CN106833043A - A kind of transparent durable super-hydrophobic new material coating and preparation method thereof - Google Patents

A kind of transparent durable super-hydrophobic new material coating and preparation method thereof Download PDF

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Publication number
CN106833043A
CN106833043A CN201710108028.0A CN201710108028A CN106833043A CN 106833043 A CN106833043 A CN 106833043A CN 201710108028 A CN201710108028 A CN 201710108028A CN 106833043 A CN106833043 A CN 106833043A
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coating
preparation
hydrophobic
ceramic particle
water
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甄建生
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Super Technology (beijing) Co Ltd
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Super Technology (beijing) Co Ltd
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Priority to CN201710108028.0A priority Critical patent/CN106833043A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic

Abstract

The present invention relates to transparent durable super-hydrophobic new material coating of one kind and preparation method thereof, by following mass percent into being grouped into:Nano-ceramic particle mixture 1 ~ 20%, fluorosilicone coupling agent 0.1 ~ 5%, esters of silicon acis 1 ~ 10%, catalyst 0.01 ~ 0.1% and water 1 ~ 10%, remaining is organic solvent.Coating range of application of the invention is quite varied, and light transmittance is high, super-hydrophobic and long service life, can be very good to be attached to metal, glass, the surface of ceramic and various organic plastics.

