CN101092289A - A super hydrophobic material with roughened surface - Google Patents
A super hydrophobic material with roughened surface Download PDFInfo
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- CN101092289A CN101092289A CN 200710040844 CN200710040844A CN101092289A CN 101092289 A CN101092289 A CN 101092289A CN 200710040844 CN200710040844 CN 200710040844 CN 200710040844 A CN200710040844 A CN 200710040844A CN 101092289 A CN101092289 A CN 101092289A
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Abstract
This invention relates to a superhydrophobic surface material with rough microporous surface. The superhydrophobic surface material is prepared from core-shell type fluorine-containing polymer by solvent evaporation on the surface of a matrix. The pore sizes of the rough microporous surface are 0.1-1.0 mu.m. The water contact angle of the superhydrophobic surface material is greater than or equal to 155 deg. The sliding angle of water drop is less than or equal to 1 deg. After thermal treatment at 60-150 deg.C, the sliding angle of water drop can be changed from less than or equal to 1 deg. to 180 deg. with the same water contact angle. The superhydrophobic surface material thus can realize conversion between free sliding state and adhesion state, and has wide applications.
Description
Technical field
The present invention relates to a kind of superhydrophobic surface material, especially a kind of superhydrophobic surface material with coarse micropore surface.
Background technology
Be called super hydrophobic surface with the contact angle of water greater than 150 ° surface.Because super hydrophobic surface (film) has unique character, has a wide range of applications in various fields.
With the material that constitutes super hydrophobic surface or constituted the textural classification of hydrophobic surface, superhydrophobic surface material can be divided into multiple.As CN 1613565A reported adopt wet chemistry method glass surface or monocrystalline silicon surface make the zinc oxide superfine structure surface superhydrophobic surface material (with water contact angle greater than 150 °, roll angle is less than 5 °); CN 1872661A has reported the superhydrophobic surface material that utilizes self-assembly layer by layer to form multilevel hierarchy; And people such as Qingdan Xie is at " Advance Material " 2004,16, No.20, reported on the 1830-1833 with polymkeric substance utilize solvent evaporation method make the superhydrophobic surface material of the micro-nano dual structure of similar lotus leaf (with the contact angle of water be 160.5+2.1 °, roll angle is 9.0 ± 2.1 °).
To sum up, find that water droplet is difficult to realize free rolling condition and sticks conversion between state on the super hydrophobic surface (same surface) of existing super hydrophobic material with roughened surface.Given this, the invention provides a kind of novel super hydrophobic material with roughened surface, fill up the prior art empty.
Summary of the invention
The invention provides the super hydrophobic material with roughened surface that a kind of super hydrophobic surface has microvoid structure, the super hydrophobic material with roughened surface of this kind microvoid structure makes water droplet roll angle thereon from increasing to 180 ° (being that super hydrophobic surface upset back water droplet still sticks and not landing) less than 1 ° by the intensity of variation (can realize by the thermal treatment of specified conditions) of the microvoid structure of control surface; By thermal treatment, the roll angle of water droplet can be reduced to less than 1 ° again, is implemented on the same surface the free rolling condition of water droplet and stick conversion between state.
The said super hydrophobic material with roughened surface with microvoid structure of the present invention is characterized in that, said super hydrophobic material with roughened surface adopts the solvent evaporation method film forming to make in substrate surface by hud typed fluoropolymer; Prepared super hydrophobic material with roughened surface with microvoid structure:
The micropore size that it had (diameter) is 0.1 μ m～1.0 μ m; With the contact angle of water more than or equal to 155 °; The roll angle of water droplet is less than or equal to 1 °, and keep with the constant condition of the contact angle of water under, through the roll angle of 60 ℃～150 ℃ thermal treatments, water droplet from being less than or equal to 1 ° to 180 ° conversion.
