CN111218153A - Method for producing structure having superhydrophobic surface - Google Patents

Method for producing structure having superhydrophobic surface Download PDF

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CN111218153A
CN111218153A CN201911131973.8A CN201911131973A CN111218153A CN 111218153 A CN111218153 A CN 111218153A CN 201911131973 A CN201911131973 A CN 201911131973A CN 111218153 A CN111218153 A CN 111218153A
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particles
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李岩康
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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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Abstract

The invention provides a preparation method of a structural body with a super-hydrophobic surface, belonging to the technical field of materials and comprising the following steps: with nano SiO2Preparation of modified nano SiO by using particles as raw material2Particles and SiO2Alcohol sol, modifying nano SiO2Particles and SiO2Preparing alcohol sol into a prepolymer solution, coating the prepolymer solution on a clean matrix structure, and curing the prepolymer solution on the matrix structure to form a structure body with a stable super-hydrophobic surface; the above-mentioned superhydrophobic surface exhibits a contact angle of not less than 158 ° and a rolling angle of less than 5 °. The preparation method provided by the invention can increase the rough structure and roughness of the super-hydrophobic surface, increase the water contact angle, reduce the rolling angle and the viscous force to water, improve the wear resistance, durability and high-temperature stability, enhance the ultraviolet aging resistance to reduce the contact angle loss rate under ultraviolet weathering, prolong the service life and enhance the waterproof and antifouling effects.

Description

Method for producing structure having superhydrophobic surface
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a structure body with a super-hydrophobic surface.
Background
Superhydrophobicity is an extreme phenomenon of wetting. Generally, superhydrophobic refers to a contact angle of a droplet on a solid surface of greater than 150 °. Further, if a surface exhibits a water droplet rolling (sliding) angle of less than 10 °, the surface is considered to be: the cleaning is automatic. Generally, hydrophobicity is expressed by covering the surface with a molecular residue having a low surface tension, and superhydrophobicity is difficult to express with only a molecular residue having a low surface tension. Due to the unique wetting characteristic of the super-hydrophobic surface, the super-hydrophobic surface has wide potential applications, such as anti-icing, self-cleaning, drag reduction, anti-fog, corrosion resistance and the like, and has great application value in the fields of building, textile, communication, navigation, aviation and the like. As is well known, the combined action of the micro-nano binary structure on the surface of lotus leaves and the like and the waxy material is the main reason for forming super-hydrophobicity.
The superhydrophobic material reported at present can realize the superhydrophobic performance under relatively mild conditions, but the special micro-nano binary structure of the superhydrophobic surface has poor adaptability to external environments, and the surface structure can be polluted or damaged under complex working conditions of strong acid, strong base, high-concentration salt, high temperature, organic solvent and gas, particle or bacteria pollution, ultraviolet light irradiation or some mechanical abrasion and the like, for example, particles dissolved in the process of moisture evaporation are separated and deposited on the surface due to deposition of industrial dust or salt, so that the superhydrophobic performance is lost, however, the damage to the surface caused by accumulation of high temperature, acid-base environment, ultraviolet rays, pollutants such as dust, particles or bacteria cannot be prevented by the conventional technology, and the practical application of the superhydrophobic surface is severely limited. Although many publicly known documents frequently mention superhydrophobic films and methods for producing them, many of them are equivalent to a method for processing the surface roughness of a substrate, and the surface treatment process is easy to be complicated and costly. In addition, in the case of a superhydrophobic surface based on an organic polymer, although the cost is low, the resulting superhydrophobic surface has a practical problem because the solvent resistance and corrosion resistance are low.
