CN102849962A - Preparation method of SiO2 super-hydrophobic film and super-hydrophobic material - Google Patents
Preparation method of SiO2 super-hydrophobic film and super-hydrophobic material Download PDFInfo
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Abstract
A preparation method of SiO2 super-hydrophobic film includes preparing SiO2 acidic sol by mixing Si(OR)4, acid catalyst, solvent and water; preparing a nano SiO2 film by coating the SiO2 acidic sol on a matrix and sintering to form the nano SiO2 film on surface of the matrix; preparing SiO2 alkaline sol by mixing Si(OR)4, alkali catalyst, solvent and water and adding low-surface energy modifier; and preparing a micro film by coating the SiO2 alkaline sol on the nano SiO2 film and drying to form the SiO2 super-hydrophobic film on surface of the matrix. The invention also provides a super-hydrophobic material. The SiO2 super-hydrophobic film obtained by the inventive method has strong adhesive force and good hydrophobic effect.
Description
Technical field
The present invention relates to the super hydrophobic material field, more particularly, relate to a kind of preparation method and a kind of super hydrophobic material of silicon-dioxide based superhydrophobic thin films.
Background technology
The wetting property of material surface is a key property of material, a lot of physical and chemical processes, and such as: friction, dispersion, bonding, absorption etc., all closely related with the material surface wetting property.Usually, with the contact angle of water greater than 150 °, the while lagging angle is considered to super hydrophobic surface less than 10 ° solid surface, and described super hydrophobic surface is the surface with certain roughness, and has the finishing low surface energy modifier of certain roughness at this.In recent years, caused great concern with the contact angle of water greater than 150 ° super hydrophobic surface, because super hydrophobic surface can be used widely, and in many fields such as self-cleaning material, microfluidic device and biomaterial extremely important application prospect be arranged in automatically cleaning, anti-icing, antifog, waterproof, snow defence, the field such as anticorrosive.
At present, the super hydrophobic material based on differing materials such as polymkeric substance, glass, metal, inorganic oxide, carbon nanotubes all is produced out.The method that adopts comprises: micromachined method, laser or plasma etching method, physics or chemical Vapor deposition process, anonizing, electrochemical deposition method, electrostatic spinning method, polyelectrolyte alternating deposit method etc.Yet existing these methods need special processing units and complicated technological process mostly.
Studies show that silicon-dioxide has good biocompatibility, ultraviolet light stability and thermostability, be fit to make based superhydrophobic thin films, prepare the silicon-dioxide based superhydrophobic thin films by making methods such as electrophoresis, mull techniques in the prior art, but come with some shortcomings.Specifically, a kind of method is with SiO
2Particle and alcoholic solution mix and blend, ultra-sonic dispersion is regulated potential of hydrogen, obtains colloid electrophoresis liquid, again with electrophoretic liquid deposition on glass substrate, obtain SiO
2Film then will be with SiO
2The glass of film is put into low table and can be modified by modifier, obtains super-hydrophobic SiO
2Film.Although this technology can form the silicon-dioxide based superhydrophobic thin films on the surface of glass, weak point is will prepare SiO first
2Solid particulate dissolves in solid particulate and prepares SiO in the solvent
2Colloid electrophoresis liquid, last electrophoretic deposition SiO
2Film carries out hydrophobization again and processes, and this method does not form the micro nano structure of the excellent property of super-drainage structure indispensability, and technique is more loaded down with trivial details, and preparation cycle is longer.Another kind method is to adopt mull technique that the micron order powder of super-hydrophobic layer and the mixed powder of nano level powder are embedded in the tack coat of matrix surface, make super-hydrophobic layer by alternately and embed tack coat form micron order projection and nano level projection micron order and nano-scale particle form, prepare micro-nano super-drainage structure, obtain based superhydrophobic thin films; Although this method has obtained desirable micro nano structure, weak point is micron order powder and the nano level powder mixed powder that will obtain through the modification of low table energy material, at first will prepare the SiO that contains the low surface energy modifier
2Colloid, again through grind, sieving obtains, complex process, cost is higher.