In the present invention, the base material that constitutes said microvoid structure superhydrophobic surface material be there is no particular restriction, the existing base material that is used to prepare superhydrophobic surface material all is applicable to the present invention, and the base material that the present invention recommends to use is glass.Used solvent is fluorochloroparaffins (C in the said solvent evaporation method
2～C
6Fluorochloroparaffins, preferred C
2～C
4Fluorochloroparaffins) or N, dinethylformamide (DMF).
In optimal technical scheme of the present invention, the nuclear of said hud typed fluoropolymer is by a kind of in acrylic ester monomer, styrene monomer, vinyl cyanide monomer or the vinyl acetate between to for plastic esters monomer, two or more is through the polymkeric substance of homopolymerization or copolymerization gained, and preferred nuclear is the polymkeric substance that is formed by monomer polymerization shown in the formula (1)
In the formula (1), R
1Be H or CH
3, R
2Be C
1～C
6Alkyl.
The shell of said hud typed fluoropolymer is by a kind of in fluoro acrylic ester class monomer, fluoroolefins monomer, fluorostyrene class monomer or the fluoric vinyl ethers monomer, two or more is through the polymkeric substance of homopolymerization or copolymerization gained, and preferred shell is the polymkeric substance that is formed by monomer polymerization shown in the formula (2).
In the formula (2), R
3Be H or CH
3, R
4Be C
1～C
8Perfluoroalkyl, a=0,1,2 or 3.
Wherein said fluoroolefins monomer is as (but being not limited to): tetrafluoroethylene, R 1216, fluorine vinylchlorid partially; Said fluorostyrene class monomer is meant the fluorochemicals that all or part of hydrogen atom is replaced atom or replaced by trifluoromethyl by fluorine on the cinnamic phenyl ring.
Description of drawings
Fig. 1. the electron scanning micrograph (big scale) of the uneven surface in the example 1 of the present invention
Fig. 2. the electron scanning micrograph (small scale) of the uneven surface in the example 1 of the present invention
Fig. 3. in the example 1 of the present invention through the electron scanning micrograph of 2 hours uneven surface of thermal treatment
Fig. 4. the contact angle photo of water droplet on the uneven surface in the example 1 of the present invention
Fig. 5. the electron scanning micrograph of the solid surface in the example 4 of the present invention
Embodiment
Prepare the said method of the present invention, comprise the steps: with microvoid structure super hydrophobic material with roughened surface
(1) preparation of hud typed fluorine-containing copolymer emulsion:
Nuclear monomer (methyl methacrylate, n-butyl acrylate, ethyl propenoate are or/and methyl acrylate) is made nuclear monomer pre-emulsion and shell monomer pre-emulsion through the pre-emulsification of ultrasonic wave respectively with shell monomer (vinylformic acid perfluoro alkyl ethyl or methacrylic acid perfluoro alkyl ethyl).Adopt the emulsion polymerisation process of existing hud typed polymkeric substance to obtain hud typed fluorine-containing copolymer emulsion.
As: the nuclear monomer pre-emulsion is under 40 ℃ of conditions, polymerization gets the nuclear monomer polymerized emulsion in redox initiator system (Potassium Persulphate-sodium bisulfite-copper sulfate is initiator), (the shell monomer pre-emulsion is at 30 ℃ to drip the shell monomer polymerized emulsion in this nuclear monomer polymerized emulsion, at 1 of perfluor-α-positive propoxy propionyl superoxide, 1,2-three fluoro-1,2, polymerization in the 2-trichloroethane solution and get), drip off and finish, be incubated 2 hours, regulate pH value to 7～8, back discharging gets hud typed fluorine-containing copolymer emulsion, and wherein the weight ratio of nuclear monomer and shell monomer is (0.5～3): 1;
(2) have the preparation of the super hydrophobic material with roughened surface of microvoid structure:
To be added drop-wise to the MgSO that concentration is 2wt% by the hud typed fluorine-containing copolymer emulsion that step (1) makes
4Solution in carry out breakdown of emulsion, behind suction filtration, obtain hud typed fluoropolymer, this fluoropolymer through methyl alcohol and deionized water wash and 40 ℃ of vacuum-dryings to constant weight.
