CN115322597B - Self-cleaning ceramic coating with lotus leaf-like structure and preparation and application methods thereof - Google Patents
Self-cleaning ceramic coating with lotus leaf-like structure and preparation and application methods thereof Download PDFInfo
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- CN115322597B CN115322597B CN202211048052.7A CN202211048052A CN115322597B CN 115322597 B CN115322597 B CN 115322597B CN 202211048052 A CN202211048052 A CN 202211048052A CN 115322597 B CN115322597 B CN 115322597B
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- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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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
- B05D3/002—Pretreatement
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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
- B05D3/02—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 by baking
- B05D3/0218—Pretreatment, e.g. heating the substrate
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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
- B05D3/02—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 by baking
- B05D3/0254—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
- B05D7/14—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 to metal, e.g. car bodies
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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
- C09D7/65—Additives macromolecular
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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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Abstract
The invention discloses a self-cleaning ceramic coating with a lotus leaf-like structure and a preparation and application method thereof; comprising, based on 100% of the total weight: silica sol: 25-27%,1% NaOH solution: 4-5% of pigment: 10-12% of filler: 8-10% of dispersing agent: 1-1.2%, silane: 25-27%, isopropanol: 3-3.5 percent of silicone oil microcapsule: 6-8%,25% formic acid: 0.7-1%, deionized water: the balance. The micro-nano secondary roughness structure is formed on the surface of the ceramic coating, and the silicone oil microcapsule with the shell-core structure is prepared, so that the water contact angle of the ceramic coating is larger than 150 degrees, the rolling angle is larger than 140 degrees, and the ceramic coating has excellent superhydrophobicity, self-cleaning property and good durability.
Description
Technical Field
The invention belongs to the technical field of coatings, and relates to a self-cleaning ceramic coating with a lotus leaf-like structure and a preparation and application method thereof.
Background
When water drops fall on the lotus leaves, the approximately spherical water drops are formed on the lotus leaves to roll off without wetting the lotus leaves, and when the lotus leaves are observed by an electron microscope, the surface of the lotus leaves is found to have micro-protrusions with a micron-scale, and a nano-scale protrusion is formed on the micro-scale protrusions, so that the lotus leaves are of a micron-nano two-scale protrusion structure. The structure ensures that the water drops adsorb dust on the surface of the blade in the rolling process and roll out of the blade surface, thereby achieving the effect of cleaning the blade surface. The lotus leaf imitation technology has penetrated into various industries and fields of textile, chemical industry and the like. Various super-hydrophobic self-cleaning surfaces are manufactured by imitating lotus leaf structures, so that the manual maintenance cost can be reduced.
At present, materials commonly used for constructing the superhydrophobic surface comprise polytetrafluoroethylene, fluorosilane, stearic acid and other low-surface-energy organic matters, but the organic matters often face a plurality of problems, such as higher VOC emission, friction resistance, weakening or even losing of the hydrophobicity at a high Wen Xiachao level, and the like, so that the use scene is limited. The ceramic coating is a coating with an Si-O-Si inorganic structure, is a material with safety, environmental protection, good high temperature resistance and good wear resistance, and contains a small amount of-CH on the surface 3 The group has hydrophobicity, but the water contact angle of the surface of the ceramic coating can only reach about 100 degrees, and the ceramic coating cannot be used as a super-hydrophobic self-cleaning coating.
The technical means for forming the lotus leaf-like surface micro-nano secondary structure comprises a template method, a laser etching method, a chemical vapor deposition method, a phase separation and self-assembly method and the like, and the technical means is larger in gap from the traditional construction process of the coating, and is not suitable for large-area industrial production as the search of the existing patent literature finds that the Chinese patent application number 202010751086.7 discloses a technical scheme for forming the lotus leaf-like superhydrophobic surface and the template method forms the lotus leaf-like structure superhydrophobic surface; the Chinese patent with application number 202210049774.8 discloses a preparation method and application of a super-hydrophobic coating with a lotus leaf-like structure, which adopts a high-voltage electrostatic spraying method to form the lotus leaf-like structure, but under the condition of fixed voltage in electrostatic spraying, the electric field force applied by paint particles is constant, and the force of the electric field force applied to each paint particle is the same, so that the particles cannot move directionally to form the lotus leaf-like structure. The technical means which is close to the coating construction process and can be realized is the key point of preparing the lotus leaf structure imitating super-hydrophobic self-cleaning coating.
