CN113881253A - Fluoride-free self-repairing super-hydrophobic spray enhanced by inorganic binder and preparation and use methods thereof - Google Patents
Fluoride-free self-repairing super-hydrophobic spray enhanced by inorganic binder and preparation and use methods thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Abstract
The invention discloses a super-hydrophobic coating spray which is prepared from the following raw materials, by weight, 0.3-1 part of inorganic nano particles, 0-1.7 parts of inorganic particles, 0-4 parts of inorganic binder, 1-20 parts of hydrophobic agent and 79.2-95.1 parts of solvent. The super-hydrophobic spray contains an inorganic binder, and the super-hydrophobic nano particles are firmly bound on the surface of a substrate through covalent bonds formed by crosslinking with the nano particles; the formed super-hydrophobic film has a micron-nano composite binary structure similar to the lotus leaf surface, has a contact angle with water of not less than 150 degrees and a rolling angle of less than 10 degrees, and has excellent hydrophobic performance. The super-hydrophobic spray provided by the invention is low in cost, free of fluorine, environment-friendly in material and process, simple in preparation process, convenient to use, free of limitation of the shape and structure of a substrate or facility, easy to realize industrialization and good in protection effect durability, and a substrate can be subjected to hydrophobic protection operation by adopting a simple spraying process.
Description
Technical Field
The invention belongs to the technical field of preparation of super-hydrophobic spray, and particularly relates to a fluorine-free self-repairing durable super-hydrophobic spray enhanced by an inorganic binder and a preparation and use method thereof,
background
Under the action of physical or chemical factors such as atmosphere, sunlight, acid rain, salt fog, high and low temperature and the like, various problems can occur in the use process of material facilities such as metal, glass, concrete, stone, textiles, wood, plastics and the like. For example, the metal surface is corroded to generate rust, concrete and stone are easily corroded to generate weathering and cracking under the action of water, high and low temperature changes and alkaline and acid, the glass surface is fogged and frosted, the textile surface can absorb a large amount of pollutants, wood is easily hygroscopic to generate swelling, deformation and mildew, the surface of metal, electric wires and the like is easily frozen at low temperature, and the like. These phenomena cause great troubles to people's daily life and work, and pose great threats to the normal operation and safe production of engineering and equipment. In order to improve working and living environments, reduce waste of resources and energy sources and improve durability of related facilities and projects, a large amount of manpower, material resources and financial resources are invested in a plurality of scientific research institutions to research and develop surface protection materials to solve the problems and practical problems.
The super-hydrophobic material is concerned by people by effectively inhibiting the oxidation, corrosion, pollutant attachment, icing and frosting of the surface of the material, reducing the current conduction of the surface of the material and the like, and the special performances of the super-hydrophobic material enable the super-hydrophobic material to have great application value in the surface protection aspect of buildings, ships, electrical equipment, sanitary wares, satellite antennas, cables, glass and the like. It was found that the superhydrophobic properties are determined by both the surface microstructure of the material and the surface chemical composition of the material. The method comprises the steps of constructing a firm super-hydrophobic coating on the surface of a base material made of metal, glass, concrete, stone, textile, wood, plastic and the like by adopting a method such as an etching method, a sol-gel method, a vapor deposition method, an electrochemical method, a heterogeneous nucleation method, a plasma treatment method, an alternate deposition method, a template method, a self-assembly method, a solvent-non-solvent method and the like, and preventing the materials from contacting with moisture and harmful substances, so that the base materials can be protected, the durability of the related base materials can be improved, the service life is prolonged, and the materials and corresponding facilities are endowed with the performances of water resistance, corrosion resistance, pollution prevention, self-cleaning, icing prevention, self-repairing and the like.
The patent publication No. CN101935834A and CN101007304A are made by processing aluminum material with boiling water or nitric acid and its copper-nickel salt, and then modifying with hydrophobic property, so as to obtain super-hydrophobic aluminum and aluminum alloy surface, however, the method is limited to super-hydrophobic modification of aluminum product surface.
The patent with publication number CN111621049A is to form a poly-dopamine bonding layer by soaking PVC material in dopamine mixed solution, and then attach the hydrophobic treated nanoparticles on the surface of the base material to obtain the PVC super-hydrophobic coating material, however, the preparation process of the method is complicated, the application field is small, and the application range is narrow.
