CN102849962B - 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 super hydrophobic material field, more particularly, relate to a kind of preparation method of silicon dioxide super-hydrophobic thin film and a kind of super hydrophobic material.
Background technology
The wetting property of material surface is a key property of material, a lot of physical and chemical process, such as: friction, dispersion, bonding, absorption etc., all closely related with material surface wetting property.Usually, 150 ° are greater than with the contact angle of water, the solid surface that simultaneously lagging angle is less than 10 ° is considered to super hydrophobic 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, the super hydrophobic surface being greater than 150 ° with the contact angle of water causes great concern, because super hydrophobic surface can be applied widely, and have extremely important application prospect in many fields such as self-cleaning material, microfluidic device and biomaterial 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 is produced out all.The method adopted comprises: micromachined method, laser or plasma etching method, physics or chemical Vapor deposition process, anonizing, electrochemical deposition method, electrospinning process, polyelectrolyte alternating deposit method etc.But these methods existing need special processing units and complicated technological process mostly.
Research shows, silicon-dioxide has good biocompatibility, ultraviolet light stability and thermostability, is applicable to making based superhydrophobic thin films, prepares silicon dioxide super-hydrophobic thin film, but come with some shortcomings in prior art by the making method such as electrophoresis, mull technique.Specifically, a kind of method is by SiO
2particle and alcoholic solution mix and blend, ultrasonic disperse, regulates potential of hydrogen, obtains colloid electrophoresis liquid, then by electrophoretic liquid deposition in glass substrate, obtains SiO
2film, then will with SiO
2the glass of film is put into low table energy modifier and is modified, and obtains super-hydrophobic SiO
2film.Although this technology can form silicon dioxide super-hydrophobic thin film on the surface of glass, weak point is first will prepare SiO
2solid particulate, then solid particulate is dissolved in solvent prepare SiO
2colloid electrophoresis liquid, last electrophoretic deposition SiO
2film, then carry out hydrophobization process, this method does not form the micro nano structure of the excellent property of super-drainage structure indispensability, and technics comparing is loaded down with trivial details, and preparation cycle is longer.Another kind method adopts mull technique to embed in the tack coat of matrix surface by the mixed powder of the micron order powder of super-hydrophobic layer and nano level powder, make super-hydrophobic layer by alternately and embed tack coat formed the protruding and nano level projection of micron order micron order and nano-scale particle form, prepare micro-nano super-drainage structure, obtain based superhydrophobic thin films; Although this method obtains desirable micro nano structure, weak point is the micron order powder and nano level powder mixed powder that will obtain modifying through low table energy material, first will prepare the SiO containing low surface energy modifier
2colloid, then through grinding, 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, utilization acid, alkali two-step approach hydrolytic polymerization obtain colloidal sol, adding comparatively multi-solvent in process stops premature gelation to produce, after colloidal sol is fully aging, add the degree that is separated that a certain amount of water regulates colloidal sol skeleton and solvent, film prepared by colloidal sol thus surface presentation certain roughness after the drying, is greater than 150 ° to the static contact angle of water, and roll angle is less than 10 ° simultaneously.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, in the process of soda acid mixing, colloidal sol easily reacts generation gel, cannot film; Further, after alkaline sol is added acidic sol, the pH value of original acidic sol changes, and cause mixing rear nano-scale particle sizes and likely continue to grow up, particle size is wayward, is difficult to the micro nano structure obtaining ideal dimensions.
Summary of the invention
The present invention prepares silicon dioxide super-hydrophobic thin film to solve existing sol-gel method, apply after adopting soda acid mixing, in the process of soda acid mixing, colloidal sol easily reacts generation gel, cannot film, and in the process of soda acid mixing, the size of nano-scale particle is wayward, is difficult to the technical problem obtaining 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 super-hydrophobic thin film, it is characterized in that, described method comprises the steps:
Step 1, prepare acidic sol: positive silicon ester, an acidic catalyst, solvent and water are mixed, be mixed with SiO
2acidic sol;
Step 2, prepare nano-level thin-membrane: by described SiO
2acidic sol is coated in the surface of matrix, forms nano level SiO after sintering on the surface of matrix
2film;
Step 3, prepare alkaline sol: by positive silicon ester, basic catalyst, solvent, water mixing, then add low surface energy modifier, be mixed with SiO
2alkaline sol;
Step 4, prepare micron order film: by described SiO
2alkaline sol is coated in above-mentioned nano level SiO
2on film, the surface at matrix after oven dry obtains silicon dioxide super-hydrophobic thin film.