Disclosure of Invention
The method similar to the coating construction process is adopted to form a lotus leaf-like micron-nanometer secondary structure on the surface of the ceramic coating to prepare the self-cleaning super-hydrophobic coating, and the coating has good self-cleaning performance and durability, which is a key technical problem to be solved. The invention provides a lotus leaf-like self-cleaning ceramic coating and a preparation and construction method thereof.
The invention aims at realizing the following technical scheme:
< first aspect >
The invention relates to a self-cleaning ceramic coating composition for forming a lotus leaf-like structure, which comprises the following components in percentage by weight, based on 100 percent:
silica sol: 25-27%,1% NaOH solution: 4-5% of pigment: 10-12% of filler: 8-10% of dispersing agent: 1-1.2%, silane: 25-27%, isopropanol: 3-3.5 percent of silicone oil microcapsule: 6-8%,25% formic acid: 0.7-1%, deionized water: the balance.
In the system of the invention, silica sol is a main film forming substance of ceramic paint, and common commercial products such as: bindzil 2034DI, ST-O-40, nissan chemical, graves
HS-40, etc.
The pH value of the color paste is adjusted to 9-10.5 by using 1% NaOH solution as a pH value regulator, the pH value of the silica sol can be reduced in the storage process after the color paste is ground, and when the pH value is reduced to below 8.5 and approaches neutrality, the silica sol can be gelled to cause the deterioration of the color paste, so that the pH value of the color paste is required to be adjusted to 9-10 by using alkaline solution, and the color paste can not be deteriorated in the storage process.
The pigment endows the paint with different colors, common inorganic pigment is selected, and the inorganic pigment has good temperature resistance, good safety and is suitable for the high temperature resistant field.
The filler has the effects of reducing the cost of the paint, increasing the solid content of the paint, and the like, and common fillers are selected, for example: mica powder, silica micropowder, kaolin, alumina powder, fumed silica, and the like.
The dispersant plays roles of reducing pigment dispersion time, stabilizing pigment dispersion, improving pigment tinting strength and hiding power, and the like, for example: BYK180, BYK190, BYK2010, BYK2001, and the like.
The silane is auxiliary film forming material, and can be methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, etc.
The silicone oil microcapsule is a component for providing hydrophobicity of a ceramic coating, is a microcapsule with a shell-core structure, and can gradually diffuse out of the shell structure in the heating process of the coating, slowly release and prolong the hydrophobic durability of the coating.
The 25% formic acid solution is used as a catalyst for ceramic coating sol-gel reaction, and silane is hydrolyzed under acidic condition and then undergoes polycondensation reaction with silica sol to produce ceramic coating.
Extruding with the total weight of the silicone oil microcapsule as 100%, wherein the silicone oil microcapsule comprises the following components:
silicone oil: 43-45%,
silane: 48-50%,
and (2) a surfactant: 4 to 4.5 percent,
25% formic acid solution: the balance.
Silicone oil microcapsules in which silicone oil is used to provide hydrophobicity to ceramic coating, silicone oils are commonly used, for example: methyl silicone oil, hydroxy silicone oil, etc.
Silane is prepared from 1:1-2:1 and a difunctional silane. The trifunctional silane is short-chain trifunctional silane, including methyltrimethoxysilane and methyltriethoxysilane; the difunctional silane is short-chain difunctional silane, including dimethyl dimethoxy silane, dimethyl diethoxy silane and the like. In the system, the trifunctional silane and the difunctional silane are matched for use, so that a regular porous structure with a three-dimensional cross-linked structure can be formed, the diameters of the pores are larger, the diffusion of silicone oil molecules is facilitated, and if the trifunctional silane is fully selected, the formed cross-linked structure is compact, the pore diameter is smaller, and the outward diffusion of the silicone oil molecules is not facilitated. The silane with short chain alkyl can avoid the steric hindrance effect of premature polymerization, so that the shell structure is more complete and more regular, and the silane with long chain alkyl is difficult to form a complete shell structure during polymerization due to the steric hindrance effect.
The surfactant is selected from cationic surfactants, and can exist stably under weak acidic conditions. For example: cetyl trimethyl quaternary ammonium bromide, stearyl dimethyl benzyl quaternary ammonium chloride, benzalkonium bromide and other organic quaternary ammonium salt structural surfactants. The gel phenomenon can be generated if the anionic surfactant is added into the system; if nonionic surfactant is added, the stabilizing effect is poor.