CN101817980A discloses a kind of preparation method of silica-based superhydrophobic thin films.The method is with alkylalkoxy silane R
nSi (OR ')
4-nWith methyl trialkoxysilane CH
3Si (OR)
3(or positive silicon ester Si (OR ')
4) mixture is precursor, utilize acid, alkali two-step approach hydrolytic polymerization to obtain colloidal sol, adding in the process than multi-solvent stops premature gelation to produce, after colloidal sol is fully aging, add a certain amount of water and regulate the degree that is separated of colloidal sol skeleton and solvent, so that the film of colloidal sol preparation presents certain roughness in dry rear surface thus, greater than 150 °, roll angle is less than 10 ° simultaneously to the static contact angle of water.This sol-gel method prepares the method for silica-based superhydrophobic thin films compared to above-mentioned two kinds, and technique is comparatively simple, and process is easy to control, and its shortcoming is, the colloidal sol generation gel that reacts easily can't be filmed in the process that soda acid mixes; And behind alkaline colloidal sol adding acidic sol, the pH value of original acidic sol changes, and causes mixing rear nano-scale particle sizes and might continue to grow up, and particle size is wayward, is difficult to obtain the micro nano structure of ideal dimensions.
Summary of the invention
The present invention prepares the silicon-dioxide based superhydrophobic thin films in order to solve existing sol-gel method, apply after adopting soda acid to mix, the colloidal sol generation gel that reacts easily in the process that soda acid mixes, can't film, and in the process that soda acid mixes, the size of nano-scale particle is wayward, is difficult to obtain the technical problem of desirable micro nano structure.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of silicon-dioxide based superhydrophobic thin films, it is characterized in that described method comprises the steps:
Step 1, preparation acidic sol: positive silicon ester, an acidic catalyst, solvent and water are mixed, be mixed with SiO
2Acidic sol;
Step 2, preparation nano level film: with described SiO
2Acidic sol is coated in the surface of matrix, and the surface at matrix behind the sintering forms nano level SiO
2Film;
Step 3, prepare alkaline colloidal sol: positive silicon ester, basic catalyst, solvent, water are mixed, then add the low surface energy modifier, be mixed with SiO
2Alkalescence colloidal sol;
Step 4, preparation micron order film: with described SiO
2Alkalescence colloidal sol is coated in above-mentioned nano level SiO
2On the film, obtain the silicon-dioxide based superhydrophobic thin films on the surface of matrix after the oven dry.
In above-mentioned preparation method, the mol ratio of described positive silicon ester, an acidic catalyst, solvent and water is 1:0.35-1:20-25:3-4.5.
In above-mentioned preparation method, in step 3, the mol ratio of described positive silicon ester, basic catalyst, solvent, water is 1:0.11-0.5:17.2-30:2.4-3.2; And the mol ratio of described positive silicon ester and low surface energy modifier is 1:0.1-0.2.
In above-mentioned preparation method, the composed as follows of described positive silicon ester stated shown in the general formula: Si(OR)
4, R is methyl, ethyl or propyl group.
In above-mentioned preparation method, described low surface energy modifier is alkylalkoxy silane, and its composed as follows stating shown in the general formula: R ' Si(OR)
4-n, wherein, R ' is alkyl, R is methyl, ethyl or propyl group, n=1 or 2.
In above-mentioned preparation method, described solvent is selected from one or more in ethanol, Virahol, methyl alcohol, propyl alcohol, the butanols.
In above-mentioned preparation method, described an acidic catalyst is selected from one or more in hydrochloric acid, acetic acid, the nitric acid.
In above-mentioned preparation method, described basic catalyst is selected from ammoniacal liquor and/or Tetramethylammonium hydroxide.
In above-mentioned preparation method, described SiO
2SiO in the acidic sol
2The particle diameter of particle is 5-10nm; Described SiO
2SiO in the alkalescence colloidal sol
2The particle diameter of particle is 5-10 μ m.
In above-mentioned preparation method, the method for described coating is dip-coating method, and pull rate is 10-15cm/min.
In above-mentioned preparation method, the temperature of described sintering is 500 ℃-550 ℃, and sintering time is 1-1.5 hour; Described oven dry is carried out under inert gas atmosphere, and temperature is 220 ℃-300 ℃.
The present invention also provides a kind of super hydrophobic material, the silicon-dioxide based superhydrophobic thin films that described super hydrophobic material comprises matrix and is coated on described matrix surface, and described silicon-dioxide based superhydrophobic thin films prepares by aforesaid method.
