CN102795786B - Super hydrophobic self-cleaning coating and preparation method thereof - Google Patents
Super hydrophobic self-cleaning coating and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of nano materials, and in particular relates to a super hydrophobic self-cleaning coating and a preparation method thereof. The method comprises the following steps of: dispersing hydrophobic silicon resin and hydrophilic nano SiO2 particles into an organic solvent to obtain dispersion; and spraying the dispersion on a clean and dry glass sheet substrate, drying, and thus obtaining the super hydrophobic self-cleaning coating. The coating has a hierarchical structure compounded by using organic and inorganic components, namely the hydrophobic silicon resin and the hydrophilic nano SiO2 particles, and the structure has compound micro-nano surface topography; and the compound micro-nano hierarchical structure is constructed by spheroid-like protrusions with the diameters of 1 to 10 microns and agglomerate spheres with the diameters of 20 to 100 nanometers on the surface of the coating, wherein the spheroid-like protrusions are constructed by agglomerate spheres with the diameters of 20 to 100 nanometers. The contact angle between the coating and water is 140 to 155 degrees, and the rolling angles of water drops on the surface of the coating are less than 2 degrees.
Description
Technical field
The invention belongs to nano material preparing technical field, particularly super-hydrophobic automatic cleaning coating and preparation method thereof.
Background technology
The phenomenons such as knot mist, knot dirt, frosting have caused very large puzzlement to people's routine work and life, certainly will cause the consumption of resource and the energy and the pollution of environment.Therefore, be improvement work and living environment, reduce waste, the protection of the environment of resource and the energy, many scientific research institutions have dropped into a large amount of human and material resources and have solved these difficult problems.In recent years, the research work development on self-cleaning function surface is rapid, and the broad prospect of application having.
The self-cleaning property of material surface is the unique physical chemical property that a kind of material surface possesses, and this material surface is without manual cleaning, only need to utilize rainwater, wind energy etc. in physical environment just can reach the effect of lasting cleaning.Self-cleaning material is divided into again super hydrophilic and super-hydrophobic two types, and on Superhydrophilic surface, little water droplet can be sprawled rapidly formation uniform water film, has good embodiment at the aspect such as anti-reflection, antifog; Super hydrophobic surface is defined as with the static contact angle of water and is greater than 150 °, and roll angle is less than 10 °.Possess the material surface of super-hydrophobicity and the contact area of water is very little, can produce as drop free rolling phenomenon on lotus leaf surface.On the super hydrophobic surface of inclination certain angle, water droplet can roll and leaves owing to being subject to action of gravity, and utilizes self surface tension to adhere to take away the dirts such as the dust that deposits on material surface, thereby keeps the clean of material surface.Therefore, the super-hydrophobicity of material surface possesses many good performances and wide application prospect, and oxidation, the burn into pollutent that super-hydrophobic automatic cleaning surface can suppress material surface effectively adheres to, frost, reduces material surface conduction of current etc.Super hydrophobic surface is applied on outdoor antenna can be in case accumulated snow, thereby ensure to receive in high quality signal; If super hydrophobic surface is used on wheel barnacle or liquid conveying pipe inwall, can reduce the resistance of surperficial convection cell; Be applied to biomedical devices, microfluidic device, cooker, clothes, indicating meter, high-rise and fuel reserve tank surface etc., can reach antifouling, antifog, rot-resistant effect.