The patent with publication number CN 11474895A adopts D5/SiO2 to carry out in-situ polymerization, uses KH570 to modify the in-situ polymerization, and adopts an air spraying method to successfully prepare the super-hydrophobic coating on the surface of the glass. However, the method requires in-situ ring-opening polymerization to prepare a slight emulsion type spraying liquid, the substrate is limited to glass, and the glass needs to be subjected to surface pretreatment by a specific process.
Patent publication No. CN 11474895A uses a flat plate to press micro-scale powder particles and nano-scale powder particles modified by low surface energy substances onto the surface of a thermoplastic matrix softened by heating, so as to form a firmly embedded super-hydrophobic surface layer. However, the micron-sized powder particles and the nanometer-sized powder particles used in the method are polytetrafluoroethylene and perfluoroethylene propylene micro powder, and the low-surface-energy substances used for modification are fluorine-containing silane coupling agents or fluorine-containing acrylate, and the super-hydrophobic film can be prepared only on the surface of the thermoplastic resin matrix.
The patent with publication number CN104987520A adopts organic solvent, inorganic nanoparticles, dispersant, cross-linking agent, additive and low surface energy polymer to obtain super-hydrophobic coating, which is coated on the surface of solid base material by organic/inorganic hybrid method, and then is dried and cured at low temperature to obtain super-hydrophobic nano transparent coating with excellent super-hydrophobic property. However, the preparation process of the method is complex, xylene is also contained in the used solvent, most of low surface energy polymers are fluorine-containing compounds, and the durability and the self-repairing performance of the coating cannot be shown.
The super-hydrophobic coating is prepared by a complex process of polymers such as EVA, silicone-acrylic emulsion or polytetrafluoroethylene powder and tetraethoxysilane, inorganic nano particles, a silane coupling agent and the like under the action of an acidic or alkaline catalyst, and a fluorine-containing substance is mostly used in patents with publication numbers of CN101649152A, CN101307210A, CN101157809, CN101117713, CN101205439A, CN201310078920.0 and CN104046217A, and in U.S. Pat. No. 6,6068911 and the like.
Patents with publication numbers CN101734945, CN103923561, CN104231916A, CN102795786A, and CN104650725 use organic silicon, surface modified nanoparticles, graphene, etc. to prepare protective agents, and the coating film thereof has small contact angle promotion to water, poor hydrophobic effect or short protection time, and is limited in practicability when applied to engineering.
However, the existing methods have more or less the following problems: (1) expensive materials (such as low-surface energy fluorine polymer and the like) or equipment are used, so that the cost is high and the practical utilization value is low; (2) toxic solvents (such as toluene, xylene and the like) are used, which is not beneficial to construction and environmental protection application requirements; (3) before the protective agent is applied, the surface of a base material needs to be subjected to complex treatments such as grinding, polishing, cleaning and the like; (4) the excellent hydrophobic effect is difficult to achieve or the super-hydrophobic coating is not firmly attached, is easy to damage under the action of external force and has short protection time; (5) the method needs a complex preparation process, is difficult to construct on large-area engineering surfaces, has limited practicability when applied to engineering, and the like. The method adopted in practice generally requires low cost of raw materials, preparation equipment and the like, environment-friendly materials and process, simple preparation process, good durability of the protection effect and the like. Therefore, at present, the super-hydrophobic materials for surface protection really having practicability, high efficiency, environmental protection, durability and self-repairing performance are rare, and the invention of the technology for preparing the super-hydrophobic coating spray with simplicity, low cost and wide application range and the technology for preparing the protective coating in a large area through a simple spraying process is necessary.
Disclosure of Invention
In view of the above, the present invention provides a durable super-hydrophobic coating spray for protecting the surface of a substrate made of metal, concrete, glass, stone, textile, plastic, wood, etc., so as to ensure that the substrate and corresponding equipment are protected from or less corroded by physical or chemical factors such as atmosphere, sunlight, acid rain, salt fog, high and low temperatures, etc., thereby avoiding the problems of rusting, mildew, deformation, weathering cracking, water seepage, fogging/frosting/icing, pollutant adsorption, etc.
The invention also aims to provide a preparation method of the super-hydrophobic coating spray, which is used for protecting the surface of the base material, has low cost, is environment-friendly, has a simple preparation process and has a lasting protection effect.