Description

A kind of transparent durable super-hydrophobic new material coating and preparation method thereof
Technical field
The invention belongs to coating preparation field, and in particular to a kind of transparent durable super-hydrophobic new material coating and its preparation Method.
Background technology
It is hydrophobic and it is hydrophilic be describe water and solid contact when wetting phenomena.When liquid soaks the surface of solids, script gas- Solid interface replaced by liquid-solid interface, and the gas-solid difference with liquid-solid interfacial tension, referred to as " wetting tension ".When When gas-solid interfacial tension is more than liquid-solid interfacial tension, that is, attraction between solid and liquid is more than solid and gas Between attraction when, the interfacial tension between solid and gas can stretch liquid-solid interface.In other words, the solid table being wet There is relatively low interfacial tension in face, therefore liquid can be expanded in the surface of solids.When liquid drop on a solid surface when, the surface of solids and The angle of tangent, is exactly so-called contact angle.And the relation of wetting tension and contact angle, can be stated with young's formula:
Gas-solid interface tension force,Liquid-solid interface tension force,Liquid-vapor interface tension force,Young contact angle.
Young's formula is only applicable to the surface of solids being completely smooth.Wenzel is determined when liquid directly contact micro-structural Surface when, θ angles can be changed into θ W,
Wherein, r is the ratio of real area and projected area.The equation of Wenzel shows that one surface of micro-structural will put Large surface tension force.Hydrophobic surface(With the contact angle more than 90 °)Can become more hydrophobic after micro-structural, its is new Contact angle will be than original increase.However, a hydrophilic surface(With the contact angle less than 90 °)But can after micro-structural Become more hydrophilic, its new contact angle will be than original reduction.
Cassie and Baxter have been found that liquid suspension in micro-structure surface, and θ angles will be changed into θ CB,
Wherein, φ is the ratio that solid and liquid contact surface are accumulated.Liquid under Cassie-Baxter states is than Wenzel state Motility is had more down.Even the equation of Cassie-Baxter shows a hydrophilic surface, in suspended microstructures, its New contact angle can also show hydrophobicity.
By the new contact angle calculated with two above equation, we can predict Wenzel states or Cassie- Whether Baxter states should be present.Due to the limitation for having minimization of free energy, the shape with smaller new contact angle is predicted State will more likely there are.Mathematically, there is Cassie-Baxter stable states, inequality below is necessary Set up.
From microstructure angle, judge that the alternate standard that Cassie-Baxter states whether there is is:1) contact line is made every effort to overcome Take the gravity of the non-supported portion of drop point;2) the sufficiently high substrate so as to prevent drop contact micro-structural of micro-structural.
Contact angle is the hydrophobic method of static measurement, and contact angle hysteresis and slide angle are then to hydrophobic dynamic measurement Method.Contact angle hysteresis is a kind of phenomenon for identifying surface heterogeneous medium.When liquid note is arrived the surface of solids by pipettor, liquid will Form certain contact angle.As the increase of injection liquid, the volume of drop can increase therewith, contact angle can also become big, but three Phase boundray can keep fixed until liquid overflows suddenly.The contact angle of moment is referred to as advancing contact angle before liquid spilling.Return Moving back contact angle can be by the way that liquid to be sucked out measurement from drop.As liquid is sucked out, the volume of drop reduces, contact angle Also reduce, but three-phase boundary equally keeps fixed until being sucked back completely.The contact angle for being sucked back into moment in liquid is referred to as back Move back contact angle.And the difference between advancing contact angle and rollback contact angle is exactly contact angle hysteresis, it is used to identify surface Heterogeneous, roughening and motility.The surface of non-homogeneous has the region that can hinder contact line.Slide angle is another dynamic Measure hydrophobic method:A liquid point is placed in the surface of solids, inclined surface starts to slide until drop, inclination angle now As slide angle.Drop in Cassie-Baxter states would generally show the slide angle smaller than Wenzel state and Contact angle hysteresis.So Cassie-Baxter states are more satisfactory hydrophobic surfaces.
