lotion (7: 3 by volume ratio of the vitriol oil and hydrogen peroxide is mixed) that commercially available slide glass is put into 90 ℃ soaked 30 minutes, took out slide glass, and behind the deionized water rinsing, acetone is cleaned, and cold wind dries up.Then slide glass is immersed SiO
2In the gelating soln after 2 minutes, lift out liquid level with the speed of 14 cm per minute.After lifting out liquid level fully, this slide is placed horizontally in the retort furnace, 220 ℃ were toasted 20 seconds, then leaned against slightly obliquely on the retort furnace inwall, calcined 2 hours for 220 ℃.Take out slide after the cooling, water-bath supersound process 30～60 seconds, a large amount of deionized water rinsings, acetone is cleaned, and cold wind dries up.
(b) SiO
2/ TiO
2The preparation of compound coating: the commercially available volume percent that the commercially available butyl (tetra) titanate of 9ml is joined 36ml is in 95% ethanolic soln, stirred 5 minutes, then above-mentioned mixed solution is added drop-wise in the 12ml deionized water and 40ml Glacial acetic acid mixing solutions under the whipped state, continue to stir, until by muddy bleach, then leaving standstill, mixed solution can get TiO in 30 hours
2Gel.Get the sample that (a) step obtains, repeat the sulfuric acid lotion cleaning process, then sample is immersed TiO
2In the gel 2 minutes, lift out liquid level with the speed of 14 cm per minute.After the slide glass that lifts out liquid level fully dried up with cold wind, horizontal positioned in retort furnace, 220 ℃ of bakings 20 seconds lean against on the retort furnace inwall more slightly obliquely, 500 ℃ of calcinings 30 minutes.Take out slide, airbath supersound process 5 minutes, behind the deionized water rinsing, acetone is cleaned, and cold wind dries up.
(c) SiO
2/ TiO
2The modification of compound coating: get the sample that (b) step obtains, be immersed in (perfluoro capryl trichloromethyl silane and normal hexane volume ratio are 1: 10 silicon fluoride solution) in the silicon fluoride solution, solution need flood whole surface, place dark place after 30 minutes, with thieving paper softly, rapidly the unnecessary silicon fluoride of sample surfaces is removed, placed 15 minutes in the dark place again, after surperficial seasoning, get final product.
This coating has the light-operated close and distant water of good ultraviolet and close and distant oily reversible transformation ability, faint ultraviolet luminous energy causes the conversion of 140 °/30 ° of coatingsurface and water contact angles, with the conversion of 100 °/30 ° of kerosene contact angles, and the conversion of above-mentioned light-operated wetting property is through repeatedly repeatedly still unattenuated after ultraviolet/dark cycle.Find that by observing under the emission Electronic Speculum on the scene a lot of beads are wrapped in large ball proper alignment at sample surfaces.Large ball is SiO among the figure
2, diameter is about 200nm, the regular bottom that is arranged in; Bead is TiO
2, diameter is about 10nm, is wrapped in SiO Uniform Dispersion
2The surface of ball.This coating has the composite micro-nano rice structure of similar lotus leaf surface, as shown in drawings.Exactly because have the surface topography of this composite micro-nano rice structure, so that this coating has good close and distant water and close and distant oily transfer capability.The SiO of bottom
2Large ball can deposit more TiO so that coating has larger specific surface area
2Nano particle.During hydrophobic oleophobic, form air cushion between adjacent two nanometer beads of composite micro-nano rice structure, steadily oil droplet or water droplet are held up, strengthened the hydrophobic oleophobic performance; During hydrophilic and oleophilic, form nanotube capillaries between adjacent two nanometer beads, further strengthened surperficial hydrophilic and oleophilic performance.
Find that in test the compound method of each reaction solution and the sample draw speed in gelating soln has strong correlation to the quality of forming film (comprising the light-operated reversible effect) of composite membrane, the present invention program is actually a kind of comprehensive preferred processing condition.
Adopt general planning of the present invention, in reality is implemented multiple change routinely can be arranged, test shows, adopts commercially available Aquapel anti-fog agent for wind-screen of automobile (U.S. PPG company) also can reach good effect in (c) of above-described embodiment step.Obviously, the silicon matrix sample can comprise conventional glass, pottery etc., and broader understanding should comprise that the surface has inorganic structure and the functional materials of hydroxyl enrichment after sulfuric acid lotion cleans.
The SiO of the light-operated profit wetting property reversible transformation that the present invention obtains
2/ TiO
2Compound coating is significant in function nano boundary material research field.This achievement in research has very wide application prospect in fields such as gene delivery, the conveying of free of losses liquid, microfluid, biochip, medicament slow release, petrochemical complex, material of construction.