In order to achieve the purpose, the invention adopts the technical scheme that:
the super-hydrophobic coating spray comprises 0.3-1 part by weight of inorganic nanoparticles, 0-1.7 parts by weight of inorganic particles, 0-4 parts by weight of inorganic binder, 1-20 parts by weight of hydrophobic agent and 79.2-95.1 parts by weight of solvent.
The inorganic nano particles are at least one of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide and nano zinc oxide with the particle size of 10-80 nm.
The inorganic particles are at least one of talcum powder, wollastonite, mica powder and calcium carbonate with the particle size of 0.5-15 mu m.
The inorganic binder is at least one of phosphate, silicate and alumina, and is prepared into an aqueous solution or sol with the mass-volume concentration of 0.5-0.67 g/ml.
The hydrophobic agent is at least one of alkyl silicon alkoxide, alkyl sodium silicate, alkyl/alkoxy silane, siloxane, dopamine, octylamine and octadecylamine.
The solvent is at least one of tetrahydrofuran, ethyl acetate, ethanol, acetone, isopropanol, butanone and N, N-dimethylformamide.
(II) a preparation method of the super-hydrophobic coating spray, which comprises the following steps:
(1) mixing a hydrophobizing agent and a solvent according to the mass-volume concentration of 16.5-31.5 mg/ml at normal temperature and normal pressure, and performing ultrasonic dispersion for 5min to obtain the hydrophobic liquid.
(2) The inorganic binder is prepared by mixing an inorganic binder raw material and distilled water in a mass-volume concentration of 0.5-0.67 g/ml.
(3) Adding the inorganic nano particles and the inorganic micro particles into a solvent according to the proportion of the invention under normal temperature and normal pressure, carrying out ultrasonic treatment for 5-15 min, and then dispersing for 5-8 min by using a high-speed homogenizer. And then adjusting the pH value to 4-8, under magnetic stirring, sequentially and uniformly dripping the hydrophobic liquid and the inorganic binder within 10-40 min according to the proportion of the invention, then carrying out ultrasonic reaction for 0.5-3 h to obtain the super-hydrophobic spray, and sealing and storing.
The physical and chemical parameters of the super-hydrophobic spray are as follows:
appearance: white translucent liquid
pH value: 6.0-8.0
Viscosity (20 ℃, mPa · s) of 1.0-9.0
Density (25 ℃, g/cm3) of 0.78-1.10
(III) a use method of the super-hydrophobic coating spray, which comprises the following specific steps:
(1) pretreatment of the surface of a base material: cleaning the surface of the base material by blowing, polishing and flattening by using sand paper when necessary, and then cleaning by using water, ethanol or acetone and then drying;
(2) spraying: the prepared super-hydrophobic spray is filled into an air pressure sprayer or a spray gun, air flow atomization spraying is carried out through compressed air, the distance between the spray nozzle and the surface to be sprayed of the base material is 10-30 cm, spraying is carried out sequentially from top to bottom at the speed of 2-5 cm/s from left to right, the spraying pressure is 10-80 psi, then spraying is carried out sequentially from left to right at the speed of 2-5 cm/s from top to bottom, and the spraying pressure is unchanged.
(3) And (5) maintenance: and (3) placing the base material coated with the protective layer at room temperature for 2-7 days, or treating at 120 ℃ for 0.5-3 hours to obtain a protective coating.
(4) And (4) repeating the step (2) and the step (3) for 2-3 times, and keeping the total spraying amount to be 100-200 mL/m2 to obtain the protective coating with the super-hydrophobic function.
The invention relates to the surface hydrophobization protection of substrates such as metal, glass, concrete, stone, textile, wood, plastic and the like, and has the performances of water resistance, ultraviolet resistance, aging resistance, acid and alkali resistance, ice coating resistance, self-repairing and the like. Applications range from traffic facilities, buildings, vehicles, textiles, etc.
Compared with the prior art, the invention has the following outstanding advantages and effects:
1) the raw materials used in the invention can be selected in a wide range and are easy to purchase from the market; the raw material does not contain fluorine, and the environmental pollution is small.
2) The invention does not need complex equipment, has low cost of materials and preparation equipment, simple preparation process, and safe and environment-friendly raw materials and process.