In the preparation method of silicon-dioxide based superhydrophobic thin films provided by the invention by preparing respectively SiO
2Acidic sol and SiO
2Alkalescence colloidal sol, minute two steps are with SiO
2Acidic sol and SiO
2Alkalescence colloidal sol is coated on the surface of matrix, and technique is simple, SiO
2Acidic sol and SiO
2The formation of alkalescence colloidal sol is easy to control, and is suitable for big area and films; The silicon-dioxide based superhydrophobic thin films for preparing has double-layer film structure, is desirable micro nano structure, and outer membrane modifies by the low surface energy modifier, and contact angle is 160 °-165 °, and roll angle is near zero degree, and hydrophobic properties of the surface are good; And the strong adhesion of silicon-dioxide based superhydrophobic thin films and matrix has preferably physical strength, damage-resistant energy, and higher stability.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of preparation method of silicon-dioxide based superhydrophobic thin films, adopt a kind of new sol-gel method to form the silicon-dioxide based superhydrophobic thin films on the surface of matrix; This sol-gel method is different from the sol-gel method of mentioning in the background technology, is in particular in that sol-gel method of the present invention prepares respectively SiO
2Acidic sol and SiO
2Alkalescence colloidal sol, minute two steps are with SiO
2Acidic sol and SiO
2Alkalescence colloidal sol is coated on the surface of matrix, thereby forms the micro nano structure of ideal structure, and specifically, the preparation method of Zirconium-base non-crystalline alloy compound material of the present invention comprises the steps:
Step 1, preparation acidic sol: positive silicon ester, an acidic catalyst, solvent and water are mixed, be mixed with SiO
2Acidic sol;
In this step, you mix than 1:0.35-1:20-25:3-4.5 with positive silicon ester, an acidic catalyst, solvent and hydromassage, and as solvent, stir under room temperature under the effect of an acidic catalyst with water is hydrolyzable to positive silicon ester with alcohol, churning time is 1h-2h, generates nano level SiO
2Then acidic sol was displayed aging 24-48 hour, through displaying the aging SiO that makes
2The larger silica deposit of particle obtains evengranular SiO in the acidic sol
2Acidic sol.
This step adopts acid system, obtains nano level SiO
2Acidic sol is at described nano level SiO
2In the acidic sol, SiO
2The particle diameter of particle is 5-10nm.
Described positive silicon ester preferably has the composition shown in the following general formula: Si(OR)
4, R is methyl, ethyl or propyl group, more preferably, described positive silicon ester is tetraethoxy (TEOS), has better hydrolysis property, generates easily well behaved SiO
2Acidic sol.
The effect of described an acidic catalyst is to increase speed of response, and improves SiO
2The stability of acidic sol, it is selected from the acidic solution that can volatilize under heating condition, and for example: be selected from one or more in hydrochloric acid, acetic acid, the nitric acid, preferably, described an acidic catalyst is nitric acid.Described an acidic catalyst react completely film after, under the condition of heating, preferably can from film, can vapor away, thereby select to have volatile acidic solution.
The effect of described solvent provides the place of reaction and the concentration of conditioned reaction system, can be that this area common are the machine solvent, be preferably alcoholic solvent, for example: be selected from one or more in ethanol, Virahol, methyl alcohol, propyl alcohol, the butanols, preferably, described solvent is dehydrated alcohol (C
2H
5OH), can make the dispersion effect of system better.
Step 2, preparation nano level film: with described SiO
2Acidic sol is coated in the surface of matrix, and the surface at matrix behind the sintering forms nano level SiO
2Film.
In this step, adopt dip-coating method with SiO
2Acidic sol evenly is coated on the matrix, and pull rate is 10-15cm/min, dries up with rare gas element after applying, and then is positioned in the retort furnace under 500 ℃-550 ℃ temperature, sintering 1-1.5 hour, can form nano level SiO on the surface of matrix
2Film, in this step, by at the nano level SiO of the surface-coated of matrix
2Acidic sol can access nano level SiO
2Film, behind sintering under 500 ℃-550 ℃ the temperature, nano level SiO
2The sticking power of film and matrix surface is stronger, is conducive to the processing of subsequent film.
In the present invention, the method for coating is not limited to dip-coating method, can also be that spin-coating, spray application, brushing etc. well known to a person skilled in the art coating method, but is preferably dip-coating method, and the coated rete of dip-coating method is more even.
In this step, described matrix can be the goods of the various types of materials such as glass, metal, pottery, semi-conductor, the present invention has no particular limits for the material of matrix, all can form the silicon-dioxide based superhydrophobic thin films on its surface by preparation method of the present invention, it is worth mentioning that, because silicon-dioxide based superhydrophobic thin films of the present invention demonstrates good properties of transparency in the ultraviolet-visible optical band, can not affect transparent matrix, for example the transmittance of glass can be applicable to transparent base well.
Step 3, prepare alkaline colloidal sol: positive silicon ester, basic catalyst, solvent, water are mixed, then add the low surface energy modifier, be mixed with SiO
2Alkalescence colloidal sol.
Described positive silicon ester preferably has the composition shown in the following general formula: Si(OR)
4, R is methyl, ethyl or propyl group, more preferably, described positive silicon ester is tetraethoxy (TEOS), has better hydrolysis property, generates easily well behaved SiO
2Acidic sol.