The hud typed fluoropolymer of above-mentioned drying is dissolved in 1,1,2-three fluoro-1,2,2-trichloroethane (F113) or N, dinethylformamide, film forming promptly gets target material after on the clean sheet glass.
The super hydrophobic material with roughened surface that the present invention adopts hud typed fluoropolymer to make is implemented on the same surface, the free rolling condition of water droplet and stick conversion between state.Fill up the blank in the existing superhydrophobic surface material, widened the Application Areas of superhydrophobic surface material.
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention, and unrestricted protection scope of the present invention:
Embodiment 1
(1) fluorinated acrylate core-shell emulsion polymerization:
Nuclear monomer (methyl methacrylate) is 3: 1 with shell monomer (methacrylic acid perfluoro alkyl ethyl) proportioning that add the back.
Shell monomer is through auto-polymerization: at N
2Protection adds the F113 solution of perfluor-α-positive propoxy propionyl superoxide down in through the pre-emulsified fluorine monomer emulsion of ultrasonic wave, consumption is that 30%, 30 ℃ of monomer mass stirs down, carries out polymerization 1h.
Whole emulsifying agents are mixed with the 10ml deionized water, stir, it is fully dissolved.Get 1/3 of this solution, pour in the beaker, place ultrasonic generator, carry out the pre-emulsification of ultrasonic wave of 0.5h with load weighted nuclear monomer.
5ml deionized water and pH buffer reagent sodium bicarbonate are added in the four-hole boiling flask of 100ml, mechanical stirring, vacuumize logical nitrogen 3 times to remove oxygen, warming-in-water to 40 ℃, maintenance system malleation, add nuclear monomer methyl methacrylate pre-emulsion, next inject 1/3 of initiator solution, treat that emulsion occurs beginning constant speed dropping initiator (stopping after half an hour dripping) behind the blue opalescence.Be incubated after 2 hours, drip shell monomer methacrylic acid perfluoro alkyl ethyl emulsion polymerization liquid and residue initiator, until all dripping off, cooling is regulated the back discharging of pH value with ammoniacal liquor.
(2) to be added drop-wise to concentration be 2% MgSO to the fluorinated acrylate core-shell emulsion
4Solution in carry out breakdown of emulsion, through obtaining fluoropolymer behind the vacuum filtration, wash with dissolve with methanol again.Behind deionized water wash, 40 ℃ of following vacuum-dryings to constant weight.
(3) fluorinated acrylate polymer is dissolved in 1,1,2-three fluoro-1 with 1% massfraction concentration, 2, in the 2-trichloroethane, at room temperature, drying and forming-film on clean sheet glass obtains the super hydrophobic surface that the surface is covered with coarse microvoid structure, and its diameter is 0.1 μ m～1.0 μ m.
(4) polymeric film was 130 ℃ of following thermal treatments 2 hours.
Be 162 ° to the contact angle of water droplet before the polymeric film that makes in this example is not heat-treated, roll angle＜1 °), promptly polymer film surface has very little adhesive power to water droplet.Under 130 ℃ behind thermal treatment 2h, polymeric film is 155 ° to the contact angle of water droplet, roll angle is from increasing to 180 ° less than 1 °, i.e. surface upset back water droplet still sticks not landing °
Accompanying drawing 1, accompanying drawing 2, accompanying drawing 3 is respectively the electron scanning micrograph (big scale) of uneven surface, the electron scanning micrograph of uneven surface (small scale), electron scanning micrograph with the uneven surface of thermal treatment 2h, accompanying drawing 4 is the contact angle photo of water droplet on the uneven surface, and contact angle is 162 °.
Embodiment 2
(1) fluorinated acrylate core-shell emulsion polymerization: nuclear monomer (methyl methacrylate) is 3: 1 with shell monomer (methacrylic acid perfluoro alkyl ethyl) proportioning that add the back.