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; Further, 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 is stated shown in 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 it is composed as follows states shown in general formula: R ' Si(OR)
4-n, wherein, R ' is alkyl, and R is methyl, ethyl or propyl group, n=1 or 2.
One or more in above-mentioned preparation method, in described solvent selected from ethanol, Virahol, methyl alcohol, propyl alcohol, butanols.
In above-mentioned preparation method, described an acidic catalyst is selected from one or more in hydrochloric acid, acetic acid, 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 acidic sol
2the particle diameter of particle is 5-10nm; Described SiO
2siO in alkaline sol
2the particle diameter of particle is 5-10 μm.
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 DEG C-550 DEG C, and sintering time is 1-1.5 hour; Described oven dry is carried out under inert gas atmosphere, and temperature is 220 DEG C-300 DEG C.
Present invention also offers a kind of super hydrophobic material, described super hydrophobic material comprises matrix and is coated on the silicon dioxide super-hydrophobic thin film of described matrix surface, and described silicon dioxide super-hydrophobic thin film is prepared by method as above.
Pass through to prepare SiO respectively in the preparation method of silicon dioxide super-hydrophobic thin film provided by the invention
2acidic sol and SiO
2alkaline sol, point two steps are by SiO
2acidic sol and SiO
2alkaline sol is coated on the surface of matrix, and technique is simple, SiO
2acidic sol and SiO
2the formation of alkaline sol is easy to control, and is suitable for big area film; The silicon dioxide super-hydrophobic thin film prepared has double-layer film structure, be desirable micro nano structure, and outer membrane is modified by low surface energy modifier, and contact angle is 160 °-165 °, and roll angle is close to zero degree, and hydrophobic properties of the surface are good; And the strong adhesion of silicon dioxide super-hydrophobic thin film and matrix, has good physical strength, antibody Monoclonal performance, and higher stability.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, 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, be not intended to limit the present invention.
The invention provides a kind of preparation method of silicon dioxide super-hydrophobic thin film, adopt a kind of new sol-gel method to form silicon dioxide super-hydrophobic thin film on the surface of matrix; This sol-gel method is different from the sol-gel method mentioned in background technology, is in particular in that sol-gel method of the present invention prepares SiO respectively
2acidic sol and SiO
2alkaline sol, point two steps are by SiO
2acidic sol and SiO
2alkaline sol is coated on the surface of matrix, thus 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, prepare acidic sol: positive silicon ester, an acidic catalyst, solvent and water are mixed, be mixed with SiO
2acidic sol;
In this step, by positive silicon ester, an acidic catalyst, solvent and hydromassage you than 1:0.35-1:20-25:3-4.5 mixing, positive silicon ester using alcohol as solvent, with water stirred at ambient temperature and hydrolyzable under the effect of an acidic catalyst, churning time is 1h-2h, generates nano level SiO
2acidic sol, then displays aging 24-48 hour, agingly makes SiO through displaying
2the silica deposit that in acidic sol, particle is larger, obtains evengranular SiO
2acidic sol.
This step adopts acid system, obtains nano level SiO
2acidic sol, at described nano level SiO
2in acidic sol, SiO
2the particle diameter of particle is 5-10nm.
Described positive silicon ester preferably has the composition shown in following general formula: Si(OR)
4, R is methyl, ethyl or propyl group, and more preferably, described positive silicon ester is tetraethoxy (TEOS), has better hydrolysis property, easily generates SiO of good performance
2acidic sol.
The effect of described an acidic catalyst increases speed of response, and improve SiO
2the stability of acidic sol, it is selected from the acidic solution that can volatilize in a heated condition, and such as: be selected from one or more in hydrochloric acid, acetic acid, nitric acid, preferably, described an acidic catalyst is nitric acid.Described an acidic catalyst, after the film that reacts completely, preferably can be able to vapor away under the condition of heating from film, thus selects to have volatile acidic solution.
The effect of described solvent is to provide the place of reaction and regulates the concentration of reaction system, can be that this area common are machine solvent, be preferably alcoholic solvent, such as: be selected from one or more in ethanol, Virahol, methyl alcohol, propyl alcohol, butanols, preferably, described solvent is dehydrated alcohol (C
2h
5oH), the dispersion effect of system can be made better.