Described low surface energy modifier is preferably alkylalkoxy silane, and its composed as follows stating shown in the general formula: R ' Si(OR)
4-n, wherein, R ' is alkyl, is preferably methyl, ethyl, propyl group, butyl or chain alkyl, R is methyl, ethyl or propyl group, and n=1 or 2, described low surface energy modifier more preferably is Union carbide A-162 (MTES), has better modification effect.Certain described low surface energy modifier can also adopt low surface energy modifier that can modification of surfaces known in those skilled in the art, such as: fluorine-containing alkyl sulfonic ester, ptfe phthalate fluorinated ester, octadecyl trichlorosilane alkane, trimethylchlorosilane fluoroalkyl sulphonate etc.
Described basic catalyst is selected from the basic solution that can volatilize under heating condition, for example: be selected from ammoniacal liquor and/or Tetramethylammonium hydroxide, preferably, described basic catalyst is ammoniacal liquor.Described basic catalyst react completely film after, under the condition of heating, preferably can from film, can vapor away, thereby select to have volatile basic solution.
The effect of described solvent provides the place of reaction and the concentration of conditioned reaction system, can be that this area common are the machine solvent, be preferably alcoholic solvent, for example: be selected from one or more in ethanol, Virahol, methyl alcohol, propyl alcohol, the butanols, preferably, described solvent is dehydrated alcohol (C
2H
5OH), can make the dispersion effect of system better.
In this step, it is the positive silicon ester of 1:0.11-0.5:17.2-30:2.4-3.2:0.1-0.2 that mol ratio is provided, basic catalyst, solvent, water and alkylalkoxy silane, at first with basic catalyst, solvent and water mix, stir, after being warming up to 60 ℃-70 ℃, slowly drip positive silicon ester, time for adding is 1h, by the mode that drips so that the hydrolysis of positive silicon ester is more abundant, after constant temperature stirs 2h, continue to drip alkylalkoxy silane, time for adding is 0.5h, by the mode that drips so that the dispersion effect of low surface energy modifier is better, so that the modification effect of low surface energy modifier is better; Then ageing 24h-48h at room temperature is through displaying the aging SiO that makes
2The larger silica deposit of particle in the alkalescence colloidal sol can obtain evengranular micron-sized hydrophobic SiO
2Alkalescence colloidal sol is by directly adding SiO with the low surface energy modifier
2In the alkalescence colloidal sol, can directly obtain based superhydrophobic thin films after filming, need not the follow-up low surface energy modifier that adopts again and modify.
In this step, adopt alkaline system to obtain micron-sized SiO
2Alkalescence colloidal sol is at described micron-sized SiO
2In the alkalescence colloidal sol, SiO
2The particle diameter of particle is the 5-10 micron.
Step 4, preparation micron order film: with described SiO
2Alkalescence colloidal sol is coated in above-mentioned nano level SiO
2On the film, oven dry is rear at nano level SiO
2Form micron order SiO on the film
2Film makes the silicon-dioxide based superhydrophobic thin films on the surface of matrix.
In this step, by at nano level SiO
2The micron-sized SiO of the surface-coated of film
2Alkalescence colloidal sol can access micron-sized SiO
2Film.
In this step, adopt dip-coating method with SiO
2Alkalescence colloidal sol evenly is coated in the nano level SiO of matrix surface
2On the film, pull rate is 10-15cm/min, dries under inert gas atmosphere after applying, and by drying the mechanical stability of further enhanced film, the temperature of oven dry is 220 ℃-300 ℃, can form micron order SiO after the oven dry
2Film makes the silicon-dioxide based superhydrophobic thin films on the surface of matrix, because the low surface energy modifier decomposes during sintering under comparatively high temps easily, lose hydrophobic effect, thereby under 220 ℃-300 ℃ temperature, dry, make the basic catalyst volatilization by oven dry, strengthen simultaneously micron order SiO
2Film and nano level SiO
2Adhesion of thin film, and the low surface energy modifier is decomposed.
This silicon-dioxide based superhydrophobic thin films is for comprising nano level SiO
2Film and micron order SiO
2The double-layer films structure of film, this double-layer films structure is desirable micro nano structure, has better physical strength, stability, and because outer microtube meter level SiO
2Contain the low surface energy modifier in the film, so that the hydrophobic properties of the surface of silica-based superhydrophobic thin films and anti-stick antifouling property are good, contact angle is 160 °-165 °, and roll angle is near zero degree.