Disclosure of Invention
The invention aims to provide a preparation method of a structural body with a super-hydrophobic surface, which can increase the rough structure and roughness of the surface, increase the water contact angle, reduce the rolling angle and the viscous force to water, improve the wear resistance, durability and high-temperature stability, enhance the ultraviolet aging resistance to reduce the contact angle loss rate under ultraviolet weathering, prolong the service life and have excellent waterproof and antifouling effects.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the preparation method of the powder with super hydrophobicity comprises the following steps: in nanometerSiO2Respectively preparing modified nano SiO by using particles as raw materials2Particles and SiO2Alcohol sol of the above SiO2The alcohol sol comprises photocatalyst and the modified nano SiO2The particles are prepared by mixing nano SiO2The particles are prepared in the environment of a modifier and a gain agent, wherein the gain agent is diphenyl ethanone and hexahydrophthalic anhydride; the super-hydrophobic surface prepared from the powder shows a contact angle of not less than 158 degrees and a rolling angle of less than 5 degrees. The method improves the roughness of the super-hydrophobic surface formed by the powder, enlarges the contact angle, increases the wear resistance durability and the high-temperature stability of the super-hydrophobic surface, is beneficial to enhancing the heat resistance, the wear resistance durability and the service life of the super-hydrophobic surface or the structure body with the super-hydrophobic surface, and can be used for preparing a film or a surface coating with super-hydrophobicity and low viscous force.
For the present invention, the addition amount of the modifier is nano SiO23-15% of the weight of the particles; the addition amount of the gain agent is nano SiO20.03-0.15% of the weight of the particles, wherein the weight ratio of the diphenyl ethanone to the hexahydrophthalic anhydride is 1: 0.5-1.5. The gain agent utilizes conjugated pi bonds in phenyl and nano SiO2The particles are bonded to form a stable Si-C bond, and simultaneously form an aggregate with a multi-unit structure with a modifier, the intermolecular force of the aggregate makes the space shape of the aggregate irregular, the roughness of the super-hydrophobic surface is increased, the contact angle of the super-hydrophobic surface is enlarged, and the wear resistance of the super-hydrophobic surface is also increased; in addition, the Si-C bond is stable in a high-temperature environment, so that the super-hydrophobic surface loses the super-hydrophobic characteristic only at 480 ℃, the surface can still keep the super-hydrophobic characteristic of a contact angle not less than 155 degrees after being subjected to high-temperature heat treatment at 450 ℃ for 24 hours, and the high-temperature stability and the durability of the structure body with the super-hydrophobic surface are enhanced.
For the purposes of the present invention, examples of modifiers are not limited to n-octyltriethoxysilane, polydimethylsiloxane, methyltriethoxysilane, phenyltrimethoxysilane; preferably, the modifier is phenyltrimethoxysilane.
For the present invention, nano SiO2The particle preparation conditions were: the weight ratio of the raw materials is silicon source to waterAmmonia water and alcohol in the ratio of 1:4-6:1-3:10-13, the reaction temperature is 40-50 ℃, and the reaction time is 4-6 h.
Further, the alcohol is absolute ethyl alcohol, and the weight fraction of the ammonia water is 20-30%; the silicon source is selected from one or more of methyl orthosilicate and ethyl orthosilicate, and examples are not limited to methyl orthosilicate and ethyl orthosilicate; preferably, the silicon source is tetraethyl orthosilicate.
For the purposes of the present invention, the amount of photocatalyst in the alcosol is from 15 to 35% by weight, examples of photocatalysts not being restricted to Bi2O3-TiO2、Co-TiO2、Fe2O3-TiO2、V2O5-TiO2(ii) a Preferably, the photocatalyst is TiO2. The photocatalyst can generate free radicals under illumination or ultraviolet rays, so that the ultraviolet protection effect is achieved, the heat accumulation of the super-hydrophobic surface is reduced, the heat resistance of the structure body is enhanced, negative oxygen ions are released outwards, and the environment is favorably influenced.
For the purposes of the present invention, SiO2The alcohol sol is prepared by the following method: taking nano SiO2Placing the particles in ethanol, adding 4-8 wt% hydrochloric acid and photocatalyst, stirring, dispersing, aging at 35-60 deg.C for 24-48 hr to obtain SiO2Alcohol sol. SiO 22After the alcohol sol is aged and cured, porous gel is formed inside the super-hydrophobic surface structure, and after the surface is worn, the porous structure of the internal gel is exposed, so that the surface has a new rough structure and roughness, the super-hydrophobic performance is maintained, the wear resistance and durability of the super-hydrophobic surface are improved, and the service life of the super-hydrophobic surface is prolonged.