Coating is a kind of method of the efficiency-cost ratio high for changing existing material wettability.- as super-hydrophobic coating and water Contact angle is less than 10 ° more than 150 °, roll angle.Super-hydrophobic coat has the excellent tables such as self-cleaning, antifouling grease proofness, anti-corrosive properties Face performance, has broad application prospects in actual production and life.Super-hydrophobic coat can be used for automobile, aircraft, steamer Deng exterior wall glass and its shell coating, can effectively reach waterproof it is antifog, reduce coefficient of friction, increase anticorrosion and antifouling performance Deng;Petroleum pipeline and some be used to be applied in the inwall of shipping container, reduction friction, anti-sticking, anti-clogging, impermeable can be played Deng;When being applied in weaving and leather industry, waterproof and oilproof and weather resistance etc. can be played.Using the low material of surface energy such as Fluorine silicon materials, using lithographic technique, collosol and gel, chemical vapor deposition, polymer solution film forming, mould plate technique, electrospinning, The simple effective methods such as electrochemical method construct and regulation and control film dual microtexture, so as to obtain surface roughness and microcosmic Construct suitable Cassie-Baxter states to exist, be to realize the feasible way that super-hydrophobic film coating industry metaplasia is produced.
Self-cleaning waterproof coating has been developed two generation products.It is good it is auspicious it is good be to compare the generation self-cleaning coat having with table.It Self-cleaning mechanism be a kind of Passive Mode.Good auspicious good coating is in itself hydrophilic, there is good adhesive force, and its self-cleaning function comes Moisture is catalytically decomposed from the nano particle in coating, this passive self-cleaning mode takes long enough and specified conditions ability Play a role, such as in the case of no light, water just evaporates before being decomposed, and the impurity in water will stay in implements table On face.Second generation coating is that ULTRADRY such as produced in USA, its surface can be very low, and moisture is difficult to based on hydrophobic material Adhere to its surface, but coating adhesive force in itself is also very poor, generally requires intermediate medium, and nonetheless, service life is general Also only 1 year or so.
And common super hydrophobic surface is due to the coarse structure on surface and opaque, so as to limit its range of application, There is attraction on the good surface of the transparency to existing super-hydrophobicity very much in application fields such as eyeglass, windshield in visible-range again Power.High transmission rate typically has two kinds of approach:1. coating surface macro structural scale is controlled in the range of 30-100 nm, micro-structural Size is much smaller than the wavelength of visible ray, so the transparency is very well.2. many that average-size is for about 100-500nm is introduced in coating Hole, and most aperture is spaced apart.This method also shows high transparency in most of wave-length coverages, but prepares It is relatively costly.
The content of the invention
In order to solve problems of the prior art, the present invention provides a kind of light transmittance material high, super-hydrophobic, durable Coating and preparation method thereof.
The present invention is adopted the following technical scheme that:A kind of transparent durable super-hydrophobic new material coating, by following quality percentage Ratio into being grouped into:Nano-ceramic particle mixture 1 ~ 20%, fluorosilicone coupling agent 0.1 ~ 5%, esters of silicon acis 1 ~ 10%, catalyst 0.01 ~ 0.1% and water 1 ~ 10%, remaining is organic solvent.
In a preferred embodiment of the present invention, the diameter of described nano-ceramic particle is more excellent at 5 to 200 nanometers Choosing is 10 to 150 nanometers, and most preferably 30 to 100 nanometers, it is preferably circular in shape.
In a preferred embodiment of the present invention, described nano-ceramic particle is selected from TiO2, SnO, Al2O3, SiO2In The combination of one or more, more preferably SnO, Al2O3, SiO2In the combination of one or more, preferably Al2O3, SiO2 In one or more.
The present invention also protects the preparation method of above-mentioned transparent durable super-hydrophobic new material coating, mixes each component by proportioning Conjunction obtains coating mix, in room temperature to stirring 90 ~ 180 minutes at 60 DEG C, then by coating mix using air spraying or It is direct invasion, then is drying 15-60 minutes or placing more than 24h at room temperature at 80-120 DEG C.
In a preferred embodiment of the present invention, because nano-ceramic particle is that high temperature sintering is formed, and do not connect Wet air was touched, then nano-ceramic particle must do surface activation process.The purpose of activation process is to increase surface-OH keys Number, because nano-metal-oxide surface is very active, described activation process is to be contacted with water.Receiving after activation process The very easy conglomeration of rice grain, it is necessary to carry out sequent surface treatment in time.The key of surface treatment is silane coupler.This is one In the molecule simultaneously containing two kinds of organo-silicon compound of different chemical property groups, its classical product can use general formula R SiX to class3 Represent.In formula, R is non-hydrolytic group, including alkenyl(Predominantly vinyl), and end is with Cl, NH2, SH, epoxy, N3、(Methyl)The alkyl of the functional groups such as acryloxy, NCO, i.e. carbon functional group;X is hydrolyzable groups, including Cl, OMe, OEt, OC2H4OCH3, OSiMe3, and OAc etc..Due to this special construction, have simultaneously in silane coupled agent molecule Energy and inanimate matter material(Such as glass, silica sand, metal and metal oxide)Chemically combined reactive group and there is low-surface-energy Organic matter group, be very suitable for surface treatment.