The present invention also provides a kind of super hydrophobic material, the silicon-dioxide based superhydrophobic thin films that described super hydrophobic material comprises matrix and is coated on described matrix surface, described silicon-dioxide based superhydrophobic thin films is by preparation method's preparation of silicon-dioxide based superhydrophobic thin films of the present invention; Described matrix can be the goods of the various types of materials such as glass, metal, pottery, semi-conductor, the present invention has no particular limits for the material of matrix, all can form the silicon-dioxide based superhydrophobic thin films on its surface by preparation method of the present invention, it is worth mentioning that, because silicon-dioxide based superhydrophobic thin films of the present invention demonstrates good properties of transparency in the ultraviolet-visible optical band, can not affect transparent matrix, for example the transmittance of glass can be applicable to transparent base well.
As from the foregoing, the preparation method of silicon-dioxide based superhydrophobic thin films of the present invention has following characteristics: described nano level SiO
2Acidic sol and micron-sized SiO
2Alkalescence colloidal sol applies step by step, wherein, and nano level SiO
2Acidic sol is coated in first the surface of matrix, thereby need not the modification of low surface energy modifier, only needs at micron-sized SiO
2Adding low surface energy modifier is modified and is got final product in the alkalescence colloidal sol, so also can obtain the silicon-dioxide based superhydrophobic thin films that the low surface energy modifier is modified; Secondly, because the SiO of substep coated with nano level
2Acidic sol and micron-sized SiO
2Alkalescence colloidal sol forms respectively nano level SiO
2Film and micron order SiO
2Film, so easier control of micro nano structure size, avoided existing sol-gel method colloidal sol in the process that soda acid mixes generation gel that reacts easily, can't film, and with behind the alkaline colloidal sol adding acidic sol, the pH value of original acidic sol changes, and causes mixing rear nano-scale particle sizes and might continue to grow up, the uppity shortcoming of particle size.
The present invention prepares respectively SiO
2Acidic sol and SiO
2Alkalescence colloidal sol, SiO
2The size of particle is easy to control, need not the pH value of regulation system, and technique is simple, then divides two steps with SiO
2Acidic sol and SiO
2Alkalescence colloidal sol is coated on the surface of matrix, can access desirable micro nano structure, and the sticking power between each layer is good, and outer field micron-sized SiO
2Alkalescence colloidal sol is modified through the low surface energy modifier, so that the hydrophobic effect of silicon-dioxide based superhydrophobic thin films is better; In a word, preparation method of the present invention has obtained nano level SiO by the preparation acidic sol
2Colloidal sol, the nano level film of rear formation of filming is by applying micron-sized SiO
2Alkalescence colloidal sol obtains micron-sized film, thereby forms the micro nano structure of based superhydrophobic thin films indispensability on the surface of matrix; And, the low surface energy modifier is added SiO
2In the alkalescence colloidal sol, can directly obtain based superhydrophobic thin films after filming, the contact angle of based superhydrophobic thin films can reach 160 °-165 °, roll angle is near zero degree, and hydrophobic effect is good, and adhesion of thin film is strong, the physical strength of rete is good, be not easy to be damaged, and the film of preparation demonstrates good properties of transparency in the ultraviolet-visible optical band, can be good at being applicable to transparent base, and is for example on glass; In addition, preparation method's technique of the present invention is simple, easy to operate, is fit to big area and applies, and has shortened the preparation cycle of based superhydrophobic thin films.
The below adopts the mode of embodiment that the present invention is described in further detail.
Embodiment 1
Present embodiment 1 is used for illustrating the preparation method of silicon-dioxide based superhydrophobic thin films provided by the present invention, the needed raw material of preparation method of the described silicon-dioxide based superhydrophobic thin films of present embodiment 1 comprises: methyl three ethoxy silane (MTES), tetraethoxy (TEOS), dehydrated alcohol (C
2H
5OH), ammoniacal liquor (NH
3H
2O) (25wt%), nitric acid (HNO
3), distilled water (H
2O), comprise the steps:
Step 1, prepare acid SiO
2Colloidal sol: with TEOS, HNO
3, H
2O and C
2H
5OH in molar ratio 1:0.35:3:20 mixes, and the preparation granular size is the nano level SiO of 5nm
2Acidic sol is displayed aging 24h;
Step 2, preparation nano level film: aging SiO is displayed in the glass immersion that cleans up
2In the acidic sol, evenly be coated in the glass surface that cleans up with crystal pulling method, pull rate is 10cm/min, uses N after filming
2Dry up, then be placed on sintering 1h in 500 ℃ of retort furnaces, can obtain nano level SiO
2Film;
Step 3, prepare alkaline colloidal sol: with C
2H
5OH, NH
3H
2O and H
2O is that the ratio of 17.2:0.11:2.4 is mixed in molar ratio, stir, after being warming up to 60 ℃, slowly drip mol ratio and be 1 TEOS, time for adding is 1h, after constant temperature stirs 2h, continuation dropping mol ratio is 0.1 MTHS, time for adding is 0.5h, ageing 24h at room temperature then, and can obtain granular size is the micron-sized hydrophobic SiO of 5 μ m
2Alkalescence colloidal sol;
Step 4, the super-hydrophobic micron order film of preparation: with dip-coating method with SiO
2Alkalescence colloidal sol evenly is coated in the glass surface through step 2 preparation, at N
2300 ℃ of oven dry can form SiO at glass surface in the atmosphere
2Based superhydrophobic thin films A1.Through the test of video optics contact angle measurement, described SiO
2The contact angle of based superhydrophobic thin films can reach 165 °, and roll angle is near 0 °.