3) The inorganic binder used in the invention is water-based paint, has the characteristics of large viscosity, no toxicity, harmlessness, good biological and environmental compatibility and good stability, is simple in preparation process, and can firmly bond the super-hydrophobic nano-particles on the surface of the substrate to prepare the durable super-hydrophobic coating through the cross-linking effect of the inorganic binder and the residual hydroxyl groups after the surface of the nano-particles is hydrophobized.
4) The super-hydrophobic protective layer prepared by the invention has a micron-nano composite binary structure similar to the lotus leaf surface, the static contact angle with water is not less than 150 degrees, and the rolling angle is less than 10 degrees, so that the surface of the protected substrate presents an excellent waterproof effect, and the substrate can be endowed with the functions of self-cleaning, stain resistance, corrosion resistance, frost condensation inhibition, self-repairing and the like.
5) The invention can perform hydrophobic protection operation on the base material by adopting a simple spraying process, is not limited by the shape and the structure of the base material or facilities, can be used for protecting the surface of the base material with large size, special shape or complex shape, is convenient to use, is simple to construct and is easy to realize industrialization.
6) The invention has the advantages of working temperature of-30-50 ℃, wide suitable temperature range, long protection time on the base material, self-repairing function and good durability.
Drawings
FIG. 1: the hydrophobic effect graphs of the surfaces of different base materials sprayed by the spray of the invention are as follows: (a) steel sheet, (b) concrete, (c) glass, (d) copper sheet, (e) fabric, (f) wood block.
FIG. 2: scanning electron micrographs of the surfaces of concrete (a, b) and glass (c, d) sprayed with the spray of the invention.
FIG. 3: the performance test chart of different base materials after the spray of the invention is sprayed comprises the following steps: (a) the self-cleaning performance of the super-hydrophobic glass is as follows, (e) the self-repairing performance of the super-hydrophobic steel sheet is as follows, (f) the oil-water separation performance of the super-hydrophobic fabric is as follows.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
A super-hydrophobic spray for protecting the surface of steel is prepared from nano silicon dioxide with 30nm granularity, AP adhesive, hexadecyl trimethoxy silane and alcohol through:
adding 0.9 part by weight of nano silicon dioxide into 95.1 parts by weight of ethanol, performing ultrasonic treatment for 15min, and then dispersing for 5min by using a high-speed homogenizer. Then, nitric acid is used for adjusting the pH value to be 5, 3 parts of hexadecyl trimethoxy silane and 1 part of AP (ammonium hydroxide) binder are dropwise added at a constant speed under the magnetic stirring, the dropwise adding time is controlled to be 30min, and then the reaction is carried out for 2h under the ultrasonic condition, so that the super-hydrophobic coating spray is prepared.
And performing protection treatment on the surface of the Q235 steel sheet by using the prepared super-hydrophobic spray. Before spraying the protective agent, the surface of the steel sheet is cleaned by acetone, and then airflow atomization spraying is carried out by compressed air, wherein the distance between a nozzle and the surface of the steel sheet is 20cm, the spraying pressure is 42psi, and the spraying speed is 5 cm/s. After being sprayed once, the steel sheet is thermally treated at 120 ℃ for 0.5h, and then is sprayed and thermally treated for 2 times by the same process, 10 mu l of water, fruit juice, milk, methylene blue, methyl red and tea water are dripped on the surface of the steel sheet treated by the spray for carrying out a wetting performance test, and the test shows that the surface contact angles are all larger than 150 degrees, wherein the water contact angle is 154.2 degrees, and the rolling angle is 3 degrees. The super-hydrophobic effect of the steel sheet surface after the treatment of the spray is shown, and the hydrophobic state of the steel sheet surface is shown in figure 1 a. The anti-icing performance test effect is shown in the attached figures 3a and b, wherein the figure 3a is a state diagram of 20 mul water drops of a blank steel sheet and a super-hydrophobic steel sheet which are placed for 10min at the temperature of minus 10 ℃, the water drops on the blank steel sheet are opaque and frozen, and the water drops on the super-hydrophobic steel sheet are transparent, clear and spherical liquid; FIG. 3b is a water drop state diagram after being placed for 28min, and the water drops on the super-hydrophobic steel sheet are frozen, which shows that the super-hydrophobic steel sheet prepared in the embodiment has excellent anti-icing performance. And (3) carrying out plasma irradiation on the super-hydrophobic steel sheet for 8s, carrying out thermal repair at 120 ℃ for 20 minutes to form a self-repairing cycle, and testing the change of the contact angle. After 7 cycles, the contact angle still maintains 150 °, which indicates that the super-hydrophobic steel sheet prepared according to the embodiment has a certain self-repairing function, and the effect is shown in fig. 3 e.