The 25% formic acid solution is a catalyst for the hydrolysis of silane, which can form a colorless transparent solution under acidic conditions.
As one embodiment, the preparation of the silicone oil microcapsule comprises the steps of: mixing silicone oil, silane and surfactant, adjusting pH to 4.0-5.0 with 25% formic acid under stirring, reacting for 4-6hr, and performing ultrasonic treatment for 2-3hr to obtain silicone oil microcapsule.
The prepared microcapsule has a shell-core structure, wherein the shell is a three-dimensional cross-linked network structure of Si-O-Si formed by hydrolysis and polymerization of silane under an acidic condition, and the core is silicone oil emulsified by a surfactant. The reticular shell structure can lead the internal silicone oil molecules to slowly diffuse outwards.
Because of the action of the surfactant, the silicone oil microcapsules can be uniformly dispersed in the coating, and can be uniformly distributed in the coating after solidification, and when the upper silicone oil (the microcapsules are uniformly distributed in the coating and the upper silicone oil microcapsules are also arranged on the upper layer) is out of action in the use process, the silicone oil in the coating can slowly diffuse out to continue to exert hydrophobicity, so that the long-acting hydrophobicity of the coating is ensured. If silicone oil is directly added into the ceramic coating, the silicone oil only floats on the surface of the coating due to low density and poor compatibility with the water-based coating, and is also positioned on the surface layer of the coating after being solidified into a film, and once the ceramic coating is deactivated, the hydrophobicity is reduced, so that the hydrophobicity durability of the coating directly added with the silicone oil is poor.
The step adopts a mode of stirring and reacting for 4-6 hours and then ultrasonic for 2 hours, the reaction is carried out under stirring to generate a shell structure as a main component, the silicone oil and the surfactant are combined preliminarily, and the silicone oil and the surfactant are further emulsified under ultrasonic to form uniform and stable silicone oil microcapsule dispersion liquid.
As one embodiment, the coating of the present invention is applied to a substrate having a surface with micro-nano secondary roughness structures. The surface of the base material is firstly formed with a micron-sized raised rough surface with Ra of 2-5 mu m, and then a nanometer-sized rough structure with Ra of 200-400nm is formed on the surface.
< second aspect >
The invention relates to a preparation method of a self-cleaning ceramic coating composition for forming a lotus leaf-like structure, which comprises the following steps:
s1, preparing color paste: uniformly mixing silica sol, pigment, filler, dispersing agent and deionized water, regulating the pH value to 9.5-10.5 by using a 1% NaOH solution, and grinding to the fineness of below 20 mu m;
s2, preparing ceramic paint: evenly mixing silane, isopropanol, silicone oil microcapsule and 25% formic acid; and then adding the color paste prepared in the step S1, uniformly mixing, and reacting for 4-8 hours to obtain the ceramic coating.
As one embodiment, in the step S2, after grinding to the fineness of below 20 mu m, the pH value of the color paste is tested, and if the pH value is less than 9.0, the pH value is adjusted to be 9.0-10.0 by using 1% NaOH solution.
< third aspect >
The invention relates to a construction method of a self-cleaning ceramic coating composition for forming a lotus leaf-like structure; the method comprises the following steps:
a1, pretreatment: performing shot blasting treatment on the metal substrate by using 60-mesh steel shots, forming roughness with Ra of 3-8 mu m on the surface of the substrate, constructing a micron-sized convex rough surface, performing sand blasting treatment on the micron-sized convex rough surface by using 400-mesh corundum, and forming a nano-sized rough structure with Ra of 200-400 nm;
a2, preheating a base material: cleaning the pretreated base material, and preheating to 50-60 ℃;
a3, spraying: spraying the base material at 50-60 deg.c;
a4, curing: baking at 180-230 deg.C for 15-20 min to complete solidification.
In the step A1, the metal base material is selected from metal plates such as aluminum alloy, galvanized steel plate, nickel-plated steel plate and the like. After the two pretreatment processes in the step A1, the surface of the base material can form a micron-nanometer secondary structure similar to the surface of lotus leaves.