Shell monomer is through auto-polymerization: at N
2Protection adds the F113 solution of perfluor-α-positive propoxy propionyl superoxide down in through the pre-emulsified fluorine monomer emulsion of ultrasonic wave, quality is that 30%, 30 ℃ of monomer mass stirs down, carries out polymerization 1h.
Whole emulsifying agents are mixed with the 10ml deionized water, stir, it is fully dissolved.Get 1/3 of this solution, pour in the beaker, place ultrasonic generator, carry out the pre-emulsification of ultrasonic wave of 0.5h with load weighted nuclear monomer.
5ml deionized water and pH buffer reagent sodium bicarbonate are added in the four-hole boiling flask of 100ml, mechanical stirring, vacuumize logical nitrogen 3 times to remove oxygen, warming-in-water to 40 ℃, maintenance system malleation, add nuclear monomer methyl methacrylate pre-emulsion, next inject 1/3 of initiator solution, beginning dripped initiator (stopping after half an hour dripping) with constant speed after blue opalescence appearred in emulsion by the time.Be incubated after 2 hours, drip shell monomer methacrylic acid perfluoro alkyl ethyl emulsion polymerization liquid and residue initiator, until all dripping off, cooling is regulated the back discharging of pH value with ammoniacal liquor.
(2) to be added drop-wise to concentration be 2% MgSO to the fluorinated acrylate core-shell emulsion
4Solution in carry out breakdown of emulsion, through obtaining fluoropolymer behind the vacuum filtration, wash with dissolve with methanol again.Behind deionized water wash, 40 ℃ of following vacuum-dryings to constant weight.
(3) fluorinated acrylate polymer is dissolved in 1,1,2-three fluoro-1 with 1% massfraction concentration, 2, in the 2-trichloroethane, at room temperature, drying and forming-film on clean sheet glass obtains the super hydrophobic surface that the surface is covered with coarse microvoid structure, and its diameter is 0.1 μ m～1.0 μ m.
(4) 110 ℃ of following thermal treatments of polymeric film 2 hours.
The polymeric film that makes in this example is 155 ° to the contact angle of water droplet, under 110 ℃ behind thermal treatment 2h, polymer film surface is about 30 ° to the roll angle of water droplet.
Embodiment 3
(1) fluorinated acrylate core-shell emulsion polymerization: nuclear monomer (methyl methacrylate) is 3: 1 with shell monomer (methacrylic acid perfluoro alkyl ethyl) proportioning that add the back.
Shell monomer is through auto-polymerization: at N
2Protection adds the F113 solution of perfluor-α-positive propoxy propionyl superoxide down in through the pre-emulsified fluorine monomer emulsion of ultrasonic wave, quality is that 30%, 30 ℃ of monomer mass stirs down, carries out polymerization 1h.
Whole emulsifying agents are mixed with the 10ml deionized water, stir, it is fully dissolved.Get 1/3 of this solution, pour in the beaker, place ultrasonic generator, carry out the pre-emulsification of ultrasonic wave of 0.5h with load weighted nuclear monomer.
5ml deionized water and pH buffer reagent sodium bicarbonate are added in the four-hole boiling flask of 100ml, mechanical stirring, vacuumize logical nitrogen 3 times to remove oxygen, warming-in-water to 40 ℃, maintenance system malleation, add nuclear monomer methyl methacrylate pre-emulsion, next inject 1/3 of initiator solution, beginning dripped initiator (stopping after half an hour dripping) with constant speed after blue opalescence appearred in emulsion by the time.Be incubated after 2 hours, drip shell monomer methacrylic acid perfluoro alkyl ethyl emulsion polymerization liquid and residue initiator, until all dripping off, cooling is regulated the back discharging of pH value with ammoniacal liquor.