Embodiment 2
Present embodiment 2 is used for illustrating the preparation method of silicon-dioxide based superhydrophobic thin films provided by the present invention, the needed raw material of preparation method of the described silicon-dioxide based superhydrophobic thin films of present embodiment 2 comprises: ethyl three ethoxy silane, methyl silicate, propyl alcohol, ammoniacal liquor, hydrochloric acid, distilled water comprises the steps:
Step 1, prepare acid SiO
2Colloidal sol: with methyl silicate, HCl, H
2O and propyl alcohol in molar ratio 1:0.4:3:20 mix, and the preparation granular size is the nano level SiO of 7nm
2Acidic sol is displayed aging 24h;
Step 2, preparation nano level film: aging SiO is displayed in the glass immersion that cleans up
2In the acidic sol, evenly be coated in the glass surface that cleans up with crystal pulling method, pull rate is 12cm/min, uses N after filming
2Dry up, then be placed on sintering 1h in 550 ℃ of retort furnaces, can obtain nano level SiO
2Film;
Step 3, prepare alkaline colloidal sol: with propyl alcohol, NH
3H
2O and H
2O is that the ratio of 21:0.15:2.7 is mixed in molar ratio, stir, after being warming up to 60 ℃, slowly drip mol ratio and be 1 methyl silicate, time for adding is 1h, after constant temperature stirs 2h, continuation dropping mol ratio is 0.15 ethyl three ethoxy silane, time for adding is 0.5h, ageing 40h at room temperature then, and can obtain granular size is the micron-sized hydrophobic SiO of 7 μ m
2Alkalescence colloidal sol;
Step 4, the super-hydrophobic micron order film of preparation: with dip-coating method with SiO
2Alkalescence colloidal sol evenly is coated in the glass surface through step 2 preparation, at N
2250 ℃ of oven dry can form SiO at glass surface in the atmosphere
2Based superhydrophobic thin films A2.Through the test of video optics contact angle measurement, described SiO
2The contact angle of based superhydrophobic thin films can reach 163 °, and roll angle is 1 °.
Embodiment 3
Present embodiment 3 is used for illustrating the preparation method of silicon-dioxide based superhydrophobic thin films provided by the present invention, the needed raw material of preparation method of the described silicon-dioxide based superhydrophobic thin films of present embodiment 3 comprises: methyl octadecyl trichlorosilane alkane (OTS), tetraethoxy (TEOS), dehydrated alcohol (C
2H
5OH), ammoniacal liquor (NH
3H
2O) (25wt%), nitric acid (HNO
3), distilled water (H
2O), comprise the steps:
Step 1, prepare acid SiO
2Colloidal sol: with TEOS, HNO
3, H
2O and C
2H
5OH in molar ratio 1:0.9:4.5:25 mixes, and the preparation granular size is the nano level SiO of 10nm
2Acidic sol is displayed aging 48h;
Step 2, preparation nano level film: aging SiO is displayed in the glass immersion that cleans up
2In the acidic sol, evenly be coated in the glass surface that cleans up with crystal pulling method, pull rate is 15cm/min, uses N after filming
2Dry up, then be placed on sintering 1.5h in 550 ℃ of retort furnaces, can obtain nano level SiO
2Film;
Step 3, prepare alkaline colloidal sol: with C
2H
5OH, NH
3H
2O and H
2O is that the ratio of 17.2:0.15:2.4 is mixed in molar ratio, stir, after being warming up to 60 ℃, slowly drip mol ratio and be 1 TEOS, time for adding is 1h, after constant temperature stirs 2h, continuation dropping mol ratio is 0.2 OTS, time for adding is 0.5h, ageing 24h at room temperature then, and can obtain granular size is the micron-sized hydrophobic SiO of 10 μ m
2Alkalescence colloidal sol;
Step 4, the super-hydrophobic micron order film of preparation: with dip-coating method with SiO
2Alkalescence colloidal sol evenly is coated in the glass surface through step 2 preparation, at N
2300 ℃ of oven dry can form SiO at glass surface in the atmosphere
2Based superhydrophobic thin films A3.Through the test of video optics contact angle measurement, described SiO
2The contact angle of based superhydrophobic thin films can reach 165 °, and roll angle is 1 °.