For the purposes of the present invention, the use of powders having superhydrophobicity for the preparation of films or surface coatings having superhydrophobicity and low viscosity. More specifically, the present invention is applicable to a protective film for structures such as buildings, vehicle bodies, ship bodies, containers, and fluid ducts, and also applicable to a surface coating for household electric appliances such as refrigerators, microwave ovens, and washing machines, and for electronic products for communication such as computers, televisions, and cellular phones.
The present invention also provides a method for preparing a structure having a superhydrophobic surface, comprising: coating a prepolymer solution on a clean matrix structure; and curing the prepolymer solution on the matrix structure to form a structure with a stable superhydrophobic surface; the solute of the prepolymer solution is powder with super-hydrophobicity. The super-hydrophobic surface of the structure prepared by the method can prevent water from forming a continuous film, and can enable the water to form water flow on the surface to remove dust, so that the structure has excellent waterproof and antifouling effects, can be used for preparing a container for moving fluid, and has excellent ultraviolet aging resistance and long service life.
For purposes of the present invention, a base structure is any shape of dielectric, semiconductor, insulator or conductor structure, including but not limited to polymers, ceramics, metals and their compounds, fibers, leather, glass, plastics, wood, and the like.
For the purposes of the present invention, the particular manner of coating is not limited to dip coating, spin coating, spray coating, lacquer coating, knife coating.
For the present invention, the curing conditions of the prepolymer solution are as follows: the temperature is 100-120 ℃, and the time is 2-6 h.
The invention has the beneficial effects that:
1) the powder prepared by the method has super-hydrophobicity, large contact angle, wear resistance, durability and long service life, and can be used for preparing a film or a surface coating with super-hydrophobicity and low viscous force;
2) the preparation method can increase the high-temperature stability of the super-hydrophobic surface prepared from the powder, so that the super-hydrophobic surface begins to lose the super-hydrophobic characteristic at 480 ℃, and the surface can still keep the super-hydrophobic characteristic of a contact angle not less than 155 degrees after heat treatment at 450 ℃ for 24 hours;
3) the structure body prepared by the invention has a stable super-hydrophobic surface and excellent waterproof and antifouling effects, can be used for preparing a container for moving fluid, shows excellent ultraviolet aging resistance and long service life, has no limitation on materials and shapes of a matrix structure, and breaks through the use limitation of the structure body under complex working conditions such as high temperature, ultraviolet irradiation, mechanical abrasion and the like.
The invention adopts the technical scheme to provide the preparation method of the structural body with the super-hydrophobic surface, makes up the defects of the prior art, and has reasonable design and convenient operation.
Drawings
FIG. 1 is a schematic representation of the variation of water contact angles of different superhydrophobic surfaces in a wear test;
FIG. 2 is a schematic graph showing the relationship between contact angle and heat treatment temperature for different superhydrophobic surfaces;
FIG. 3 is a schematic representation of the durability of contact angles of different superhydrophobic surfaces at high temperatures of 450 ℃;
FIG. 4 is a graph showing the relationship between the contact angle of different superhydrophobic surfaces and the UV aging treatment time.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the preparation method of the powder with super hydrophobicity comprises the following steps: with nano SiO2Respectively preparing modified nano SiO by using particles as raw materials2Particles and SiO2Alcohol sol of the above SiO2The alcohol sol comprises photocatalyst and the modified nano SiO2The particles are prepared by mixing nano SiO2The particles are prepared in the environment of a modifier and a gain agent, wherein the gain agent is diphenyl ethanone and hexahydrophthalic anhydride; the super-hydrophobic surface prepared from the powder shows a contact angle of not less than 158 degrees and a rolling angle of less than 5 degrees. The method improves the roughness of the super-hydrophobic surface formed by the powder, enlarges the contact angle, increases the wear resistance durability and the high-temperature stability of the super-hydrophobic surface, is beneficial to enhancing the heat resistance, the wear resistance durability and the service life of the super-hydrophobic surface or the structure body with the super-hydrophobic surface, and can be used for preparing a film or a surface coating with super-hydrophobicity and low viscous force.