The control of the preheating temperature of the substrate in the steps A2 and A3 is important. That is, the coating of the present invention is applied by preheating the substrate to 50-60 ℃. When the coating contacts the surface of the preheated substrate, the fluidity is slowed down, and the coating is primarily solidified after reaching the leveling, so that the micro-nano secondary coarse structure formed on the surface of the substrate is maintained; if the base material is not preheated and sprayed at normal temperature, the coating tends to be leveled and filled in the concave part of the rough surface, the nanoscale rough structure disappears, and a micron-nanoscale secondary structure cannot be formed; if the preheating temperature of the substrate is too high, the coating layer has the defects of drying, light loss and the like.
And (C) directly curing at high temperature after spraying in the step A4, so as to quickly finish curing the coating to form the coating with the micron-nanometer secondary structure. The thickness of the coating can not be too thick, otherwise, the curing speed is slow, and the nano-scale structure on the surface can disappear; too thin a coating can also cause defects such as drying out, loss of light, etc.
In one embodiment, in step A4, the coating thickness after curing is 20-30 μm.
Compared with the prior art, the invention has the following beneficial effects:
(1) Adopting steel shots and corundum sand with different particle sizes, constructing a lotus leaf-like micron-nanometer secondary roughness structure on the surface of a base material through twice pretreatment processes of shot blasting and sand blasting, and forming a lotus leaf-like ceramic coating through controlling the preheating temperature, the curing temperature and the thickness of the ceramic coating of the base material; the construction process and the construction method provided by the invention are simple and feasible, have short time and are suitable for large-area industrial production.
(2) The silicone oil microcapsule with a shell-core structure is prepared by a hydrolysis polymerization technology of silane and an emulsification technology of surfactant on silicone oil, wherein the shell is a three-dimensional cross-linked porous structure of Si-O-Si formed by hydrolysis polymerization of silane, and the core is silicone oil emulsified by the surfactant, so that the silicone oil has good compatibility with the water-based ceramic coating, can be uniformly dispersed in the whole ceramic coating, and can be uniformly distributed in the whole coating after solidification. In the use process, the silicone oil can slowly diffuse out of the shell structure, the hydrophobicity of the coating is continuously exerted, and the self-cleaning effect is achieved; the silicone oil microcapsule with the shell-core structure can also increase the addition amount of the silicone oil and improve the self-cleaning durability of the coating.
(3) The silicon oil microcapsule with the shell-core structure is prepared by forming the micron-nanometer secondary roughness structure on the surface of the ceramic coating, so that the water contact angle of the ceramic coating is more than 150 degrees, and the ceramic coating has excellent superhydrophobicity, self-cleaning property and good durability.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a schematic diagram of a network structure of silicone oil microcapsules;
fig. 2 is a schematic representation of a coating micro-nanostructure.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Examples 1 to 3
The present examples 1-3 provide a self-cleaning ceramic coating composition for forming a lotus leaf like structure; the composition was as shown in Table 1.
The self-cleaning ceramic paint of this embodiment is prepared as follows:
(1) And (3) color paste preparation: mixing silica sol, pigment, filler, dispersant and deionized water uniformly, regulating pH value to 10 with 1% NaOH solution, grinding to fineness below 20 μm, testing pH value of color paste, and regulating pH value to 10.0 with 1% NaOH solution if the pH value is less than 9.0 for later use.
(2) Preparing a ceramic coating: and (3) uniformly mixing silane, isopropanol, silicone oil microcapsules and 25% formic acid, measuring and recording the pH value of the solution, then adding the color paste prepared in the step (1), uniformly mixing, reacting on a roller frame for 4-8 hours to obtain the ceramic coating, and measuring and recording the pH value of the ceramic coating.
The construction steps of the self-cleaning ceramic coating of the embodiment are as follows:
(1) The pretreatment process comprises the following steps: the method comprises the steps of selecting a galvanized steel plate as a base material, performing shot blasting treatment on the base material by using 60-mesh steel shots, forming roughness with Ra of 3-8 mu m on the surface of the base material, constructing a micron-sized convex rough surface, performing sand blasting treatment on the surface of the micron-sized convex rough surface by using 400-mesh corundum, and forming a nano-sized rough structure with Ra of 300 nm.
(2) Preheating a base material: cleaning the pretreated base material with tap water, putting the base material into an oven, and preheating the base material to 55 ℃;
(3) Spraying: spraying the base material at 55 ℃;
(4) Curing: baking at 210 deg.c for 20 min to complete the curing, and the thickness of the cured coating is 20-30 microns.