As far back as 19 beginnings of the century, the research work of material surface wettability is carried out with regard to starting in fact, and always very active.The people such as (Germany) Hollyway analyze the surface chemistry composition of occurring in nature 20,000 various plants, the main component of finding majority of plant epidermis is all hydrophobicity grease (91 ° of the static contact angle CA ≈ of biological wax crystalline substance (hexatriacontane) and water, 87 ° of roll angle SA ≈), wherein the hydrophobicity of lotus leaf (160.4 ° of CA ≈) is best.The people such as (Germany) Barthlott have observed the pattern of the biological wax crystalline substance of lotus leaf surface, find this surface three-dimensional structure of micron order near-spherical projection, and guess that this structure is exactly the reason that plant surface manifests super-hydrophobicity (150 ° of CA >, 10 ° of SA <).And the people such as Chinese Jiang Lei work by bionics modeling effort, and the structure of different surfaces model structure, contrast find: on the hydrophobic surface of plant, ubiquity equally distributed micron order projection, the nano level secondary structure that simultaneously also has these projections to disperse around, therefore draws the basic reason compound hierarchical structure of above-mentioned micron-nanometer just that determines ultra-hydrophobicity.This structure has not only reduced the real contact area between solid, liquid two-phase, and makes the reaction force attenuation of surface and pollutent (powder or drop).In the time that coatingsurface has drop to roll, pollutent is just easy to be pulled away.Although preparation and the theoretical investigation aspect of super-hydrophobic coating have all obtained huge progress at present, utilize a lot of methods to prepare the super-hydrophobic coating of excellent performance, but also existed many problems and limited popularization and the practical application of super-hydrophobic technology.
Development in recent years a large amount of super-hydrophobic coat technologies of preparing, as sol-gel method, surface fluorination method, chemical Vapor deposition process, electrochemical deposition method, electrostatic self-assembled method, plasma processing method, chemical etching method etc.Super-hydrophobic coat need to possess two large key elements in theory: hydrophobic material (low surface energy material is as fluoropolymer, silicon-oxygen polymer) and suitable coarse structure (hierarchical structure as compound in micron-meter Na, acicular structure etc.).
The method adopting in reality requires technique simply conventionally and starting material are easy to get.The automatic cleaning coating that really possesses at present practicality, high efficiency, the feature of environmental protection is actually rare.Disclosed in Chinese invention patent CN101007304A: at 100 DEG C, to utilize mantoquita and the nickel salt corrosion aluminium sheet of nitric acid and nitric acid, obtain super-hydrophobic aluminium and aluminum alloy surface.The method is only confined to the super-hydrophobic modification on aluminum products surface, and needs sand papering aluminium surface before preparation, and rubbing paste polishing the much technique such as washes in ultrasonic middle washing, acetone repeatedly.In CN101649152A, use the reaction starting material such as organosilicon crylic acid latex, tetraethoxy, organosilane, basic catalyst, poly-(methyl) acrylate of water-based, in preparation process, relate to the steps such as the reactions such as hydrolysis, catalysis and stirring, pH regulator, heated drying.The raw material types that this invention relates to is various, and the control of each reaction is had relatively high expectations, and these are all unfavorable for actual utilization.Similar Chinese patent CN101307210A in addition, in this invention, use organosilicon crylic acid latex, water-based fluororesin emulsion nano oxide particle, inorganic drilling compound, mineral acid to be mixed with the water-based fluorine silicon-acrylic coatings of certain pH, in the time of preparation coating, also need to use wet film preparing device (containing the super-hydrophobic water-based fluorine silicon-acrylic coatings of nanoparticle).A kind of preparation method of super-hydrophobic EVA paint is disclosed in CN101157809, by in thermosol EVA dissolving and aromatic solvent (as dimethylbenzene, toluene, benzene), mixed with nano level bicarbonate of ammonia again, adopt casting method to prepare coating, then need to be 60%～75% in relative humidity, under atmosphere at room temperature environment, be dried and obtain final coating after 18～30 hours.CN200510095423.7 discloses ultra-fine fibre enhancing fluorine-containing coat and has possessed the advantages such as super-hydrophobic and oleophobic, but preparation method is more loaded down with trivial details, is difficult in large-area engineering surface construction.