For the present invention, the addition amount of the modifier is nano SiO23-15% of the weight of the particles; the addition amount of the gain agent is nano SiO20.03-0.15% of the weight of the particles, wherein the weight ratio of the diphenyl ethanone to the hexahydrophthalic anhydride is 1:0.5-1.5 (such as 1:0.65 or 1:0.8 or 1:1.15 or 1: 1.2). The gain agent utilizes conjugated pi bonds in phenyl and nano SiO2Stabilization of particle bondingThe Si-C bond and the modifier form an aggregate with a multi-unit structure, the intermolecular force of the aggregate makes the space shape of the aggregate irregular, increases the roughness of the super-hydrophobic surface, increases the contact angle of the super-hydrophobic surface and also increases the wear resistance of the super-hydrophobic surface; in addition, the Si-C bond is stable in a high-temperature environment, so that the super-hydrophobic surface loses the super-hydrophobic characteristic only at 480 ℃, the surface can still keep the super-hydrophobic characteristic of a contact angle not less than 155 degrees after being subjected to high-temperature heat treatment at 450 ℃ for 24 hours, and the high-temperature stability and the durability of the structure body with the super-hydrophobic surface are enhanced.
For the purposes of the present invention, examples of modifiers are not limited to n-octyltriethoxysilane, polydimethylsiloxane, methyltriethoxysilane, phenyltrimethoxysilane; preferably, the modifier is phenyltrimethoxysilane.
For the present invention, nano SiO2The particle preparation conditions were: the weight ratio of the raw materials is that the silicon source is water, ammonia water and alcohol is 1:4-6:1-3:10-13 (such as 1:4.5:1.5:11 or 1:5:2.5:12.5 or 1:5.5:3: 11.5), the reaction temperature is 40-50 ℃, and the reaction time is 4-6 h.
Further, the alcohol is absolute ethyl alcohol, and the weight fraction of the ammonia water is 20-30%; the silicon source is selected from one or more of methyl orthosilicate and ethyl orthosilicate, and examples are not limited to methyl orthosilicate and ethyl orthosilicate; preferably, the silicon source is tetraethyl orthosilicate.
Further, the prepared nano SiO 23/4 application of particles in preparation of modified nano SiO2Particles, remaining 1/4 for preparing SiO2Alcohol sol.
For the purposes of the present invention, the amount of photocatalyst in the alcosol is from 15 to 35% by weight, examples of photocatalysts not being restricted to Bi2O3-TiO2、Co-TiO2、Fe2O3-TiO2、V2O5-TiO2(ii) a Preferably, the photocatalyst is TiO2. The photocatalyst can generate free radicals under illumination or ultraviolet rays, so that the ultraviolet protection effect is achieved, the heat accumulation of the super-hydrophobic surface is reduced, the heat resistance of the structure body is enhanced, negative oxygen ions are released outwards, and a ring is pairedThe environment has a beneficial effect.
For the purposes of the present invention, SiO2The alcohol sol is prepared by the following method: taking nano SiO2Placing the particles in ethanol, adding 4-8 wt% hydrochloric acid and photocatalyst, stirring, dispersing, aging at 35-60 deg.C for 24-48 hr to obtain SiO2Alcohol sol. SiO 22After the alcohol sol is aged and cured, porous gel is formed inside the super-hydrophobic surface structure, and after the surface is worn, the porous structure of the internal gel is exposed, so that the surface has a new rough structure and roughness, the super-hydrophobic performance is maintained, the wear resistance and durability of the super-hydrophobic surface are improved, and the service life of the super-hydrophobic surface is prolonged.
For the purposes of the present invention, the use of powders having superhydrophobicity for the preparation of films or surface coatings having superhydrophobicity and low viscosity. More specifically, the present invention is applicable to a protective film for structures such as buildings, vehicle bodies, ship bodies, containers, and fluid ducts, and also applicable to a surface coating for household electric appliances such as refrigerators, microwave ovens, and washing machines, and for electronic products for communication such as computers, televisions, and cellular phones.