Step 2, prepare nano-level thin-membrane: by described SiO
2acidic sol is coated in the surface of matrix, forms nano level SiO after sintering on the surface of matrix
2film.
In this step, adopt dip-coating method by SiO
2acidic sol is evenly coated on matrix, and pull rate is 10-15cm/min, dries up after coating with rare gas element, is then positioned in retort furnace at the temperature of 500 DEG C-550 DEG C, sintering 1-1.5 hour, can form nano level SiO on the surface of matrix
2film, in this step, by the nano level SiO of the surface-coated of matrix
2acidic sol can obtain nano level SiO
2film, at the temperature of 500 DEG C-550 DEG C after sintering, nano level SiO
2the sticking power of film and matrix surface is stronger, is conducive to the process 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 be preferably dip-coating method, the rete coated by dip-coating method evenly.
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 silicon dioxide super-hydrophobic thin film by preparation method of the present invention on its surface, it is worth mentioning that, because silicon dioxide super-hydrophobic thin film of the present invention demonstrates good properties of transparency in ultraviolet-visible optical band, transparent matrix can not be affected, the transmittance of such as glass, can be applicable to transparent base well.
Step 3, prepare alkaline sol: by positive silicon ester, basic catalyst, solvent, water mixing, then add low surface energy modifier, be mixed with SiO
2alkaline sol.
Described positive silicon ester preferably has the composition shown in following general formula: Si(OR)
4, R is methyl, ethyl or propyl group, and more preferably, described positive silicon ester is tetraethoxy (TEOS), has better hydrolysis property, easily generates SiO of good performance
2acidic sol.
Described low surface energy modifier is preferably alkylalkoxy silane, and it is composed as follows states shown in general formula: R ' Si(OR)
4-n, wherein, R ' is alkyl, and be preferably methyl, ethyl, propyl group, butyl or chain alkyl, R is methyl, ethyl or propyl group, n=1 or 2, and described low surface energy modifier is more preferably Union carbide A-162 (MTES), has better modification effect.Certain described low surface energy modifier can also adopt known in those skilled in the art can the low surface energy modifier of modification of surfaces, such as: fluorine-containing alkyl sulfonic ester, ptfe phthalate fluorinated ester, octadecyl trichlorosilane alkane, trimethylchlorosilane fluoroalkyl sulfonic acids ester etc.
Described basic catalyst is selected from the basic solution that can volatilize in a heated condition, and such as: be selected from ammoniacal liquor and/or Tetramethylammonium hydroxide, preferably, described basic catalyst is ammoniacal liquor.Described basic catalyst, after the film that reacts completely, preferably can be able to vapor away under the condition of heating from film, thus selects to have volatile basic solution.
The effect of described solvent is to provide the place of reaction and regulates the concentration of reaction system, can be that this area common are machine solvent, be preferably alcoholic solvent, such as: be selected from one or more in ethanol, Virahol, methyl alcohol, propyl alcohol, butanols, preferably, described solvent is dehydrated alcohol (C
2h
5oH), the dispersion effect of system can be made better.
In this step, mol ratio is provided to be the positive silicon ester of 1:0.11-0.5:17.2-30:2.4-3.2:0.1-0.2, basic catalyst, solvent, water and alkylalkoxy silane, first by basic catalyst, solvent and water mixing, stir, after being warming up to 60 DEG C-70 DEG C, slowly drip positive silicon ester, time for adding is 1h, make positive silicic acid ester hydrolysis more abundant by the mode dripped, after constant temperature stirs 2h, continue to drip alkylalkoxy silane, time for adding is 0.5h, make the dispersion effect of low surface energy modifier better by the mode dripped, make the modification effect of low surface energy modifier better, then at room temperature ageing 24h-48h, agingly makes SiO through displaying
2the silica deposit that in alkaline sol, particle is larger, can obtain evengranular micron-sized hydrophobic SiO
2alkaline sol, by directly adding SiO by low surface energy modifier
2in alkaline sol, film directly can obtain based superhydrophobic thin films later, modifies without the need to the follow-up low surface energy modifier that adopts again.
In this step, alkaline system is adopted to obtain micron-sized SiO
2alkaline sol, at described micron-sized SiO
2in alkaline sol, SiO
2the particle diameter of particle is 5-10 micron.