Example 2
A super-hydrophobic coating spray for concrete surface protection and a preparation and use method thereof are provided, the super-hydrophobic spray is composed of nano silicon dioxide with the particle size of 60nm, 12 mu m of talcum powder, octadecyl trimethoxy silane and ethanol, and the preparation process and the method are as follows:
adding 0.5 part of nano silicon dioxide and 0.2 part of talcum powder in a weight ratio into 87.3 parts of ethanol, performing ultrasonic treatment for 10min, and then dispersing for 8min by using a high-speed homogenizer. Then, nitric acid is used for adjusting the pH value to be 6, 12 parts of octadecyl trimethoxy silane is dripped at a constant speed under the magnetic stirring, the dripping time is controlled to be 25min, and then the reaction is carried out for 2h under the ultrasonic condition, so as to prepare the super-hydrophobic coating spray.
The prepared super-hydrophobic spray is used for carrying out protection treatment on the surface of C25 concrete. Before the protective agent is sprayed, the broken slag, floating dust and the like on the surface of the concrete are cleaned by a brush, then airflow atomization spraying is carried out by compressed air, the distance between a nozzle and the surface of the concrete is 12cm, the spraying pressure is 50psi, and the spraying speed is 4 cm/s. Spraying twice with 4h interval. After the spraying is finished, the concrete block is placed at room temperature for 6d, and the test shows that the contact angle of the surface of the concrete block is 153.3 degrees and the rolling angle is 4 degrees. The concrete surface treated by the spray is shown to be super-hydrophobic, the hydrophobic state is shown in figure 1b, and the scanning electron micrographs of the surface are shown in figures 2a and 2 b.
Example 3
The super-hydrophobic spray for glass surface protection comprises nano silicon dioxide with the particle size of 30nm, AP binder, hexadecyl trimethoxy silane and ethanol, and the preparation process and the use method thereof are as follows:
adding 0.9 part by weight of nano silicon dioxide into 95.1 parts by weight of ethanol, performing ultrasonic treatment for 15min, and then dispersing for 5min by using a high-speed homogenizer. Then, nitric acid is used for adjusting the pH value to be 5, 3 parts of hexadecyl trimethoxy silane and 1 part of AP (ammonium hydroxide) binder are dropwise added at a constant speed under the magnetic stirring, the dropwise adding time is controlled to be 30min, and then the reaction is carried out for 2h under the ultrasonic condition, so that the super-hydrophobic coating spray is prepared.
The prepared super-hydrophobic spray is used for carrying out protection treatment on the surface of the glass. Before spraying the protective agent, the surface of the glass is cleaned by acetone, and then airflow atomization spraying is carried out by compressed air, wherein the distance between a nozzle and the surface of the glass is 25cm, the spraying pressure is 40psi, and the spraying speed is 5 cm/s. Spraying for three times with the interval time of 0.5 h. After the spraying is finished, the glass is placed for 4 days at room temperature, 10 mu l of water is dripped on the surface of the glass sheet treated by the spraying agent for carrying out the wetting performance test, and the contact angle of the water is 154.2 degrees and the rolling angle is 3 degrees. The glass surface treated by the spray has a super-hydrophobic effect, the hydrophobic effect is shown in figure 1c, and the surface scanning electron micrographs are shown in figures 2c and 2 d. The self-cleaning was tested with chalk powder simulating dust and the effect is shown in figures 3c and 3 d.
Example 4
A super-hydrophobic coating spray for copper material surface protection and a preparation and use method thereof are provided, the super-hydrophobic spray is composed of nano zinc oxide with the particle size of 40nm, mica powder with the particle size of 8 mu m, isopropyl triethoxysilane and isopropanol, and the preparation process and the method are as follows:
adding 0.5 part of nano zinc oxide and 0.3 part of mica powder in weight ratio into 79.2 parts of isopropanol, performing ultrasonic treatment for 8min, and then dispersing for 8min by using a high-speed homogenizer. And adjusting the pH to 6, dropwise adding 20 parts of isopropyl triethoxysilane at a constant speed under magnetic stirring, controlling the dropwise adding time to be 30min, and then reacting for 2h under ultrasound to obtain the super-hydrophobic coating spray.