(2) to be added drop-wise to concentration be 2% MgSO to the fluorinated acrylate core-shell emulsion
4Solution in carry out breakdown of emulsion, through obtaining fluoropolymer behind the vacuum filtration, wash with dissolve with methanol again.Behind deionized water wash, 40 ℃ of following vacuum-dryings to constant weight.
(3) fluorinated acrylate polymer is dissolved in 1,1,2-three fluoro-1 with 1% massfraction concentration, 2, in the 2-trichloroethane, at room temperature, drying and forming-film on clean sheet glass obtains the super hydrophobic surface that the surface is covered with coarse microvoid structure, and its diameter is 0.1 μ m～1.0 μ m.
(4) 140 ℃ of following thermal treatments of polymeric film 2 hours.
The polymeric film that makes in this example is 155 ° to the contact angle of water droplet, under 140 ℃ behind thermal treatment 2h, polymer film surface is about 75 ° to the roll angle of water droplet.
Embodiment 4
(1) fluorinated acrylate core-shell emulsion polymerization: nuclear monomer (methyl methacrylate) is 3: 1 with shell monomer (methacrylic acid perfluoro alkyl ethyl) proportioning that add the back.
Shell monomer is through auto-polymerization: at N
2Protection adds the F113 solution of perfluor-α-positive propoxy propionyl superoxide down in through the pre-emulsified fluorine monomer emulsion of ultrasonic wave, quality is that 30%, 30 ℃ of monomer mass stirs down, carries out polymerization 1h.
Whole emulsifying agents are mixed with the 10ml deionized water, stir, it is fully dissolved.Get 1/3 of this solution, pour in the beaker, place ultrasonic generator, carry out the pre-emulsification of ultrasonic wave of 0.5h with load weighted nuclear monomer.
5ml deionized water and pH buffer reagent sodium bicarbonate are added in the four-hole boiling flask of 100ml, mechanical stirring, vacuumize logical nitrogen 3 times to remove oxygen, warming-in-water to 40 ℃, maintenance system malleation, add nuclear monomer methyl methacrylate pre-emulsion, next inject 1/3 of initiator solution, beginning dripped initiator (stopping after half an hour dripping) with constant speed after blue opalescence appearred in emulsion by the time.Be incubated after 2 hours, drip shell monomer methacrylic acid perfluoro alkyl ethyl emulsion polymerization liquid and residue initiator, until all dripping off, cooling is regulated the back discharging of pH value with ammoniacal liquor.
(2) to be added drop-wise to concentration be 2% MgSO to the fluorinated acrylate core-shell emulsion
4Solution in carry out breakdown of emulsion, through obtaining fluoropolymer behind the vacuum filtration, wash with dissolve with methanol again.Behind deionized water wash, 40 ℃ of following vacuum-dryings to constant weight.
(3) fluorinated acrylate polymer is dissolved in 1,1,2-three fluoro-1 with 1% massfraction concentration, 2, in the 2-trichloroethane, at room temperature, drying and forming-film on clean sheet glass obtains the super hydrophobic surface that the surface is covered with coarse microvoid structure, and its diameter is 0.1 μ m～1.0 μ m.
(4) 130 ℃ of following thermal treatments of polymeric film 6 hours.
The polymeric film that makes in this example is 155 ° to the contact angle of water droplet, under 130 ℃ behind thermal treatment 6h, polymer film surface to the roll angle of water droplet less than 1 °.Accompanying drawing 5 is the electron scanning micrograph of the uneven surface behind the thermal treatment 6h.
Embodiment 5
(1) fluorinated acrylate core-shell emulsion polymerization: nuclear monomer (methyl methacrylate) is 3: 1 with shell monomer (vinylformic acid perfluoro alkyl ethyl) proportioning that add the back.
Shell monomer is through auto-polymerization: at N
2Protection adds the F113 solution of perfluor-α-positive propoxy propionyl superoxide down in through the pre-emulsified fluorine monomer emulsion of ultrasonic wave, quality is that 30%, 30 ℃ of monomer mass stirs down, carries out polymerization 1h.