CN101117713 discloses a kind of employing immersion-self-assembly and has prepared modifying super hydrophobicity SiO
2the method of-polyurethane composite coating, the method is passed through at SiO
2after surface utilizes silane coupling agent to modify, make it with active group (NH
2), make modification SiO
2-dimethylbenzene liquid; Then on the matrix existing at one deck A Luoding film, brush polyurethane coating; Finally be immersed in modification SiO
2in-dimethylbenzene liquid, make super hydrophobic composite coating.CN101205439A has used the starting material such as polytetrafluoroethylene powder, urethane resin, silane coupling agent to be mixed with the super hydrophobic coating of milk yellow, also can prepare coating with the spraying method that is conducive to big area operation, and technological operation is simple.But in coating, use special solvent acetone, be unfavorable for the environmental protection of construction and application, similarly also had the furfuryl-alcohol-resin-based super hydrophobic coating described in CN101643622A.In US Patent No. 6068911, disclose: the resin by UV photocuring containing non-reacted nanoparticle and fluoropolymer, has been prepared into the super-hydrophobic coat that possesses certain surface roughness; The formula of coating is by least two kinds of solvent compositions, and easy volatile solvent can be by low surface energy fluorine polymer belt to surface, and the non-reacted nanoparticle of inertia is the Main Components that forms surface roughness.In this patented technology scheme, not only need fluoropolymer that cost is higher as starting material, but also need extra UV light to be used for solidified coating, be very restricted in use.
But, existing these methods or use expensive material (ostentatious siloxanes as extremely low in surface) or poisonous solvent (as toluene, dimethylbenzene etc.), need special processing units (as plasma body, electrochemical deposition, laser radiation etc.) or complicated technological process, thereby actual utility value is low, the cost of starting material and equipment is higher, is difficult to extensive industrialization.Therefore inventing a kind of simple and low technology of cost prepares super-hydrophobic coat and is necessary.
Summary of the invention
The object of the present invention is to provide that a kind of manufacturing operation is simple, the super-hydrophobicity automatic cleaning coating of the premium properties such as low cost, environmental friendliness, antifouling, mildew-resistant, antifog, moistureproof, drag reduction and preparation method thereof.
Super-hydrophobicity automatic cleaning coating of the present invention is white coating, and described coating is by hydrophobicity silicone resin and hydrophilic nano SiO
2the surface topography that two kinds of components of particle organic-inorganic are composited has the compound hierarchical structure (as Fig. 1) of the micron-nanometer similar with occurring in nature lotus leaf surface; The particle diameter that the reunion bead that the compound hierarchical structure of described micron-nanometer is is 20～100nm by particle diameter is built into be 1～10 μ m near-spherical projection (as Fig. 2 a), and the reunion bead that the equally distributed particle diameter of described coatingsurface is 20～100nm is (as Fig. 2 b) combines and is built into.
Described reunion bead is by described hydrophobicity silicone resin and hydrophilic nano SiO
2particle is built into.
Described hydrophobicity silicone resin and hydrophilic nano SiO
2the quality ratio of particle is 0.3～3.3.
The chemical structural formula of described hydrophobicity silicone resin is (R
2siO)
n, wherein: R is the one in methyl, methoxyl group, ethyl or oxyethyl group, n is 3～50; Described hydrophilic nano SiO
2the good dispersity of particle, particle diameter is: 15～25nm (as Fig. 4).
Described coating and the contact angle of water be (as Fig. 3 a-e, measuring droplet size is 15 μ L) between 140 °～155 °, and water droplet is less than 2 ° (measuring droplet size is 15 μ L) in the roll angle of described coatingsurface.The water droplet existing on described coatingsurface can Free-rolling, the pollutents such as surface dirt can be taken away, thereby reach the multiple premium properties such as antifog, antifouling, anti-oxidation simultaneously.
Super-hydrophobicity automatic cleaning coating stable in properties of the present invention is soaked after 120 hours and is dried up immediately test in tap water, and the super-hydrophobic wettability that records coating changes in 5 °.