The prepared super-hydrophobic spray is used for carrying out protection treatment on the surface of the copper material. Before the protective agent is sprayed, the surface of the glass is cleaned by isopropanol and dried, and then super-hydrophobic spray is sprayed, wherein the distance between a nozzle and the surface of the copper material is 12cm, the spraying pressure is 16psi, and the spraying speed is 4 cm/s. After the spraying is finished, the copper material is treated at 100 ℃ for 1.5h, and the surface contact angle of the copper material with the protective layer is tested to be 155.6 degrees, as shown in the attached figure 1 d.
Example 5
A super-hydrophobic coating spray for textile surface protection and a preparation and use method thereof are provided, the super-hydrophobic spray is composed of nano silicon dioxide with the particle size of 50nm, kaolin with the particle size of 12 μm, dopamine, octylamine and ethanol, and the preparation process and the method are as follows:
adding 0.3 part of nano silicon dioxide and 0.4 part of kaolin into 79.3 parts of ethanol, performing ultrasonic treatment for 12min, and then dispersing for 7min by using a high-speed homogenizer. Then, nitric acid is used for adjusting the pH value to be 5, under the magnetic stirring, a mixture of 8 parts of dopamine and 12 parts of octylamine is dripped at a constant speed, the dripping time is controlled to be 25min, and then the mixture reacts for 1.5h under ultrasound to prepare the super-hydrophobic spray.
The prepared super-hydrophobic coating spray is used for spraying polyester fiber cloth, the distance between a nozzle and the fiber cloth is 15cm, the spraying pressure is 60psi, and the spraying speed is 2 cm/s. Spraying twice. After the spraying is finished, the cloth is placed at room temperature for 5d, and the contact angle of the surface of the polyester fiber cloth with the protective layer is tested to be 156.7 degrees, as shown in the attached figure 1 e. 10ml of methylene blue aqueous solution and 10ml of rhodamine B dyed edible oil are mixed, and a self-made simple device is used for testing the oil-water separation performance of the super-hydrophobic textile, the effect is shown in figure 3f, and the separation efficiency is as high as 98%.
Example 6
A super-hydrophobic coating spray is composed of nano titanium dioxide with the particle size of 50nm, calcium carbonate with the particle size of 15 mu m, alkyl sodium silicate and N, N-dimethylformamide, and the preparation process and the method are as follows:
adding 1 part by weight of nano titanium dioxide and 1 part by weight of calcium carbonate into 85 parts by weight of N, N-dimethylformamide, carrying out ultrasonic treatment for 15min, and then dispersing for 8min by using a high-speed homogenizer. Then, nitric acid is used for adjusting the pH value to be 8, 13 parts of alkyl sodium silicate is dripped at a constant speed under the magnetic stirring, the dripping time is controlled to be 40min, and then the reaction is carried out for 3h under the ultrasonic condition, so as to prepare the super-hydrophobic spray.
The prepared super-hydrophobic coating spray is used for spraying wood, the distance between a spray nozzle and the wood is 30cm, the spraying pressure is 80psi, and the spraying speed is 5 cm/s. Spraying twice. And after the spraying is finished, standing at room temperature for 7d to obtain the super-hydrophobic protective coating.
Example 7
A hydrophobic spray is composed of nano zinc oxide with the particle size of 10nm, aluminum oxide, octadecylamine and acetone, and the preparation method is as follows:
adding 0.5 part by weight of nano zinc oxide into 85 parts by weight of acetone, performing ultrasonic treatment for 10min, and then dispersing for 6min by using a high-speed homogenizer. Then, adjusting the pH value to 4 by nitric acid, dropwise adding 10.5 parts of octadecylamine and 4 parts of alumina at a constant speed under magnetic stirring, controlling the dropwise adding time to be 30min, and then reacting for 3h under ultrasound to prepare the super-hydrophobic coating spray.
The prepared super-hydrophobic spray is used for carrying out protection treatment on the surface of the glass. Before spraying the protective agent, the surface of the glass is cleaned by ethanol, and then airflow atomization spraying is carried out by compressed air, wherein the distance between a nozzle and the surface of the glass is 10cm, the spraying pressure is 10psi, and the spraying speed is 2 cm/s. Spraying for three times with the interval time of 0.5 h. And after the spraying is finished, placing the glass at room temperature for 2 days to obtain the super-hydrophobic protective coating.