Step 4, prepare micron order film: by described SiO
2alkaline sol is coated in above-mentioned nano level SiO
2on film, at nano level SiO after oven dry
2film is formed micron order SiO
2film, obtains silicon dioxide super-hydrophobic thin film on the surface of matrix.
In this step, by nano level SiO
2the micron-sized SiO of surface-coated of film
2alkaline sol can obtain micron-sized SiO
2film.
In this step, adopt dip-coating method by SiO
2alkaline sol is evenly coated in the nano level SiO of matrix surface
2on film, pull rate is 10-15cm/min, dries under inert gas atmosphere after coating, and by drying the mechanical stability of further enhanced film, the temperature of oven dry is 220 DEG C-300 DEG C, can form micron order SiO after oven dry
2film, obtains silicon dioxide super-hydrophobic thin film on the surface of matrix, owing to easily decomposing when low surface energy modifier sinters at relatively high temperatures, lose hydrophobic effect, thus dry at the temperature of 220 DEG C-300 DEG C, by drying, basic catalyst being volatilized, strengthening micron order SiO simultaneously
2film and nano level SiO
2adhesion of thin film, and low surface energy modifier can not be made to decompose.
This silicon dioxide super-hydrophobic thin film 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 preferably physical strength, stability, and due to outer microtube meter level SiO
2containing low surface energy modifier in film, make the hydrophobic properties of the surface of silica-based superhydrophobic thin films and anti-stick antifouling property good, contact angle is 160 °-165 °, and roll angle is close to zero degree.
Present invention also offers a kind of super hydrophobic material, described super hydrophobic material comprises matrix and is coated on the silicon dioxide super-hydrophobic thin film of described matrix surface, and described silicon dioxide super-hydrophobic thin film is prepared by the preparation method of silicon dioxide super-hydrophobic thin film 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 silicon dioxide super-hydrophobic thin film by preparation method of the present invention on its surface, it is worth mentioning that, because silicon dioxide super-hydrophobic thin film of the present invention demonstrates good properties of transparency in ultraviolet-visible optical band, transparent matrix can not be affected, the transmittance of such as glass, transparent base can be applicable to well.
As from the foregoing, the preparation method of silicon dioxide super-hydrophobic thin film of the present invention has following characteristics: described nano level SiO
2acidic sol and micron-sized SiO
2the coating of alkaline sol substep, wherein, nano level SiO
2acidic sol is first coated in the surface of matrix, thus modifies without the need to low surface energy modifier, only need at micron-sized SiO
2add low surface energy modifier in alkaline sol to carry out modifying, so also can obtain the silicon dioxide super-hydrophobic thin film that low surface energy modifier is modified; Secondly, due to the SiO of substep coated with nano level
2acidic sol and micron-sized SiO
2alkaline sol, forms nano level SiO respectively
2film and micron order SiO
2film, such micro nano structure size more easily controls, avoid colloidal sol in the process that existing sol-gel method mixes at soda acid easily to react generation gel, cannot film, and after alkaline sol is added acidic sol, the pH value of original acidic sol changes, and causes mixing rear nano-scale particle sizes and likely continues to grow up, the uppity shortcoming of particle size.
The present invention prepares SiO respectively
2acidic sol and SiO
2alkaline sol, SiO
2the size of particle is easy to control, and without the need to the pH value of regulation system, technique is simple, then divides two steps by SiO
2acidic sol and SiO
2alkaline sol is coated on the surface of matrix, can obtain desirable micro nano structure, and the sticking power between each layer is good, and outer field micron-sized SiO
2alkaline sol is modified through low surface energy modifier, makes the hydrophobic effect of silicon dioxide super-hydrophobic thin film better; In a word, preparation method of the present invention obtains nano level SiO by preparation acidic sol
2colloidal sol, forms nano level film after film, by applying micron-sized SiO
2alkaline sol obtains micron-sized film, thus forms the micro nano structure of based superhydrophobic thin films indispensability on the surface of matrix; Further, low surface energy modifier is added SiO
2in alkaline sol, film directly can obtain based superhydrophobic thin films later, the contact angle of based superhydrophobic thin films can reach 160 °-165 °, roll angle is close to 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, such as, and the film of preparation demonstrates good properties of transparency in ultraviolet-visible optical band, can be good at being applicable to transparent base, on glass; In addition, preparation method's technique of the present invention is simple, easy to operate, is applicable to big area coating, shortens the preparation cycle of based superhydrophobic thin films.