Embodiment 4
Present embodiment 4 is used for illustrating the preparation method of silicon-dioxide based superhydrophobic thin films provided by the present invention, the needed raw material of preparation method of the described silicon-dioxide based superhydrophobic thin films of present embodiment 4 comprises: methyl octadecyl trichlorosilane alkane, positive silicic acid propyl ester, methyl alcohol, Tetramethylammonium hydroxide, nitric acid, distilled water comprises the steps:
Step 1, prepare acid SiO
2Colloidal sol: with the in molar ratio 1:0.45:3:25 mixing of positive silicic acid propyl ester, nitric acid, water and methyl alcohol, the preparation granular size is the nano level SiO of 8nm
2Acidic sol is displayed aging 36h;
Step 2, preparation nano level film: aging SiO is displayed in the glass immersion that cleans up
2In the acidic sol, evenly be coated in the glass surface that cleans up with crystal pulling method, pull rate is 15cm/min, uses N after filming
2Dry up, then be placed on sintering 1.5h in 520 ℃ of retort furnaces, can obtain nano level SiO
2Film;
Step 3, prepare alkaline colloidal sol: you mix than the ratio for 17.2:0.45:2.4 with methyl alcohol, Tetramethylammonium hydroxide and hydromassage, stir, after being warming up to 60 ℃, slowly drip mol ratio and be 1 positive silicic acid propyl ester, time for adding is 1h, after constant temperature stirs 2h, continuation dropping mol ratio is 0.2 octadecyl trichlorosilane alkane, time for adding is 0.5h, ageing 36h at room temperature then, and can obtain granular size is the micron-sized hydrophobic SiO of 3 μ m
2Alkalescence colloidal sol;
Step 4, the super-hydrophobic micron order film of preparation: with dip-coating method with SiO
2Alkalescence colloidal sol evenly is coated in the glass surface through step 2 preparation, at N
2220 ℃ of oven dry can form SiO at glass surface in the atmosphere
2Based superhydrophobic thin films A4.Through the test of video optics contact angle measurement, described SiO
2The contact angle of based superhydrophobic thin films can reach 164 °, and roll angle is 1 °.
Comparative Examples 1
Adopt the method for disclosed embodiment 1 among the CN101817980A, form SiO at glass surface
2Based superhydrophobic thin films DA1.
Performance test
The based superhydrophobic thin films A1-A4 of embodiment 1-4 preparation and the based superhydrophobic thin films DA1 of Comparative Examples 1 preparation are carried out respectively following pencil hardness test, sticking power test and wear-resisting test, and test result is as shown in table 1.
1, pencil hardness test
Adopt Mitsubishi (UNI) cover hardness to be respectively the pencil of 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, on sample, apply 1000 gram forces by 45 ° of directions, 10 millimeters strokes, different positions is drawn 3 roads, whether have obvious cut, the hardness take the hard pencil that can not scratch paint film number as paint film if observing sample appearance.
2, sticking power test
Testing standard: ISO 2409;
Testing method: use the knife back of surgical knife to draw 12 road cuts in coating, wherein at least two cuts and other cut at an angle of 90, to form from the teeth outwards grid, the length of side of grid is 1 millimeter.Guarantee that every cut all is cut to body material.Both direction along cut is respectively brushed 5 times with brush.3M adhesive tape (Dongguan Ao Mike company, the adhesive tape model is 3M600) glue from the teeth outwards, with finger tip that wiping belt is tight, guarantee the good contact with coating, in 5 minutes from the free end of adhesive tape the angle with 60 ° tear well-regulated the opening of adhesive tape off adhesive tape at 0.5-1 in second;
Grade classification:
0 grade: the edge of otch is fully level and smooth, and the square of grid does not all peel off;
1 grade: the area that peels off part is not more than and 5% of the adhesive tape area of Surface Contact;
2 grades: the area that peels off part greater than with 5% of the adhesive tape area of Surface Contact, and be no more than 15%;
3 grades: the area that peels off part greater than with 15% of the adhesive tape area of Surface Contact, and be no more than 35%;
4 grades: the area that peels off part greater than with 35% of the adhesive tape area of Surface Contact, and be no more than 65%.