Present invention utilizes two kinds of different coupling agents:Fluorosilicone coupling agent and esters of silicon acis(Non-fluorine).Fluorosilicone idol The organic group for joining agent can provide 20mJ/m for coating2Ultra-low surface energy.The general surface of esters of silicon acis organic group can be 40mJ/m2.But compare with fluorosilicone coupling agent, cheap many of esters of silicon acis and also can provide more firmly with The connection of matrix.
In a preferred embodiment of the present invention, described fluorosilicone coupling agent is:
Wherein, between 4 to 17, between 1 to 4, R has 1 to 6 carbon atoms to m to n.Representational commercial product is ten Trifluoro octyltri-ethoxysilane.
In a preferred embodiment of the present invention, described esters of silicon acis is:
Wherein, R is hydrophobic group, and X is hydrophilic group.Representational commercial product is tetraethyl orthosilicate.
In a preferred embodiment of the present invention, the mass percent of described esters of silicon acis is 1-5%.
In a preferred embodiment of the present invention, for realize on nano particle grow one layer of continuous organic film, silicon Oxygen alkane coupling agent summation is 1 with nanoparticle mass ratio:5;More preferably 1:2.
Produced coating surface be able to can be calculated with below equation
Wherein,fIt is the ratio of fluorosilicone coupling agent.And then can be hydrophobic using Cassie-Baxter equations control coating Degree.
Silane coupler surface treatment can be described as four-step reaction model:(1)3 Si-X bases being connected with silicon are hydrolyzed into Si-OH;(2)Between Si-OH dehydrating condensation into containing Si-OH oligosiloxane;(3)Si-OH and substrate surface in oligomer On OH formed hydrogen bond;(4)Covalent bond connection, but the silane on interface are formed in heat curing process with dehydration Silicone hydroxyl is bonded with substrate surface only one of which, is left two Si-OH or is condensed with the Si-OH in other silane, Huo Zheyou From state.
In a preferred embodiment of the present invention, the first step is to carry out a certain degree of pre- water to silane coupler before the use Solution.In hydrolytic process, it is to avoid condensation reaction can not occur between silane, oligosiloxane is generated.Oligosiloxane is excessive, Then make the muddy even precipitation of inorganic agent, reduce coupling agent stability and influence treatment quality.So silane prehydrolysis(Reaction 1), Condensation reaction(Reaction 2)Can be completed with a step with nanoparticulate activated treatment.Concrete technology is nano-ceramic particle, fluorosilicone Coupling agent, esters of silicon acis, water and organic solvent are mixed by 1 ~ 20%, 0.1 ~ 15%, 1 ~ 15%, 1 ~ 10% and 70 ~ 80% mass percent Close.
In a preferred embodiment of the present invention, the organic solvent is selected from ethanol, propyl alcohol, in isopropanol and butanol One or more.
In a preferred embodiment of the present invention, described catalyst is selected from nitric acid, acetate and hydrochloride.
In a preferred embodiment of the present invention, catalyst is eventually adding, and regulation pH values are 1 ~ 4, then under 60C Stirring 90 ~ 180 minutes.
Film formation reaction is the committed step for influenceing silanization quality, and the quality that film formation reaction is carried out directly affects the property of coating Energy and quality.Therefore, for pH value, temperature, the state modulator such as time is particularly significant, and workpieces surface condition is proposed more Requirement high:1st, oil removing is complete;2nd, workpiece can not carry metal fragment or other impurities;3rd, silanization pre-treatment is preferably with going Ionized water.
In a preferred embodiment of the present invention, the air spraying is existed using 0.2 ~ 0.5mm jet pipes and pressure The compressed air of 0.15 ~ 0.5MPa, optimal jet length is 15 ~ 20cm.Under such preferred spraying scheme, coating dispersion Into micro droplets, most of organic solvent has evaporated before base material is reached, so that micro-shape is preserved.
In a preferred embodiment of the present invention, coating dries 24 hours or drying 15 minutes at 120 DEG C in room temperature.
Compared with prior art, advantage of the invention is that coating range of application of the invention is quite varied, light transmittance is high, Super-hydrophobic and long service life, can be very good to be attached to metal, glass, the surface of ceramic and various organic plastics, coating Naked eyes itself is invisible, but can be that protection materials are not adhered to by water and other liquid in itself, implements surface is kept cleaning, no Haze.Other coating life of the invention increases significantly compared with prior art, and its outdoor normal service life can reach 5 years More than.