Fig. 2 is a schematic diagram of a micro-nano structure of a cured coating, and as can be seen from fig. 2, the coating forms a primary coarse structure of 2-5 μm, and a secondary coarse structure of 100-150nm is formed on the surface of the micro structure, so that the coating is a lotus leaf-like micro-nano secondary coarse structure.
The paint prepared in example 1 was subjected to the above construction and adjustment: spraying is carried out at normal temperature, and as a result, it is found that: sagging of the paint occurs.
The paint prepared in example 1 was subjected to the above construction and adjustment: spraying was carried out at 70 ℃, and as a result, it was found that: the coating has paint film defects such as dry, rough surface, light loss and the like.
The paint prepared in example 1 was subjected to the above construction and adjustment: the sprayed coating had a thickness of 50 μm, and as a result it was found that: the surface nano-scale roughness disappears, and the contact angle and the rolling angle become smaller.
The paint prepared in example 1 was subjected to the above construction and adjustment: the curing temperature was 150 ℃, as a result of which it was found that: baking for 40 minutes was required to achieve the same hardness.
The paint prepared in example 1 was subjected to the above construction and adjustment: the surface of the substrate is formed into a roughness with Ra of 3 μm during pretreatment, and the roughness is constructed into a micrometer-scale raised rough surface. The performance test results show that: the contact angle and the rolling angle become smaller.
The paint prepared in example 1 was subjected to the above construction and adjustment: during pretreatment, the surface of the base material is directly subjected to sand blasting treatment by using 400-mesh corundum to form a nanoscale coarse structure with Ra of 300 nm. The performance test results show that: the contact angle and the rolling angle become smaller.
Comparative examples 1 to 6
Comparative examples 1-6 provide ceramic coating compositions; the composition was as shown in Table 1.
The preparation and construction method of the ceramic coating are the same as in example 1.
Comparative example 7
Comparative example 7 provides a ceramic coating composition; the composition was as shown in Table 1.
The construction method of the ceramic paint is the same as in example 1.
The preparation method of the ceramic coating comprises the following steps:
(1) And (3) color paste preparation: mixing silica sol, pigment, filler, dispersant and deionized water uniformly, regulating pH value to 10 with 1% NaOH solution, grinding to fineness below 20 μm, testing pH value of color paste, and regulating pH value to 10.0 with 1% NaOH solution if the pH value is less than 9.0 for later use.
(2) Preparing a ceramic coating: and (3) uniformly mixing silane 1, hydroxy silicone oil, a surfactant cetyl trimethyl ammonium bromide, isopropanol and 25% formic acid, measuring and recording the pH value of the solution, then adding the color paste prepared in the step (1), uniformly mixing, reacting on a roller frame for 4-8 hours to obtain the ceramic coating, and measuring and recording the pH value of the ceramic coating.
The construction steps of the self-cleaning ceramic coating of the embodiment are as follows:
(1) The pretreatment process comprises the following steps: the method comprises the steps of selecting a galvanized steel plate as a base material, performing shot blasting treatment on the base material by using 60-mesh steel shots, forming roughness with Ra of 3 mu m on the surface of the base material, constructing a micron-sized convex rough surface, performing sand blasting treatment on the surface of the micron-sized convex rough surface by using 400-mesh corundum, and forming a nano-sized rough structure with Ra of 300 nm.
(2) Preheating a base material: cleaning the pretreated base material with tap water, putting the base material into an oven, and preheating the base material to 55 ℃;
(3) Spraying: spraying the base material at 55 ℃;
(4) Curing: baking at 210 deg.c for 20 min to complete the curing, the thickness of the coating layer being 25 μm.
Table 1 coating compositions and amounts (wt.%) of examples and comparative examples
In the table 1, the contents of the components,
silica sol 1 is Bindzil 2034DI of actunobel;
silica sol 2 is Graves
HS-40；
The pigment is titanium dioxide;
silane 1 is methyltrimethoxysilane and dimethyldiethoxysilane with a mass ratio of 1:1;
silicone oil microcapsule 1: uniformly mixing hydroxyl silicone oil, silane 1 and hexadecyl trimethyl ammonium bromide, regulating the pH value to 4.5 by 25% formic acid under stirring, reacting for 5hr, and then performing ultrasonic treatment for 3hr to obtain silicone oil microcapsule 1; wherein, 45% of silicone oil, 1% of silane, 4% of surfactant and the balance of 25% formic acid solution;
fig. 1 is a schematic diagram of a network structure of a silicone oil microcapsule 1, and as can be seen from fig. 1, the silicone oil microcapsule has a shell-core structure, a shell has a relatively uniform and regular network structure, the diameter of a mesh is about 100-300nm, and silicone oil molecules in the interior can be gradually released from gaps in the heating process, so that non-tackiness is continuously provided for a coating.