The preparation method of super-hydrophobicity automatic cleaning coating of the present invention comprises the following steps:
(1) taking the weight part of hydrophobicity silicone resin as benchmark, get hydrophobicity silicone resin 3～10 weight parts and hydrophilic nano SiO
2particle 3～10 weight parts are scattered in the organic solvent of 80～95 weight parts (described organic solvent is ethanol and/or hexanaphthene) and stir (preferably churning time is 6～12 hours), obtain preparing the dispersion liquid of coating, seal stand-by; In the time having obvious conglomeration to solidify phenomenon in described dispersion liquid, can make its dispersion by the method for filtered through gauze, sonic oscillation;
(2) on dispersion liquid step (1) being obtained is sprayed at the bottom of cleaning, dry glass chip (to glass chip basal surface carry out oil removing, scrubbing, dewater, oxygen plasma treatment), seasoning under atmosphere at room temperature environment (can be 5～10min time of drying), the white coating making is described super-hydrophobic automatic cleaning coating.
Described spraying is to use the carrier gas of air as spraying, and pressure range is between 0.5～1.2MPa; The dispersion liquid of preparation in step (1) is joined in the carrier fluid bucket of spray gun, spray gun is vertical with the surface at the bottom of glass chip, distance at the bottom of gun slot and glass chip is 15～20cm, and the speed that spray gun moves is about 2cm/s, ensures spraying evenly and the substrate of cover glass sheet as far as possible.While preparing laminated coating, after the seasoning of wait coating, start again to spray next time, repeat aforesaid operations step, prevent that additional pressure from causing coat-thickness inequality.
In dispersion liquid in the present invention, contain hydrophobicity silicone resin and hydrophilic nano SiO
2two kinds of components of particle, are used separately a certain component wherein can not form the required coarse three-dimensional arrangement of super-hydrophobic coat.After two components are mixed, due to macromolecular structure and two kinds of hydrophilic and hydrophobics that component is different of hydrophobicity silicone resin, in dispersion liquid, can form a kind of component and wrap up the reunion ball-like structure of another kind of component.When dispersion liquid is sprayed in substrate, due to the capillary effect of reunion bead, the reunion bead of small volume can trend towards again forming larger near-spherical body; Hydrophobicity silicone material has certain reactive force with the substrate after Cement Composite Treated by Plasma again simultaneously, and micron-sized near-spherical projection can be more firmly attached in substrate.
The invention has the advantages that preparation, coating is raw-material chooses, and the cellular structure of selected hydrophobicity silicone resin self has ensured that the circulation of steam can reach moistureproof effect; Main raw material(s) SiO
2, hydrophobicity silicone resin itself chemical stability, have again mildew-resistant, anticorrosion, the good characteristic that reduces surface current conduction etc. concurrently.Simultaneously coating starting material are common commercial product, possess that Costco Wholesale is low, construction pollution is little, the features such as environmental friendliness.Coating provided by the invention possesses the premium propertiess such as environmental friendliness, antifouling, mildew-resistant, antifog, moistureproof, drag reduction.
The invention has the advantages that the method for preparing coating chooses spraying method, the method operating procedure is simple, favorable reproducibility, without any special chemical feedstocks and solvent, there is good industrial applications prospect.
For the present invention can better be described, below in conjunction with drawings and Examples, the present invention is further introduced, but the present invention's scope required for protection is not limited to the scope of embodiment explanation.
Brief description of the drawings
Fig. 1. the scanning electron microscope (SEM) photograph of the super-hydrophobic automatic cleaning coating that the embodiment of the present invention 1 obtains.
Fig. 2. the scanning electron microscope (SEM) photograph (Fig. 2 a is micron-sized projection, and Fig. 2 b is nano level agglomerating particles) of the super-hydrophobic automatic cleaning coating micron-nanometer composite structure that the embodiment of the present invention 1 obtains.
Fig. 3. and the contact angle test pattern of embodiment of the present invention 1-5 super-hydrophobic automatic cleaning coating surface and water (15 μ L water droplet volumes, angle is above contact angle, angle is below roll angle, a-e corresponding instance 1-5 respectively in figure).