The coating that the present invention is prepared with so excellent performance, reason is the following aspects:
1. the matrix of coating is the nano particle of high rigidity, and takes full advantage of piling up naturally for nano particle, causes surface Regular out-of-flatness, is exactly so-called lotus-effect, constructs the surface microscopic that suitable Cassie-Baxter states are present Form.Coated substrate can have surface energy higher so as to the adhesive force having had, and nano-ceramic particle improves surface Hardness, therefore life of product is greatly improved in the case where function is not reduced.
2., by fluorine-containing and fluorine containing silane coupling agent precise proportions collocation, one is formed uniformly on the surface of nano particle The film of layer controlled surface energy.
3. after the surface of all sodium rice particles is all capped, 1 ~ 10% extra not fluorine-containing silicon is also had in paint ingredient Alkane coupling agent, these silane couplers will firmly connect wrapped nano particle and matrix.
4. the coating of specific composition of the invention coordinates the light transmittance that specific technological process realizes coating high, super-hydrophobic And the advantage of long service life.
Brief description of the drawings
Below in conjunction with accompanying drawing, the invention will be further described.
Fig. 1 is coating manufacture technology flow and uses schematic diagram.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with specific embodiment, to this Invention is further elaborated.It should be appreciated that specific embodiment described herein is only used to explain the present invention, without structure Into limitation of the present invention.
Embodiment 1
17 fluorine decyl triethoxysilanes:TEOS:Absolute alcohol:Water quality percentage is 13.7:11:13:1.35, water is used Hydrochloric acid allocates pH to 2.5, is stirred 90 minutes under 60C.Then the solution being made is diluted to solids content 10wt%. with propyl alcohol The solution that 25ml has diluted is taken, 8ml Nano-meter SiO_2s are added2Propanol suspension, suspension SiO2Content 30wt%, SiO2Diameter is 50 Nanometer, is eventually adding 12ml propyl alcohol and is made coating material within 60 minutes with 2000RPM stirrings at room temperature.
The coating being made is put into spray gun, jet pipe 0.2mm, and pressure in the compressed air of 0.15MPa, jet length is 15cm.Substrate glass absolute alcohol, watery hydrochloric acid is cleaned and dried.Toasted 15 minutes after spraying, then under 120C.
Preparation process is as shown in Figure 1.Gained coating all-transparent, hardness and glass are suitable(180hv), the Static Contact of water Angle can reach 155.The life-span of coating is evaluated using MHK500 tester for friction between, and using 800 mesh abrasive paper for metallograph, maneuvering load is 320N, speed 2.56m/s, 5 minutes time, the water contact angle after frictional experiment is constant;10 minutes, water contact angle 120.
Embodiment 2
17 fluorine decyl triethoxysilanes:TEOS:Absolute alcohol:Water quality percentage is 13.7:11:13:1.35, water is used Hydrochloric acid allocates pH to 2.5, is stirred 90 minutes under 60C.Then the solution being made is diluted to solids content 10wt%. with propyl alcohol It is made coating material.The application method of coating is with example 1.
Gained coating all-transparent, hardness is(50 hv), the static contact angle of water is 110.Frictional experiment is hydrophobic after 5 minutes Effect disappears.Embodiment 2 proves SiO2Nano particle is all critically important to the hydrophobic effect and service life of coating.
Embodiment 3
17 fluorine decyl triethoxysilanes:Decyl triethoxysilane:TEOS:Absolute alcohol:Water quality percentage is 6.8: 6.1:11:13:1.35, water allocates pH to 2.5 with hydrochloric acid, is stirred 90 minutes under 60C.Then it is with propyl alcohol that the solution being made is dilute Release to solids content 10wt%.The solution that 25ml has diluted is taken, 8ml Nano-meter SiO_2s are added2Propanol suspension, suspension SiO2Content 30wt%, SiO2Diameter is 50 nanometers, is eventually adding 12ml propyl alcohol and is made painting raw material within 60 minutes with 2000RPM stirrings at room temperature. The application method of coating is with example 1.
Gained coating all-transparent, hardness is(180 hv), the static contact angle of water is 140.After frictional experiment 10 minutes, water Contact angle is 130.Non- silicon fluoride can reduce the hydrophobic performance of coating, but can be raising coating life.
Certainly, described above not limitation of the present invention, the present invention is also not limited to the example above, the art The change that those of ordinary skill makes in essential scope of the invention, should all belong to protection scope of the present invention.