Silicone oil microcapsule 2: uniformly mixing hydroxyl silicone oil, silane 2 (dimethyl dimethoxy silane and dimethyl diethoxy silane with the mass ratio of 1:1) and cetyltrimethylammonium bromide, adjusting the pH value to 4.5 by 25% formic acid under stirring, reacting for 5hr, and then performing ultrasonic treatment for 3hr to obtain silicone oil microcapsule 2; wherein, 45% of silicone oil, 248% of silane, 4% of surfactant and the balance of 25% formic acid solution;
silicone oil microcapsule 3: uniformly mixing hydroxy silicone oil, silane 3 (methyltrimethoxysilane and methyltriethoxysilane with the mass ratio of 1:1) and cetyltrimethylammonium bromide, adjusting the pH value to 4.5 by 25% formic acid under stirring, reacting for 5hr, and then performing ultrasonic treatment for 3hr to obtain silicone oil microcapsule 3; wherein, 45% of silicone oil, 3% of silane, 4% of surfactant and the balance of 25% formic acid solution;
silicone oil microcapsule 4: uniformly mixing hydroxy silicone oil, silane 4 (hexadecyltrimethoxysilane and dimethyldiethoxysilane in a mass ratio of 1:1) and hexadecyltrimethylammonium bromide, adjusting the pH value to 4.5 with 25% formic acid under stirring, reacting for 5hr, and performing ultrasonic treatment for 3hr to obtain silicone oil microcapsule 4; wherein, 45% of silicone oil, 148% of silane, 4% of surfactant and the balance of 25% formic acid solution.
Silicone oil microcapsule 5: 0.25 g of sodium dodecyl sulfonate and 0.75 g of alkylphenol ethoxylate are dissolved in 100 g of deionized water, an oil phase mixture consisting of 10 g of simethicone, 10 g of TEOS and 1.5 g of octadecyl trimethoxy silane is added, the mixture is pre-emulsified and stirred for 15 minutes in an ice water bath environment, and then the mixture is subjected to ultrasonic fine emulsification for 20 minutes by using a cell pulverizer to obtain a miniemulsion. Regulating the pH value of the miniemulsion to 7.5, and stirring at high speed for 24 hours at normal temperature to obtain milky silicone oil microcapsule 5;
silicone oil microcapsule 6: uniformly mixing hydroxyl silicone oil, silane 1 and hexadecyl trimethyl ammonium bromide, regulating the pH value to 4.5 with 25% formic acid under stirring, and stirring for 8hr to obtain silicone oil microcapsule 6; wherein, 45% of silicone oil, 1% of silane, 4% of surfactant and the balance of 25% formic acid solution;
silicone oil microcapsule 7: uniformly mixing hydroxyl silicone oil, silane 1 and hexadecyl trimethyl ammonium bromide, regulating pH value to 4.5 with 25% formic acid under stirring, and performing ultrasonic treatment for 8hr to obtain silicone oil microcapsule 7; wherein, 45% of silicone oil, 1% of silane, 4% of surfactant and the balance of 25% formic acid solution.