Fig. 4. the commercial hydrophilic nano SiO described in the present invention
2the transmission electron microscope picture of particle, particle diameter is 15～25nm.
Fig. 5. the scanning electron microscope (SEM) photograph of the super-hydrophobic automatic cleaning coating that embodiment of the present invention 2-5 (a in corresponding diagram successively, b, c, d) obtains.
Fig. 6. the photo in kind (15 μ L water droplets of coatingsurface that arrow refers to) of the super-hydrophobic automatic cleaning coating that the embodiment of the present invention 1 obtains.
Embodiment
Embodiment 1.
Be (R by chemical structural formula
2siO)
nhydrophobicity silicone resin 3.5g (wherein: R is methyl; N is 3～50, and this hydrophobicity silicone resin is the product RHODORSIL-BP9400 of French Rhodia company, is a kind of polymethyl siloxane oligopolymer) and the particle diameter SiO that is 15～25nm
2particle 1.5g is scattered in the hexanaphthene of 46.5g, and magnetic agitation 6h mixes, and obtains dispersion liquid.
To glass substrate carry out oil removing, scrubbing, dewater, oxygen plasma treatment (the Chengdu PDC-M of Ming Heng development in science and technology company limited type plasma cleaning device), seal for subsequent use.
The dispersion liquid of above-mentioned preparation is joined to spray gun (the small-sized spray gun in rock field, air compressor machine is the super air compressor machine accessory of the Zhejiang Cixi City BOX0506 of company limited type, peak pressure 1.4MPa) carrier fluid bucket in, adjusting Burners Positions makes it keep vertical with the surface of glass substrate, the distance of gun slot and glass substrate is 15～20cm, and the speed that spray gun moves is about 2cm/s; Glass substrate is sprayed to described dispersion liquid, ensure that described dispersion liquid covers evenly on glass substrate as far as possible.Under atmosphere at room temperature environment after seasoning, start again to spray next time, repeat 5 above-mentioned spraying operations and the technique of seasoning under atmosphere at room temperature environment, each dry time is 5～10min, and the super-hydrophobic automatic cleaning coating obtaining is as shown in Figure 1, Figure 2 with shown in Fig. 6.
By the deionized water drop of 15 μ L in the surface of super-hydrophobic automatic cleaning coating obtained above, utilize the contact angle tester (JC2000C of Shanghai Zhongchen digital technology equipment Co., Ltd type, frame number is 30fps, instrumental error is at 0.1 °～0.5 °) record described super-hydrophobic automatic cleaning coating and the static contact angle of water is 151.5 °, water droplet the roll angle on described super-hydrophobic automatic cleaning coating surface be 0.3 ° (as Fig. 3 a).
The hydrophilic nano SiO that described super-hydrophobic automatic cleaning coating is is 15～25nm by described hydrophobicity silicone resin and particle diameter
2the surface topography that two kinds of components of particle are composited is the compound hierarchical structure of micron-nanometer (pattern as shown in Figure 1); The compound hierarchical structure of described micron-nanometer is by above-mentioned hydrophobicity silicone resin and hydrophilic nano SiO
2the particle diameter that the particle diameter that particle the forms reunion bead that is 20～100nm is built into is the near-spherical projection (pattern is as shown in Figure 1, Figure 2 shown in a) of 1～6 μ m, and the equally distributed particle diameter of described coatingsurface described reunion bead (pattern as shown in Figure 2 b) combination that is 20～100nm is built into; Coarse structure by Fig. 2 a and the known described coating of Fig. 2 b is obvious.
Embodiment 2.
Be (R by chemical structural formula
2siO)
nhydrophobicity silicone resin 3.5g (wherein: R is methyl; N is 3～50, and this hydrophobicity silicone resin is the product RHODORSIL-BP9400 of French Rhodia company, is a kind of polymethyl siloxane oligopolymer) and the particle diameter SiO that is 15～25nm
2particle 2.0g is scattered in the hexanaphthene of 46.5g, and magnetic agitation 10h mixes, and obtains dispersion liquid.