The mode of embodiment is adopted to be described in further detail the present invention below.
Embodiment 1
The present embodiment 1 is for illustration of the preparation method of silicon dioxide super-hydrophobic thin film provided by the present invention, the raw material required for preparation method of the described silicon dioxide super-hydrophobic thin film of the 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: by TEOS, HNO
3, H
2o and C
2h
5oH 1:0.35:3:20 mixing in molar ratio, preparation granular size is the nano level SiO of 5nm
2acidic sol, displays aging 24h;
Step 2, prepare nano-level thin-membrane: immersed by the glass cleaned up and display aging SiO
2in acidic sol, be evenly coated in the glass surface cleaned up with crystal pulling method, pull rate is 10cm/min, uses N after film
2dry up, be then placed in 500 DEG C of retort furnaces and sinter 1h, nano level SiO can be obtained
2film;
Step 3, prepare alkaline sol: by C
2h
5oH, NH
3h
2o and H
2o is the ratio mixing of 17.2:0.11:2.4 in molar ratio, stir, after being warming up to 60 DEG C, slowly dripping mol ratio is the TEOS of 1, and time for adding is 1h, after constant temperature stirs 2h, continuing to drip mol ratio is the MTHS of 0.1, time for adding is 0.5h, then at room temperature ageing 24h, can obtain the micron-sized hydrophobic SiO that granular size is 5 μm
2alkaline sol;
Step 4, prepare super-hydrophobic micron order film: with dip-coating method by SiO
2alkaline sol is evenly coated in the glass surface prepared through step 2, at N
2in atmosphere, 300 DEG C of oven dry, can form SiO at glass surface
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 close to 0 °.
Embodiment 2
The present embodiment 2 is for illustration of the preparation method of silicon dioxide super-hydrophobic thin film provided by the present invention, the raw material required for preparation method of the described silicon dioxide super-hydrophobic thin film of the 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: by methyl silicate, HCl, H
2the 1:0.4:3:20 mixing in molar ratio of O and propyl alcohol, preparation granular size is the nano level SiO of 7nm
2acidic sol, displays aging 24h;
Step 2, prepare nano-level thin-membrane: immersed by the glass cleaned up and display aging SiO
2in acidic sol, be evenly coated in the glass surface cleaned up with crystal pulling method, pull rate is 12cm/min, uses N after film
2dry up, be then placed in 550 DEG C of retort furnaces and sinter 1h, nano level SiO can be obtained
2film;
Step 3, prepare alkaline sol: by propyl alcohol, NH
3h
2o and H
2o is the ratio mixing of 21:0.15:2.7 in molar ratio, stir, after being warming up to 60 DEG C, slowly dripping mol ratio is the methyl silicate of 1, and time for adding is 1h, after constant temperature stirs 2h, continue to drip the ethyl three ethoxy silane that mol ratio is 0.15, time for adding is 0.5h, then at room temperature ageing 40h, can obtain the micron-sized hydrophobic SiO that granular size is 7 μm
2alkaline sol;
Step 4, prepare super-hydrophobic micron order film: with dip-coating method by SiO
2alkaline sol is evenly coated in the glass surface prepared through step 2, at N
2in atmosphere, 250 DEG C of oven dry, can form SiO at glass surface
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
The present embodiment 3 is for illustration of the preparation method of silicon dioxide super-hydrophobic thin film provided by the present invention, the raw material required for preparation method of the described silicon dioxide super-hydrophobic thin film of the 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: by TEOS, HNO
3, H
2o and C
2h
5oH 1:0.9:4.5:25 mixing in molar ratio, preparation granular size is the nano level SiO of 10nm
2acidic sol, displays aging 48h;
Step 2, prepare nano-level thin-membrane: immersed by the glass cleaned up and display aging SiO
2in acidic sol, be evenly coated in the glass surface cleaned up with crystal pulling method, pull rate is 15cm/min, uses N after film
2dry up, be then placed in 550 DEG C of retort furnaces and sinter 1.5h, nano level SiO can be obtained
2film;
Step 3, prepare alkaline sol: by C
2h
5oH, NH
3h
2o and H
2o is the ratio mixing of 17.2:0.15:2.4 in molar ratio, stir, after being warming up to 60 DEG C, slowly dripping mol ratio is the TEOS of 1, and time for adding is 1h, after constant temperature stirs 2h, continuing to drip mol ratio is the OTS of 0.2, time for adding is 0.5h, then at room temperature ageing 24h, can obtain the micron-sized hydrophobic SiO that granular size is 10 μm