The present invention also provides a method for preparing a structure having a superhydrophobic surface, comprising: coating a prepolymer solution on a clean matrix structure; and curing the prepolymer solution on the matrix structure to form a structure with a stable superhydrophobic surface; the solute of the prepolymer solution is powder with super-hydrophobicity. The super-hydrophobic surface of the structure prepared by the method can prevent water from forming a continuous film, and can enable the water to form water flow on the surface to remove dust, so that the structure has excellent waterproof and antifouling effects, can be used for preparing a container for moving fluid, and has excellent ultraviolet aging resistance and long service life.
For purposes of the present invention, a base structure is any shape of dielectric, semiconductor, insulator or conductor structure, including but not limited to polymers, ceramics, metals and their compounds, fibers, leather, glass, plastics, wood, and the like.
For the purposes of the present invention, the particular manner of coating is not limited to dip coating, spin coating, spray coating, lacquer coating, knife coating.
For the present invention, the curing conditions of the prepolymer solution are as follows: the temperature is 100-120 ℃, and the time is 2-6 h.
Furthermore, the preparation method of the structure with the super-hydrophobic surface comprises the following specific steps:
(1) mixing the raw materials according to the weight ratio of silicon source to water to ammonia water to alcohol of 1:4-6:1-3:10-13, and reacting at 40-50 ℃ for 4-6h to obtain dispersed nano SiO2Particles;
(2) taking 1/4 nano SiO2Placing the particles in 4-10 times of ethanol, adding 4-8 wt% hydrochloric acid and photocatalyst, stirring, dispersing, aging at 35-60 deg.C for 24-48 hr to obtain SiO2Alcohol sol;
(3) taking the rest 3/4 nano SiO2Dissolving the particles in 5-10 times of anhydrous ethanol, adjusting pH to 7-9, adding modifier and gain agent, stirring at 50-80 deg.C for 2-4 hr, vacuum filtering, washing with ethanol, and drying to obtain modified nanometer SiO2Particles;
(4) soaking the matrix structure in ethanol, ultrasonically cleaning for 10-30min, and drying to obtain a clean matrix structure;
(5) obtaining the obtained modified nano SiO2Particles and SiO2And uniformly mixing the alcohol sol to form a prepolymer solution, coating the prepolymer solution on the substrate structure, and curing for 2-6h in an environment with the temperature of 100-120 ℃ to obtain the structure with the super-hydrophobic surface.
While various aspects of the invention have been described in detail in the foregoing description, such description is to be considered illustrative or exemplary and not restrictive. It will be understood that changes and modifications may be effected by those of ordinary skill in the art within the scope and spirit of the appended claims. In particular, the present invention covers other embodiments having any combination of features from the different embodiments described above and below, in particular, without limiting the scope of the invention to the specific examples below.
Example 1:
the preparation method of the powder with super hydrophobicity comprises the following specific steps:
(1) the raw materials are mixed according to the weight ratio of tetraethyl orthosilicate, water, ammonia water and alcohol of 1:4.5:2.5:12, and then the mixture reacts for 6 hours at the temperature of 50 ℃ to obtain the dispersed nano SiO2Particles, wherein the alcohol is absolute ethyl alcohol, and the weight fraction of ammonia water is 25%;
(2) taking 1/4 nano SiO2The particles were put in 8 times the amount of ethanol, and then hydrochloric acid and TiO at a concentration of 6.5 wt% were added2Uniformly stirring and dispersing, and then aging for 35 hours at the temperature of 55 ℃ to obtain SiO2Alcohol sol, the addition amount of the hydrochloric acid is 8 percent of the weight of the nano particles, and TiO is used2In an amount of 20% by weight of the alcohol sol;
(3) taking the rest 3/4 nano SiO2Dissolving the particles in 5-10 times of anhydrous ethanol, adjusting pH to 8, adding modifier phenyltrimethoxysilane and a gain agent, stirring at 70 deg.C for reaction for 3.5h, vacuum filtering, washing with ethanol, and drying to obtain modified nanometer SiO2The addition amount of the phenyltrimethoxysilane is nano SiO213.5% of the weight of the particles, and the addition amount of the gain agent is nano SiO20.05% of the weight of the particles, wherein the gain agent is diphenyl ethanone and hexahydrophthalic anhydride, and the weight ratio of the gain agent to the hexahydrophthalic anhydride is 1: 1.5;
(4) mixing SiO2Drying the alcohol sol at 150 ℃, and then adding the alcohol sol into the modified nano SiO2Mixing the particles, and grinding to obtain the super-hydrophobic powder.