Then according to explanation in embodiment 1, glass substrate is processed.The raw material mixing is sprayed on the glass substrate of handling well, repeat to spray preparation coating 4 times, under atmosphere at room temperature environment after seasoning 5～10min, by the deionized water drop of 15 μ L in the surface of super-hydrophobic automatic cleaning coating obtained above, recording described super-hydrophobic automatic cleaning coating and the static contact angle of water is 142.5 °, water droplet the roll angle on described super-hydrophobic automatic cleaning coating surface be 1.0 ° (as Fig. 3 b).
The hydrophilic nano SiO that described super-hydrophobic automatic cleaning coating is is 15～25nm by described hydrophobicity silicone resin and particle diameter
2the surface topography that two kinds of components of particle are composited is the compound hierarchical structure of micron-nanometer (pattern as shown in Figure 5 a); The compound hierarchical structure of described micron-nanometer is by above-mentioned hydrophobicity silicone resin and hydrophilic nano SiO
2the particle diameter that the particle diameter that particle the forms reunion bead that is 20～100nm is built into is the near-spherical projection (pattern is as shown in Fig. 2 a, Fig. 5 a) of 2～8 μ m, and the equally distributed particle diameter of described coatingsurface described reunion bead (pattern as shown in Figure 2 b) combination that is 20～100nm is built into.
Embodiment 3.
Be (R by chemical structural formula
2siO)
nhydrophobicity silicone resin 2g (wherein: R is methyl; N is 3～50, and this hydrophobicity silicone resin is the product RHODORSIL-BP9400 of French Rhodia company, is a kind of polymethyl siloxane oligopolymer) and the particle diameter SiO that is 15～25nm
2particle 1.5g is scattered in the hexanaphthene of 48g, and magnetic agitation 8h mixes, and obtains dispersion liquid.Then according to explanation in embodiment 1, glass substrate is processed.The raw material mixing is sprayed on the glass substrate of handling well, repeat to spray preparation coating 5 times, under atmosphere at room temperature environment after seasoning 5～10min, by the deionized water drop of 15 μ L in the surface of super-hydrophobic automatic cleaning coating obtained above, recording with the static contact angle of water is 149.5 °, water droplet the roll angle on described super-hydrophobic automatic cleaning coating surface be less than 0.1 ° (as Fig. 3 c).
The hydrophilic nano SiO that described super-hydrophobic automatic cleaning coating is is 15～25nm by described hydrophobicity silicone resin and particle diameter
2the surface topography that two kinds of components of particle are composited is the compound hierarchical structure of micron-nanometer (pattern as shown in Figure 5 b); The compound hierarchical structure of described micron-nanometer is by above-mentioned hydrophobicity silicone resin and hydrophilic nano SiO
2the particle diameter that the particle diameter that particle the forms reunion bead that is 20～100nm is built into is the near-spherical projection (pattern is as shown in Fig. 2 a, Fig. 5 b) of 3～10 μ m, and the equally distributed particle diameter of described coatingsurface described reunion bead (pattern as shown in Figure 2 b) combination that is 20～100nm is built into.
Embodiment 4.
Be (R by chemical structural formula
2siO)
nhydrophobicity silicone resin 5g (wherein: R is methyl; N is 3～50, and this hydrophobicity silicone resin is the product RHODORSIL-BP9400 of French Rhodia company, is a kind of polymethyl siloxane oligopolymer) and the particle diameter SiO that is 15～25nm
2particle 1.5g is scattered in the hexanaphthene of 45g, and magnetic agitation 12h mixes, and obtains dispersion liquid.Then according to explanation in embodiment 1, glass substrate is processed.The raw material mixing is sprayed on the glass substrate of handling well, repeat to spray preparation coating 3 times, under atmosphere at room temperature environment after seasoning 5～10min, by the deionized water drop of 15 μ L in the surface of super-hydrophobic automatic cleaning coating obtained above, recording with the static contact angle of water is 144.5 °, water droplet the roll angle on described super-hydrophobic automatic cleaning coating surface be 0.5 ° (as Fig. 3 d).