Whole emulsifying agents are mixed with the 10ml deionized water, stir, it is fully dissolved.Get 1/3 of this solution, pour in the beaker, place ultrasonic generator, carry out the pre-emulsification of ultrasonic wave of 0.5h with load weighted nuclear monomer.
5ml deionized water and pH buffer reagent sodium bicarbonate are added in the four-hole boiling flask of 100ml, mechanical stirring, vacuumize logical nitrogen 3 times to remove oxygen, warming-in-water to 40 ℃, maintenance system malleation, add nuclear monomer methyl methacrylate pre-emulsion, next inject 1/3 of initiator solution, beginning dripped initiator (stopping after half an hour dripping) with constant speed after blue opalescence appearred in emulsion by the time.Be incubated after 2 hours, drip shell monomer vinylformic acid perfluoro alkyl ethyl emulsion polymerization liquid and residue initiator, until all dripping off, cooling is regulated the back discharging of pH value with ammoniacal liquor.
(2) to be added drop-wise to concentration be 2% MgSO to the fluorinated acrylate core-shell emulsion
4Solution in carry out breakdown of emulsion, through obtaining fluoropolymer behind the vacuum filtration, wash with dissolve with methanol again.Behind deionized water wash, 40 ℃ of following vacuum-dryings to constant weight.
(3) fluorinated acrylate polymer is dissolved in 1,1,2-three fluoro-1 with 1% massfraction concentration, 2, in the 2-trichloroethane, at room temperature, drying and forming-film on clean sheet glass obtains the super hydrophobic surface that the surface is covered with coarse microvoid structure, and its diameter is 0.1 μ m～1.0 μ m.
The polymeric film that makes in this example is 152 ° to the contact angle of water droplet.
Claims (7)
1, a kind of super hydrophobic material with roughened surface with microvoid structure is characterized in that, said super hydrophobic material with roughened surface adopts the solvent evaporation method film forming to make in substrate surface by hud typed fluoropolymer; Prepared super hydrophobic material with roughened surface with microvoid structure:
The aperture of the micropore that it had is 0.1 μ m～1.0 μ m; With the contact angle of water more than or equal to 155 °; The roll angle of water droplet is less than or equal to 1 °, and keep with the constant condition of the contact angle of water under, through the roll angle of 60 ℃～150 ℃ thermal treatments, water droplet from being less than or equal to 1 ° to 180 ° conversion.
As the said super hydrophobic material with roughened surface of claim 1, it is characterized in that 2, used solvent is C in the wherein said solvent evaporation method
2～C
6Fluorochloroparaffins or N, dinethylformamide.
As the said super hydrophobic material with roughened surface of claim 2, it is characterized in that 3, wherein said fluorochloroparaffins is 1,1,2-three fluoro-1,2,2-trichloroethane.
As the said super hydrophobic material with roughened surface of claim 1, it is characterized in that 4, wherein said base material is a glass.
5, as the said super hydrophobic material with roughened surface of claim 1, it is characterized in that, wherein the nuclear of said hud typed fluoropolymer is that two or more is through the polymkeric substance of homopolymerization or copolymerization gained by a kind of in acrylic ester monomer, styrene monomer, vinyl cyanide monomer or the vinyl acetate between to for plastic esters monomer;
The shell of said hud typed fluoropolymer is that two or more is through the polymkeric substance of homopolymerization or copolymerization gained by a kind of in fluoro acrylic ester class monomer, fluoroolefins monomer, fluorostyrene class monomer or the fluoric vinyl ethers monomer;
And the monomer that constitutes nuclear is (0.5～3) with the monomeric weight ratio that constitutes shell: 1.
6, as the said super hydrophobic material with roughened surface of claim 5, it is characterized in that, wherein the polymkeric substance that forms by monomer polymerization shown in the formula (1) of the nuclear of said hud typed fluoropolymer:
In the formula (1), R
1Be H or CH
3, R
2Be C
1～C
6Alkyl.