Primary performance test
The coatings prepared in the above examples and comparative examples were subjected to main performance tests, the test items and methods are shown in Table 2, and the test results are shown in tables 3 to 5:
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (5)
1. A self-cleaning ceramic coating composition for forming a lotus leaf-like structure, which is characterized by comprising the following components in percentage by weight, based on 100 percent:
silica sol: 25-27%,1% NaOH solution: 4-5% of pigment: 10-12% of filler: 8-10% of dispersing agent: 1-1.2%, silane: 25-27%, isopropanol: 3-3.5 percent of silicone oil microcapsule: 6-8%,25% formic acid: 0.7-1%, deionized water: the balance;
the silicone oil microcapsule comprises the following components in percentage by weight based on 100% of the total weight of the silicone oil microcapsule:
silicone oil: 43-45%,
silane: 48-50%,
and (2) a surfactant: 4 to 4.5 percent,
25% formic acid solution: the balance;
in the silicone oil microcapsule, the silicone oil is selected from one or more of methyl silicone oil and hydroxyl silicone oil; the silane consists of 1:1-2:1 and a difunctional silane; the trifunctional silane is short-chain trifunctional silane selected from methyltrimethoxysilane and methyltriethoxysilane; the difunctional silane is short-chain difunctional silane and is selected from dimethyl dimethoxy silane and dimethyl diethoxy silane; the surfactant is selected from cationic surfactants including one or more of cetyl trimethyl quaternary ammonium bromide, stearyl dimethyl benzyl quaternary ammonium chloride, benzalkonium chloride and benzalkonium bromide;
the preparation of the silicone oil microcapsule comprises the following steps: uniformly mixing silicone oil, silane and surfactant, regulating pH to 4.0-5.0 with 25% formic acid under stirring, reacting for 4-6hr, and performing ultrasonic treatment for 2-3hr to obtain silicone oil microcapsule;
the construction method of the composition comprises the following steps:
a1, pretreatment: performing shot blasting treatment on the metal substrate by using 60-mesh steel shots, forming roughness with Ra of 2-5 mu m on the surface of the substrate, constructing a micron-sized convex rough surface, performing sand blasting treatment on the micron-sized convex rough surface by using 400-mesh corundum, and forming a nano-sized rough structure with Ra of 200-400 nm;
a2, preheating a base material: cleaning the pretreated base material, and preheating to 50-60 ℃;
a3, spraying: spraying the base material at 50-60 deg.c;
a4, curing: baking at 180-230 deg.c for 15-20 min to complete the curing and to obtain the coating with thickness of 20-30 microns.
2. A self-cleaning ceramic coating composition for forming a lotus leaf like structure according to claim 1, wherein said filler is selected from one or more of mica powder, silica micropowder, kaolin, alumina powder, fumed silica; the pigment is an inorganic pigment; the dispersing agent is one or more selected from BYK180, BYK190, BYK2010 and BYK 2001.
3. The self-cleaning ceramic coating composition for forming a lotus leaf-like structure according to claim 1, wherein the silane in the non-silicone oil microcapsule is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane.
4. A method of preparing a self-cleaning ceramic coating composition for forming a lotus leaf like structure according to claim 1, characterized in that the method comprises the steps of:
s1, preparing color paste: uniformly mixing silica sol, pigment, filler, dispersing agent and deionized water, regulating the pH value to 9.5-10.5 by using a 1% NaOH solution, and grinding to the fineness of below 20 mu m;
s2, preparing ceramic paint: evenly mixing silane, isopropanol, silicone oil microcapsule and 25% formic acid; and then adding the color paste prepared in the step S1, uniformly mixing, and reacting for 4-8 hours to obtain the ceramic coating.
5. The method of manufacturing a self-cleaning ceramic coating composition for forming a lotus leaf like structure according to claim 4, wherein in step S1, after grinding to a fineness of 20 μm or less, the pH of the paste is measured again and if it is less than 9.0, it is adjusted to 9.0-10.0 with a 1% naoh solution.
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| CN202211048052.7A CN115322597B (en) | 2022-08-30 | 2022-08-30 | Self-cleaning ceramic coating with lotus leaf-like structure and preparation and application methods thereof |
| PCT/CN2023/113331 WO2024046129A1 (en) | 2022-08-30 | 2023-08-16 | Self-cleaning ceramic coating of lotus-leaf-like structure, preparation method therefor and application method thereof |
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| CN115770716B (en) * | 2022-11-30 | 2023-11-14 | 江门市东鹏智能家居有限公司 | Antibacterial self-cleaning toilet bowl sensor panel and preparation method thereof |
| CN116589878B (en) * | 2023-07-19 | 2023-10-24 | 北京碧海云智新材料技术有限公司 | Long-acting self-cleaning graphene ceramic water paint and preparation method and application thereof |
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| CN105949831A (en) * | 2016-06-28 | 2016-09-21 | 佛山市珀力玛高新材料有限公司 | Ceramic coating with high hardness in hot environment |
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| CN115322597B (en) * | 2022-08-30 | 2023-04-25 | 上海宜瓷龙新材料股份有限公司 | Self-cleaning ceramic coating with lotus leaf-like structure and preparation and application methods thereof |
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