The hydrophilic nano SiO that described super-hydrophobic automatic cleaning coating is is 15～25nm by described hydrophobicity silicone resin and particle diameter
2the surface topography that two kinds of components of particle are composited is the compound hierarchical structure of micron-nanometer (pattern as shown in Figure 5 c); The compound hierarchical structure of described micron-nanometer is by above-mentioned hydrophobicity silicone resin and hydrophilic nano SiO
2the particle diameter that the particle diameter that particle the forms reunion bead that is 20～100nm is built into is near-spherical projection and the elongated projections (pattern is as shown in Fig. 2 a, Fig. 5 c) of 5～10 μ m, and the equally distributed particle diameter of described coatingsurface described reunion bead (pattern as shown in Figure 2 b) combination that is 20～100nm is built into.
Embodiment 5.
Be (R by chemical structural formula
2siO)
nhydrophobicity silicone resin 1.5g (wherein: R is methyl; N is 3～50, and this hydrophobicity silicone resin is the product RHODORSIL-BP9400 of French Rhodia company, is a kind of polymethyl siloxane oligopolymer) and the particle diameter SiO that is 15～25nm
2particle 5g is scattered in the hexanaphthene of 32g and the ethanol of 16g, and magnetic agitation 10h mixes, and obtains dispersion liquid.Then according to explanation in embodiment 1, glass substrate is processed.The raw material mixing is sprayed on the glass substrate of handling well, repeat to spray preparation coating 3 times, under atmosphere at room temperature environment after seasoning 5～10min, by the deionized water drop of 15 μ L in the surface of super-hydrophobic automatic cleaning coating obtained above, recording with the static contact angle of water is 146.0 °, water droplet the roll angle on described super-hydrophobic automatic cleaning coating surface be 1.2 ° (as Fig. 3 e).
The hydrophilic nano SiO that described super-hydrophobic automatic cleaning coating is is 15～25nm by described hydrophobicity silicone resin and particle diameter
2the surface topography that two kinds of components of particle are composited is the compound hierarchical structure of micron-nanometer (pattern is as shown in Fig. 5 d); The compound hierarchical structure of described micron-nanometer is by above-mentioned hydrophobicity silicone resin and hydrophilic nano SiO
2the particle diameter that the particle diameter that particle the forms reunion bead that is 20～100nm is built into is the near-spherical projection (pattern is as shown in Fig. 2 a, Fig. 5 d) of 1～10 μ m, and the equally distributed particle diameter of described coatingsurface described reunion bead (pattern as shown in Figure 2 b) combination that is 20～100nm is built into.
Claims (5)
1. a super-hydrophobicity automatic cleaning coating, is characterized in that: described coating is by hydrophobicity silicone resin and hydrophilic nano SiO
2the surface topography that two kinds of components of particle are composited is the compound hierarchical structure of micron-nanometer; The particle diameter that the reunion bead that the compound hierarchical structure of described micron-nanometer is is 20～100nm by particle diameter is built into is the near-spherical projection of 1～10 μ m, and the particle diameter of the described coatingsurface reunion bead combination that is 20～100nm is built into;
The chemical structural formula of described hydrophobicity silicone resin is (R
2siO)
n, wherein: R is the one in methyl, methoxyl group, ethyl or oxyethyl group, n is 3～50;
Described coating and the contact angle of water are between 140 °～155 °, and water droplet is less than 2 ° in the roll angle of described coatingsurface;
Described super-hydrophobicity automatic cleaning coating is to be prepared by following methods:
(1) taking the weight part of hydrophobicity silicone resin as benchmark, by hydrophobicity silicone resin 3～10 weight parts and hydrophilic nano SiO
2particle 3～10 weight parts are scattered in the organic solvent of 80～95 weight parts and stir, and obtain preparing the dispersion liquid of coating;
(2), on dispersion liquid step (1) being obtained is sprayed at the bottom of cleaning, dry glass chip, the white coating making is described super-hydrophobic automatic cleaning coating.