Claims (4)
1. at silicon matrix surface preparation profit wetting property light-operated reversible SiO
2/ TiO
2The method of compound coating is characterized in that, adopts following step:
(a) the silicon matrix device covers SiO
2Coating: each component volume ratio is ammoniacal liquor in the reaction solution: ethanol: tetraethoxy=30:50:3; Be first that 25% ammoniacal liquor is added drop-wise in the dehydrated alcohol of 60 ° of C of constant temperature with mass ratio, slowly drip again tetraethoxy, continue to keep 60 ° of C constant temperature to stir and obtained SiO in 90 minutes
2Gel; The silicon matrix sample of the cleaning that sulfuric acid lotion cleaned immerses described SiO
2In the gelating soln 2 minutes, lift out liquid level with the speed of 5 ~ 14 cm per minute, afterwards 200 ~ 220 ° of C bakings 20 seconds, 220 ° of C calcinings are 2 hours again, take out after the cooling and clean, and obtain being covered with SiO
2The silicon matrix sample of coating;
(b) SiO
2/ TiO
2The preparation of compound coating: each component volume ratio is butyl (tetra) titanate in the reaction solution: ethanol: water: Glacial acetic acid=9:36:12:40; It is in 95% the ethanolic soln that butyl (tetra) titanate reagent is added volume percent, after mixing, be added drop-wise in the deionized water and Glacial acetic acid mixing solutions under the whipped state, in room temperature, continue to stir until mixed solution by muddy bleach, after leave standstill and obtained TiO in 30 hours
2Gel; Get the described SiO of being covered with that (a) obtains
2The silicon matrix sample of coating immerses TiO
2In the gel 2 minutes, lift out liquid level with the speed of 5 ~ 14 cm per minute, after drying up with cold wind, 220 ° of C bakings 20 seconds, sample was taken out in 450 ~ 500 ° of C calcinings in 30 minutes again;
(c) SiO
2/ TiO
2The modification of compound coating: get the sample that (b) step obtains, be immersed in an amount of silicon fluoride solution, place dark place to take out after 30 ~ 40 minutes, placed 15 ~ 20 minutes in the dark place, after surperficial seasoning, namely get target product.
2. described at silicon matrix surface preparation profit wetting property light-operated reversible SiO according to claim 1
2/ TiO
2The method of compound coating is characterized in that, described silicon fluoride solution is that mass ratio is the silicon fluoride solution of perfluoro capryl trichloromethyl silane: normal hexane=1:10.
3. described at silicon matrix surface preparation profit wetting property light-operated reversible SiO according to claim 1 and 2
2/ TiO
2The method of compound coating is characterized in that, described silicon fluoride solution is commercially available anti-fog agent for wind-screen of automobile.
4. described at silicon matrix surface preparation profit wetting property light-operated reversible SiO according to claim 1
2/ TiO
2The method of compound coating is characterized in that, described silicon matrix sample is glass, stupalith.
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| CN103540926A (en) * | 2013-09-24 | 2014-01-29 | 西南交通大学 | Light control SiO2/TiO2 composite micro-nano structure micro-channel valve and preparation method thereof |
| CN103881422B (en) * | 2014-03-21 | 2015-04-22 | 西南交通大学 | Light-operated switch type TiO2 nano-particles surfactant and preparation method thereof |
| CN104841345B (en) * | 2015-04-21 | 2017-05-17 | 西南交通大学 | Photomagnetic dual-response Pickering emulsion coalescence reaction system and application thereof |
| CN105254186A (en) * | 2015-10-29 | 2016-01-20 | 苏州市灵通玻璃制品有限公司 | Preparation method for self-cleaning glass |
| CN106630677B (en) * | 2016-12-19 | 2019-06-04 | 中国航空工业集团公司北京航空材料研究院 | A method of realizing the super hydrophilic and super-hydrophobic controllable inversion of glass surface |
| CN107502875B (en) * | 2017-07-19 | 2019-07-23 | 东南大学 | A kind of non-homogeneous super-hydrophobic coat and preparation method thereof with reinforcing dropwise condensation effect |
| CN108499551A (en) * | 2018-05-14 | 2018-09-07 | 东南大学 | A kind of catalysis material and its preparation and application method |
| CN113564528B (en) * | 2021-06-18 | 2022-06-10 | 复旦大学 | Light-operated reversible hydrophobic part and preparation method thereof |
| CN113638132B (en) * | 2021-09-03 | 2022-07-01 | 浙江嘉源针织有限公司 | Water-repellent oil-repellent high-strength antibacterial fabric and preparation method thereof |
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| CN101519278A (en) * | 2009-03-27 | 2009-09-02 | 吉林大学 | Method for preparing transparent super-hydrophobic automatic cleaning coating |
| CN101948574A (en) * | 2010-10-15 | 2011-01-19 | 上海交通大学 | Hydrophobic chitosan film containing hydrophobic nano silicon dioxide particles and preparation method thereof |
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|---|---|---|---|---|
| CN101519278A (en) * | 2009-03-27 | 2009-09-02 | 吉林大学 | Method for preparing transparent super-hydrophobic automatic cleaning coating |
| CN101948574A (en) * | 2010-10-15 | 2011-01-19 | 上海交通大学 | Hydrophobic chitosan film containing hydrophobic nano silicon dioxide particles and preparation method thereof |
| CN102153291A (en) * | 2010-12-14 | 2011-08-17 | 吉林大学 | Method for preparing antireflection antifogging wear-resistant coating by non-posterior chemical modification method |
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