Example 8
A super-hydrophobic coating spray for plastic surface protection is composed of nano alumina with the particle size of 80nm, wollastonite with the particle size of 0.5 mu m, hexadecyl trimethoxy silane and tetrahydrofuran, and the preparation method is as follows:
(1) mixing 8 parts of hexadecyl trimethoxy silane and a solvent according to the mass-volume concentration of 16.5mg/ml at normal temperature and normal pressure, and performing ultrasonic dispersion for 5min to prepare a hydrophobic liquid;
(3) adding 0.3 part of nano alumina and 1.7 parts of wollastonite into tetrahydrofuran at normal temperature and normal pressure, carrying out ultrasonic treatment for 15min, and then dispersing for 7min by using a high-speed homogenizer; and then adjusting the pH to 4, dropwise adding 90 parts by weight of tetrahydrofuran at uniform speed in turn within 10min under magnetic stirring, carrying out ultrasonic reaction for 3h to obtain the super-hydrophobic spray, and sealing and storing.
The prepared super-hydrophobic spray is used for carrying out protection treatment on the surface of the plastic. Before spraying the protective agent, the plastic surface is cleaned and dried by isopropanol, and then super-hydrophobic spray is sprayed, wherein the distance between a spray nozzle and the plastic surface is 10cm, the spraying pressure is 12psi, and the spraying speed is 3 cm/s. After the spraying, the mixture is treated at 120 ℃ for 0.5 h.
Example 9
A super-hydrophobic coating spray for concrete surface protection and a preparation and use method thereof, the material comprises nano silicon dioxide with the particle size of 10nm, AP binder, siloxane and ethyl acetate, and the preparation method comprises the following steps:
(1) mixing 10 parts of siloxane and a solvent according to the mass-volume concentration of 31.5mg/ml at normal temperature and normal pressure, and performing ultrasonic dispersion for 5min to obtain the hydrophobic liquid.
(2) 3 parts of AP binder and distilled water were mixed in a mass-volume concentration of 0.67g/ml to prepare an inorganic binder.
(3) At normal temperature and pressure, 0.5 part of nano silicon dioxide is added into ethyl acetate, ultrasonic treatment is carried out for 5min, and then a high-speed homogenizer is used for dispersion for 8 min. And then adjusting the pH value to 8, dropwise adding a hydrophobic liquid and an inorganic binder at a constant speed in turn within 25min under magnetic stirring, wherein the part of ethyl acetate is 86.5 parts, carrying out ultrasonic reaction for 0.5h to obtain the super-hydrophobic spray, and sealing and storing.
The prepared super-hydrophobic spray is used for carrying out protection treatment on the surface of C25 concrete. Before the protective agent is sprayed, the broken slag, floating dust and the like on the surface of the concrete are cleaned by a brush, then airflow atomization spraying is carried out by compressed air, the distance between a nozzle and the surface of the concrete is 15cm, the spraying pressure is 40psi, and the spraying speed is 5 cm/s. Spraying twice with 4h interval. After the spraying was completed, the concrete block was left at room temperature for 5 days.
The invention provides a fluorine-free self-repairing durable super-hydrophobic spray enhanced by an inorganic binder, and a preparation method and a use method thereof, and the spray is mainly used for the ultra-long durable protection of the surface of a material or a facility. The super-hydrophobic spray is prepared by carrying out chemical reaction on nano-structure and micro-structure particles, a hydrophobic substance and an inorganic binder. The inorganic binder contained in the super-hydrophobic spray has the characteristics of high viscosity, no toxicity, no harm and good stability, the preparation process is simple, and the super-hydrophobic nano particles are firmly bonded on the surface of the substrate through covalent bonds formed by crosslinking with the nano particles. The super-hydrophobic spray can form a layer of super-hydrophobic film on the surface of a base material to be protected through a spraying process, the film has a micron-nano composite binary structure similar to the surface of a lotus leaf, the contact angle with water is not less than 150 degrees, the rolling angle is less than 10 degrees, and the super-hydrophobic spray has excellent hydrophobic performance.