3, wear-resisting test
The 7-IBB type RCA abrasion instrument that uses U.S. Nuo Man Instrument and Equipment Company to produce, under the effect of 175 gram forces, mill is coated with the coating that installs, the number of times that rubber wheel rotates during the show-through material of record coating.
Table 1
| ? | Pencil hardness test | The sticking power test | Wear-resisting test |
| Embodiment 1 | 2H | 0 grade | 552 circles |
| Embodiment 2 | 2H | 0 grade | 531 circles |
| Embodiment 3 | 2H | 0 grade | 576 circles |
| Embodiment 4 | 2H | 0 grade | 548 circles |
| Comparative Examples 1 | F | 0 grade | 105 circles |
Compare with Comparative Examples 1 from the embodiment 1-4 of table 1, can know that the silicon-dioxide based superhydrophobic thin films of embodiment of the invention 1-4 has better hardness, wear resistance, and with matrix sticking power preferably; And through the test of video optics contact angle measurement, the contact angle of the silicon-dioxide based superhydrophobic thin films of embodiment of the invention 1-4 reaches as high as 165 °, and roll angle proves absolutely that near 0 ° its hydrophobic effect is good.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. the preparation method of a silicon-dioxide based superhydrophobic thin films is characterized in that, described method comprises the steps:
Step 1, preparation acidic sol: positive silicon ester, an acidic catalyst, solvent and water are mixed, be mixed with SiO
2Acidic sol;
Step 2, preparation nano level film: with described SiO
2Acidic sol is coated in the surface of matrix, and the surface at matrix behind the sintering forms nano level SiO
2Film;
Step 3, prepare alkaline colloidal sol: positive silicon ester, basic catalyst, solvent, water are mixed, then add the low surface energy modifier, be mixed with SiO
2Alkalescence colloidal sol;
Step 4, preparation micron order film: with described SiO
2Alkalescence colloidal sol is coated in above-mentioned nano level SiO
2On the film, obtain the silicon-dioxide based superhydrophobic thin films on the surface of matrix after the oven dry.
2. preparation method according to claim 1 is characterized in that, in step 1, the mol ratio of described positive silicon ester, an acidic catalyst, solvent and water is 1:0.35-1:20-25:3-4.5.
3. preparation method according to claim 1 is characterized in that, in step 3, the mol ratio of described positive silicon ester, basic catalyst, solvent, water is 1:0.11-0.5:17.2-30:2.4-3.2; And the mol ratio of described positive silicon ester and low surface energy modifier is 1:0.1-0.2.
4. the described preparation method of any one is characterized in that according to claim 1-3, and the composed as follows of described positive silicon ester stated shown in the general formula: Si(OR)
4, R is methyl, ethyl or propyl group.
5. according to claim 1 or 3 described preparation methods, it is characterized in that described low surface energy modifier is alkylalkoxy silane, its composed as follows stating shown in the general formula: R ' Si(OR)
4-n, wherein, R ' is alkyl, R is methyl, ethyl or propyl group, n=1 or 2.
6. the described preparation method of any one is characterized in that according to claim 1-3, and described solvent is selected from one or more in ethanol, Virahol, methyl alcohol, propyl alcohol, the butanols.
7. the described preparation method of any one is characterized in that according to claim 1-3, and described an acidic catalyst is selected from one or more in hydrochloric acid, acetic acid, the nitric acid.
8. the described preparation method of any one is characterized in that according to claim 1-3, and described basic catalyst is selected from ammoniacal liquor and/or Tetramethylammonium hydroxide.
9. preparation method according to claim 1 is characterized in that, described SiO
2SiO in the acidic sol
2The particle diameter of particle is 5-10nm; Described SiO
2SiO in the alkalescence colloidal sol
2The particle diameter of particle is 5-10 μ m.
10. preparation method according to claim 1 is characterized in that, the method for described coating is dip-coating method, and pull rate is 10-15cm/min.
11. preparation method according to claim 1 is characterized in that, the temperature of described sintering is 500 ℃-550 ℃, and sintering time is 1-1.5 hour; Described oven dry is carried out under inert gas atmosphere, and temperature is 220 ℃-300 ℃.
12. a super hydrophobic material is characterized in that, the silicon-dioxide based superhydrophobic thin films that described super hydrophobic material comprises matrix and is coated on described matrix surface, and described silicon-dioxide based superhydrophobic thin films is by preparing such as the described method of claim 1-11 any one.
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