7, as the said super hydrophobic material with roughened surface of claim 5, it is characterized in that, wherein the polymkeric substance of the shell of said hud typed fluoropolymer for forming by monomer polymerization shown in the formula (2):
In the formula (2), R
3Be H or CH
3, R
4Be C
1～C
8Perfluoroalkyl, a=0,1,2 or 3.
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| CN2007100408449A CN101092289B (en) | 2007-05-18 | 2007-05-18 | A super hydrophobic material with roughened surface |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891142A (en) * | 2010-07-12 | 2010-11-24 | 浙江工业大学 | Method for preparing active, flow impact resistant and non-lotus-like super-hydrophobic surface |
| CN101274858B (en) * | 2008-05-16 | 2011-03-23 | 景德镇陶瓷学院 | Hydrophobic self-cleaning sanitary ware glaze and preparation thereof |
| CN102625784A (en) * | 2009-05-06 | 2012-08-01 | 康宁股份有限公司 | Fingerprint-resistant glass substrates |
| CN103951277A (en) * | 2014-05-04 | 2014-07-30 | 江南大学 | Super-lyophobic anti-reflection glass surface layer and preparation method thereof |
| CN105386060A (en) * | 2015-10-29 | 2016-03-09 | 上海博物馆 | Method for constructing super-hydrophobic film on rusty bronze surface |
| CN105420735A (en) * | 2015-10-29 | 2016-03-23 | 上海博物馆 | Super-hydrophobic fluoro-alkyl silanes composite thin film and preparation method thereof |
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| AU707886B2 (en) * | 1995-07-27 | 1999-07-22 | Asahi Glass Company Limited | Water and oil repellent composition, treating method therewith and copolymer |
| CN1151226C (en) * | 2000-03-29 | 2004-05-26 | 中国科学院化学研究所 | Surface-treating agent with both super-hydrophobicity and super-oleophobicity and its application |
| DE10063739B4 (en) * | 2000-12-21 | 2009-04-02 | Ferro Gmbh | Substrates with self-cleaning surface, process for their preparation and their use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274858B (en) * | 2008-05-16 | 2011-03-23 | 景德镇陶瓷学院 | Hydrophobic self-cleaning sanitary ware glaze and preparation thereof |
| CN102625784A (en) * | 2009-05-06 | 2012-08-01 | 康宁股份有限公司 | Fingerprint-resistant glass substrates |
| CN101891142A (en) * | 2010-07-12 | 2010-11-24 | 浙江工业大学 | Method for preparing active, flow impact resistant and non-lotus-like super-hydrophobic surface |
| CN101891142B (en) * | 2010-07-12 | 2012-07-04 | 浙江工业大学 | Method for preparing active, flow impact resistant and non-lotus-like super-hydrophobic surface |
| CN103951277A (en) * | 2014-05-04 | 2014-07-30 | 江南大学 | Super-lyophobic anti-reflection glass surface layer and preparation method thereof |
| CN103951277B (en) * | 2014-05-04 | 2015-11-25 | 江南大学 | A kind of super lyophoby anti-reflective glass upper layer and preparation method thereof |
| CN105386060A (en) * | 2015-10-29 | 2016-03-09 | 上海博物馆 | Method for constructing super-hydrophobic film on rusty bronze surface |
| CN105420735A (en) * | 2015-10-29 | 2016-03-23 | 上海博物馆 | Super-hydrophobic fluoro-alkyl silanes composite thin film and preparation method thereof |
| CN105420735B (en) * | 2015-10-29 | 2018-04-03 | 上海博物馆 | A kind of super-hydrophobic silicon fluoride laminated film and preparation method thereof |
| CN105386060B (en) * | 2015-10-29 | 2018-08-28 | 上海博物馆 | A method of in band rust Bronze constructing super-drainage film |
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