2alkaline sol;
Step 4, prepare super-hydrophobic micron order film: with dip-coating method by SiO
2alkaline sol is evenly coated in the glass surface prepared through step 2, at N
2in atmosphere, 300 DEG C of oven dry, can form SiO at glass surface
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
The present embodiment 4 is for illustration of the preparation method of silicon dioxide super-hydrophobic thin film provided by the present invention, the raw material required for preparation method of the described silicon dioxide super-hydrophobic thin film of the 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: by the 1:0.45:3:25 mixing in molar ratio of positive silicic acid propyl ester, nitric acid, water and methyl alcohol, preparation granular size is the nano level SiO of 8nm
2acidic sol, displays aging 36h;
Step 2, prepare nano-level thin-membrane: immersed by the glass cleaned up and display aging SiO
2in acidic sol, be evenly coated in the glass surface cleaned up with crystal pulling method, pull rate is 15cm/min, uses N after film
2dry up, be then placed in 520 DEG C of retort furnaces and sinter 1.5h, nano level SiO can be obtained
2film;
Step 3, prepare alkaline sol: you mix than for the ratio of 17.2:0.45:2.4 by methyl alcohol, Tetramethylammonium hydroxide and hydromassage, stir, after being warming up to 60 DEG C, slowly drip the positive silicic acid propyl ester that mol ratio is 1, time for adding is 1h, after constant temperature stirs 2h, continue to drip the octadecyl trichlorosilane alkane that mol ratio is 0.2, time for adding is 0.5h, then at room temperature ageing 36h, can obtain the micron-sized hydrophobic SiO that granular size is 3 μm
2alkaline sol;
Step 4, prepare super-hydrophobic micron order film: with dip-coating method by SiO
2alkaline sol is evenly coated in the glass surface prepared through step 2, at N
2in atmosphere, 220 DEG C of oven dry, can form SiO at glass surface
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 example 1
Adopt the method for embodiment 1 disclosed in CN101817980A, form SiO at glass surface
2based superhydrophobic thin films DA1.
performance test
Based superhydrophobic thin films DA1 prepared by the based superhydrophobic thin films A1-A4 prepare embodiment 1-4 and comparative example 1 carries out following pencil hardness test, sticking power test and wear-resisting test respectively, and test result is as shown in table 1.
1, pencil hardness test
Mitsubishi (UNI) a set of hardness is adopted to be respectively the pencil of 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, on sample, 1000 gram forces are applied by 45 ° of directions, 10 millimeters of strokes, different positions draws 3 roads, observe sample appearance and whether have obvious cut, so that the most hard pencil number hardness for paint film of paint film can not be scratched.
2, sticking power test
Testing standard: ISO 2409;
Testing method: use the knife back of surgical knife at coating Shang Hua 12 road cut, wherein at least two cuts and other cut are at an angle of 90, and to form grid from the teeth outwards, the length of side of grid is 1 millimeter.Guarantee that every bar cut is all cut to body material.Along the both direction of cut respectively with brush brush 5 times.3M adhesive tape (Dongguan Ao meter Ke company, adhesive tape model is 3M600) be bonded on the surface, with finger tip, wiping belt is tight, guarantee the good contact with coating, in 5 minutes, from the free end of adhesive tape, within 0.5-1 second, tear well-regulated for adhesive tape opening off adhesive tape with the angle of 60 °;
Grade classification:
0 grade: the edge of otch is completely level and smooth, and the square of grid does not all peel off;
1 grade: the area of peeled-off portion is not more than with the adhesive tape area of surface contact 5%;
2 grades: the area of peeled-off portion is greater than with the adhesive tape area of surface contact 5%, and is no more than 15%;
3 grades: the area of peeled-off portion is greater than with the adhesive tape area of surface contact 15%, and is no more than 35%;
4 grades: the area of peeled-off portion is greater than with the adhesive tape area of surface contact 35%, and is no more than 65%.
3, wear-resisting test
Use the 7-IBB type RCA abrasion instrument that U.S. Nuo Man Instrument and Equipment Company produces, under the effect of 175 gram forces, mill is coated with the coating installed, the number of times that during record coating show-through material, rubber wheel rotates.