Claims (10)

1. a kind of transparent durable super-hydrophobic new material coating, it is characterised in that by following mass percent into being grouped into:Receive Rice ceramic particle mixture 1 ~ 20%, fluorosilicone coupling agent 0.1 ~ 5%, esters of silicon acis 1 ~ 10%, catalyst 0.01 ~ 0.1% and water 1 ~ 10%, remaining is organic solvent.
2. coating according to claim 1, it is characterised in that described nano-ceramic particle is selected from TiO2, SnO, Al2O3, SiO2In the combination of one or more, more preferably SnO, Al2O3, SiO2In the combination of one or more, preferably Al2O3, SiO2In one or more;The diameter of described nano-ceramic particle at 5 to 200 nanometers, more preferably 10 to 150 Nanometer, most preferably 30 to 100 nanometers, it is preferably circular in shape.
3. the coating according to claim 1, it is characterised in that described fluorosilicone coupling agent is:
Wherein, between 4 to 17, between 1 to 4, R has 1 to 6 carbon atoms, the preferably ethoxy of ten trifluoro octyl group three to m to n Base silane;
Described esters of silicon acis is:
Wherein, R is hydrophobic group, and X is hydrophilic group, preferably tetraethyl orthosilicate, and its mass percent is 1-5%.
4. coating according to claim 1, it is characterised in that silicone coupling agents summation is 1 with nanoparticle mass ratio: 5;More preferably 1:2.
5. coating according to claim 1, it is characterised in that described catalyst is selected from nitric acid, acetate and hydrochloride.
6. the preparation method of the coating according to any one of claim 1-5, it is characterised in that mix each component by proportioning Conjunction obtains coating mix, in room temperature to stirring 90 ~ 180 minutes at 60 DEG C, then by coating mix using air spraying or It is direct invasion, then is drying 15-60 minutes or placing more than 24h at room temperature at 80-120 DEG C.
7. preparation method according to claim 6, it is characterised in that described nano-ceramic particle by surface active at Reason, described activation process is to be contacted with water.
8. preparation method according to claim 6, it is characterised in that the first step is to carry out to silane coupler before the use A certain degree of prehydrolysis, concrete technology is:Nano-ceramic particle, fluorosilicone coupling agent, esters of silicon acis, water and organic solvent Mass percent by 1 ~ 20%, 0.1 ~ 15%, 1 ~ 15%, 1 ~ 10% and 70 ~ 80% mixes, and catalyst is eventually adding, and adjusts pH values It is 1 ~ 4, is then stirred 90 ~ 180 minutes under 60C.
9. preparation method according to claim 6, it is characterised in that the organic solvent is selected from ethanol, propyl alcohol, isopropanol With one or more in butanol.
10. preparation method according to claim 6, it is characterised in that the air spraying is to use 0.2 ~ 0.5mm jet pipes With pressure 0.15 ~ 0.5MPa compressed air, optimal jet length is 15 ~ 20cm;Coating room temperature dry 24 hours or Dried 15 minutes at 120 DEG C.
CN201710108028.0A 2017-02-27 2017-02-27 A kind of transparent durable super-hydrophobic new material coating and preparation method thereof Pending CN106833043A (en)

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CN108328937A (en) * 2018-02-26 2018-07-27 许水平 A method of using nano powder processing glass, metal, ceramic surface
CN108977067A (en) * 2018-08-13 2018-12-11 何才兵 A kind of transparent hydrophobic inorganic nano polymer composite
CN109988310A (en) * 2017-12-29 2019-07-09 乳源东阳光氟有限公司 A kind of fluorine silicon sulphur compound and its preparation method and application
CN113072877A (en) * 2021-03-24 2021-07-06 中国科学院青海盐湖研究所 Super-hydrophobic micro-nano particle with rod-dot structure, super-hydrophobic coating liquid and preparation method of super-hydrophobic anti-corrosion coating

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CN106189832A (en) * 2016-07-13 2016-12-07 华南理工大学 Organopolysilazane/inorganic nano material super-hydrophobic coat and preparation method thereof

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CN108977067A (en) * 2018-08-13 2018-12-11 何才兵 A kind of transparent hydrophobic inorganic nano polymer composite
CN113072877A (en) * 2021-03-24 2021-07-06 中国科学院青海盐湖研究所 Super-hydrophobic micro-nano particle with rod-dot structure, super-hydrophobic coating liquid and preparation method of super-hydrophobic anti-corrosion coating

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