The super-hydrophobic spray provided by the invention is low in cost, free of fluorine, environment-friendly in material and process, simple in preparation process, convenient to use, free of limitation of the shape and structure of a substrate or facility, easy to realize industrialization and good in protection effect durability, and a substrate can be subjected to hydrophobic protection operation by adopting a simple spraying process. The hydrophobic protective coating can be widely applied to hydrophobic protection of the surfaces of substrates made of metal, glass, concrete, stone, textiles, wood, plastic and the like, can enable the surfaces of the protected substrates to present a long-acting excellent hydrophobic effect, and can endow the substrates with the functions of self-cleaning, stain prevention, corrosion resistance, frost condensation inhibition, self repair and the like.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. The super-hydrophobic coating spray is characterized by comprising the following raw materials, by weight, 0.3-1 part of inorganic nano particles, 0-1.7 parts of inorganic particles, 0-4 parts of inorganic binder, 1-20 parts of hydrophobic agent and 79.2-95.1 parts of solvent.
2. The super-hydrophobic coating spray as claimed in claim 1, wherein the inorganic nanoparticles are at least one of nano-silica, nano-titania, nano-alumina, and nano-zinc oxide having a particle size of 10 to 80 nm.
3. The super-hydrophobic coating spray according to claim 1, wherein the inorganic particles are at least one of talc powder, wollastonite, mica powder and calcium carbonate with a particle size of 0.5-15 μm.
4. The super-hydrophobic coating spray according to claim 1, wherein the inorganic binder is at least one of phosphate, silicate and alumina, and is prepared into an aqueous solution or sol with a mass-volume concentration of 0.5-0.67 g/ml.
5. The super hydrophobic coating spray of claim 1, wherein the hydrophobic agent does not contain fluorine and is at least one of alkyl silicon alkoxide, sodium alkyl silicate, alkyl/alkoxy silane, siloxane, dopamine, octylamine, octadecylamine.
6. The super hydrophobic coating spray of claim 1, wherein the solvent is at least one of tetrahydrofuran, ethyl acetate, ethanol, acetone, isopropanol, butanone, N-dimethylformamide.
7. A method for preparing the super-hydrophobic coating spray of any one of claims 1 to 6, which comprises the following steps:
(1) mixing a hydrophobizing agent and a solvent according to the mass-volume concentration of 16.5-31.5 mg/ml at normal temperature and normal pressure, and performing ultrasonic dispersion for 5min to prepare a hydrophobic liquid;
(2) mixing an inorganic binder raw material and distilled water according to the mass-volume concentration of 0.5-0.67 g/ml to prepare an inorganic binder;
(3) adding inorganic nano particles and inorganic micro particles into a solvent according to a proportion at normal temperature and normal pressure, carrying out ultrasonic treatment for 5-15 min, and then dispersing for 5-8 min by using a high-speed homogenizer; and then adjusting the pH value to 4-8, sequentially and uniformly dripping the hydrophobic liquid and the inorganic binder within 10-40 min under magnetic stirring, carrying out ultrasonic reaction for 0.5-3 h to obtain the super-hydrophobic spray, and sealing and storing.
8. A method of using the superhydrophobic coating spray of any of claims 1-6, wherein the method of use comprises spraying, dipping, and brushing.
9. The method of using the superhydrophobic coating spray of claim 8, comprising the steps of:
(1) pretreatment of the surface of a base material: cleaning the surface of the base material by blowing, polishing and flattening by using sand paper when necessary, and then cleaning by using water, ethanol or acetone and then drying;
(2) spraying: the prepared super-hydrophobic spray is filled into an air pressure sprayer or a spray gun, airflow atomization spraying is carried out through compressed air, the distance between the spray nozzle and the surface to be sprayed of the base material is 10-30 cm, spraying is carried out sequentially from top to bottom at the speed of 2-5 cm/s from left to right, the spraying pressure is 10-80 psi, then spraying is carried out sequentially from left to right at the speed of 2-5 cm/s from top to bottom, and the spraying pressure is unchanged;
(3) and (5) maintenance: placing the base material coated with the protective layer at room temperature for 2-7 days, or treating at 120 ℃ for 0.5-3 hours to obtain a protective coating;
(4) repeating the steps (2) and (3) for 2-3 times, wherein the total spraying amount is kept at 100-200 mL/m2And obtaining the protective coating with the super-hydrophobic function.
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