2. super-hydrophobicity automatic cleaning coating according to claim 1, is characterized in that: described hydrophobicity silicone resin and hydrophilic nano SiO
2the quality ratio of particle is 0.3～3.3.
3. super-hydrophobicity automatic cleaning coating according to claim 1 and 2, is characterized in that: described hydrophilic nano SiO
2the particle diameter of particle is 15～25nm.
4. super-hydrophobicity automatic cleaning coating according to claim 1, is characterized in that: described organic solvent is ethanol and/or hexanaphthene.
5. super-hydrophobicity automatic cleaning coating according to claim 1, is characterized in that: described spraying is to use the carrier gas of air as spraying, and pressure range is between 0.5～1.2MPa; Spray gun is vertical with the surface at the bottom of glass chip, and the distance at the bottom of gun slot and glass chip is 15～20cm, and the speed that spray gun moves is 2cm/s.
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| CN110484104A (en) * | 2019-08-30 | 2019-11-22 | 合肥禾盛新型材料有限公司 | A kind of super hydrophobic coating and its preparation, application |
| CN112979175B (en) * | 2021-02-07 | 2023-04-28 | 兰州理工大学科技园有限公司 | Hydrophobic oleophobic coating and preparation method thereof |
| CN114437409B (en) * | 2021-12-29 | 2023-10-13 | 广东省科学院化工研究所 | Micro-nano composite structure SiO 2 Particle, super-hydrophilic coating, and preparation method and application thereof |
| CN114589795B (en) * | 2022-03-09 | 2024-04-05 | 蒙娜丽莎集团股份有限公司 | Preparation method of self-cleaning ceramic plate |
| CN114669456A (en) * | 2022-04-21 | 2022-06-28 | 杭州老板电器股份有限公司 | Super-hydrophobic composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2004353A1 (en) * | 2006-03-27 | 2008-12-24 | Georgia Tech Research Corporation | Superhydrophobic surface and method for forming same |
| CN101456016A (en) * | 2008-12-30 | 2009-06-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of polymer hydrophobic surface |
| CN101962514A (en) * | 2010-09-27 | 2011-02-02 | 复旦大学 | High-durability super-hydrophobic self-cleaning coating material and preparation method thereof |
| CN102051120A (en) * | 2009-11-03 | 2011-05-11 | 汉高股份有限及两合公司 | Super-hydrophobic coating material, preparation method thereof and super-hydrophobic coating |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10063739B4 (en) * | 2000-12-21 | 2009-04-02 | Ferro Gmbh | Substrates with self-cleaning surface, process for their preparation and their use |
-
2011
- 2011-05-24 CN CN201110135173.0A patent/CN102795786B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2004353A1 (en) * | 2006-03-27 | 2008-12-24 | Georgia Tech Research Corporation | Superhydrophobic surface and method for forming same |
| CN101456016A (en) * | 2008-12-30 | 2009-06-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of polymer hydrophobic surface |
| CN102051120A (en) * | 2009-11-03 | 2011-05-11 | 汉高股份有限及两合公司 | Super-hydrophobic coating material, preparation method thereof and super-hydrophobic coating |
| CN101962514A (en) * | 2010-09-27 | 2011-02-02 | 复旦大学 | High-durability super-hydrophobic self-cleaning coating material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《纳米SiO2-x改性涂膜疏水性及覆冰试验研究》;姚刚等;《高压电技术》;20090930;第35卷;第2256-2263页 * |
| 姚刚等.《纳米SiO2-x改性涂膜疏水性及覆冰试验研究》.《高压电技术》.2009,第35卷 * |
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