Table 1
| Pencil hardness test | Sticking power is tested | 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 example 1 | F | 0 grade | 105 circles |
From the embodiment 1-4 of table 1 compared with comparative example 1, can know that the silicon dioxide super-hydrophobic thin film of embodiment of the present invention 1-4 has preferably hardness, wear resistance, and sticking power good with matrix; And through the test of video optics contact angle measurement, the contact angle of the silicon dioxide super-hydrophobic thin film of embodiment of the present invention 1-4 reaches as high as 165 °, and roll angle, close to 0 °, absolutely proves that its hydrophobic effect is good.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (11)
1. a preparation method for silicon dioxide super-hydrophobic thin film, is characterized in that, described method comprises the steps:
Step 1, prepare acidic sol: positive silicon ester, an acidic catalyst, solvent and water are mixed, be mixed with SiO
2acidic sol; Described SiO
2siO in acidic sol
2the particle diameter of particle is 5-10nm;
Step 2, prepare nano-level thin-membrane: by described SiO
2acidic sol is coated in the surface of matrix, forms nano level SiO after sintering on the surface of matrix
2film;
Step 3, prepare alkaline sol: by positive silicon ester, basic catalyst, solvent, water mixing, then add low surface energy modifier, be mixed with SiO
2alkaline sol; Described SiO
2siO in alkaline sol
2the particle diameter of particle is 5-10 μm;
Step 4, prepare micron order film: by described SiO
2alkaline sol is coated in above-mentioned nano level SiO
2on film, the surface at matrix after oven dry obtains silicon dioxide super-hydrophobic thin film.
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; Further, the mol ratio of described positive silicon ester and low surface energy modifier is 1:0.1-0.2.
4. the preparation method according to claim 1-3 any one, is characterized in that, the composed as follows of described positive silicon ester is stated shown in general formula: Si(OR)
4, R is methyl, ethyl or propyl group.
5. the preparation method according to claim 1 or 3, is characterized in that, described low surface energy modifier is alkylalkoxy silane, and it is composed as follows states shown in general formula: R ' Si(OR)
4-n, wherein, R ' is alkyl, and R is methyl, ethyl or propyl group, n=1 or 2.
6. the preparation method according to claim 1-3 any one, is characterized in that, one or more in described solvent selected from ethanol, Virahol, methyl alcohol, propyl alcohol, butanols.
7. the preparation method according to claim 1-3 any one, is characterized in that, described an acidic catalyst is selected from one or more in hydrochloric acid, acetic acid, nitric acid.
8. the preparation method according to claim 1-3 any one, is characterized in that, described basic catalyst is selected from ammoniacal liquor and/or Tetramethylammonium hydroxide.
9. 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.
10. preparation method according to claim 1, is characterized in that, the temperature of described sintering is 500 DEG C-550 DEG C, and sintering time is 1-1.5 hour; Described oven dry is carried out under inert gas atmosphere, and temperature is 220 DEG C-300 DEG C.
11. 1 kinds of super hydrophobic materials, is characterized in that, described super hydrophobic material comprises matrix and is coated on the silicon dioxide super-hydrophobic thin film of described matrix surface, and described silicon dioxide super-hydrophobic thin film is by the method preparation as described in claim 1-10 any one.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190435A (en) * | 2006-11-29 | 2008-06-04 | 中国科学院兰州化学物理研究所 | Method for preparing super-hydrophobicity membrane on silicon face |
| CN101434709A (en) * | 2008-12-09 | 2009-05-20 | 西安交通大学 | Preparation of silastic surface hydrophobic coating |
| CN101817980A (en) * | 2010-04-22 | 2010-09-01 | 复旦大学 | Sol-gel preparation method of silica-based superhydrophobic thin films |
-
2011
- 2011-06-29 CN CN201110179240.9A patent/CN102849962B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190435A (en) * | 2006-11-29 | 2008-06-04 | 中国科学院兰州化学物理研究所 | Method for preparing super-hydrophobicity membrane on silicon face |
| CN101434709A (en) * | 2008-12-09 | 2009-05-20 | 西安交通大学 | Preparation of silastic surface hydrophobic coating |
| CN101817980A (en) * | 2010-04-22 | 2010-09-01 | 复旦大学 | Sol-gel preparation method of silica-based superhydrophobic thin films |
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