Example 2:
the present example is different from example 1 in the following point: preparing modified nano SiO in step (3)2No gain agent diphenyl ethanol ketone and hexahydrophthalic anhydride are added during the preparation of the particles.
Example 3:
the preparation method of the structure with the super-hydrophobic surface comprises the following specific steps:
(1) the raw materials are mixed according to the weight ratio of tetraethyl orthosilicate, water, ammonia water and alcohol of 1:6:2.5:11.5, and then the mixture is reacted for 5.5 hours at the temperature of 50 ℃ to obtain the dispersed nano SiO2Particles, wherein the alcohol is absolute ethyl alcohol, and the weight fraction of ammonia water is 28%;
(2) taking 1/4 nano SiO2The particles were put in 10 times of ethanol, and then hydrochloric acid and TiO at a concentration of 7 wt% were added2Uniformly stirring and dispersing, and then aging for 30h at 60 ℃ to obtain SiO2Alcohol sol, the addition amount of the hydrochloric acid is 8 percent of the weight of the nano particles, and TiO is used2In an amount of 30% by weight of the alcohol sol;
(3) taking the rest 3/4 nano SiO2Dissolving the particles in 5-10 times of anhydrous ethanol, adjusting pH to 9, adding phenyltrimethoxysilane and a gain agent, stirring at 80 deg.C for 3 hr, vacuum filtering, washing with ethanol, and drying to obtain modified nanometer SiO2The addition amount of the phenyltrimethoxysilane is nano SiO210% of the weight of the particles, and the addition amount of the gain agent is nano SiO20.1% of the weight of the particles, wherein the gain agent is diphenyl ethanone and hexahydrophthalic anhydride, and the weight ratio of the gain agent to the hexahydrophthalic anhydride is 1: 1;
(4) soaking the matrix structure in ethanol, ultrasonically cleaning for 30min, and drying to obtain a clean matrix structure;
(5) obtaining the obtained modified nano SiO2Particles and SiO2And uniformly mixing the alcohol sol to form a prepolymer solution, coating the prepolymer solution on a substrate structure, and curing for 4.5 hours at 120 ℃ to obtain the structural body with the super-hydrophobic surface.
Example 4:
the present example is different from example 3 in the method for producing a structure having a superhydrophobic surface: the step (5) is added with a binder, and the concrete measures are as follows: obtaining the obtained modified nano SiO2Particles and SiO2Mixing alcohol sol and binder uniformly to form prepolymer solution, placing the matrix structure in the prepolymer solution to be fully wetted, and then placing the matrix structure in an environment of 120 ℃ to be cured for 4.5 hours to obtain a structural body with a super-hydrophobic surface, wherein the binder is added in SiO2The weight of the alcohol sol is 0.08 percent, the adhesive is epichlorohydrin and dimethylamino propionitrile with the weight ratio of 1:0.5,the adhesive can activate and modify the nano SiO2Particles and SiO2The alcohol sol increases active sites in the aggregate solution, and further accelerates the adhesion process between the matrix structure and the super-hydrophobic surface through chemical connection, so that the roughness of the super-hydrophobic surface is increased due to the accelerated adhesion, the rolling angle of the super-hydrophobic surface and the viscous force to water are reduced, and the wear resistance and durability of the super-hydrophobic surface of the structure body are improved; meanwhile, the two components have synergistic effect, and can generate free radical polymerization inhibition in an ultraviolet environment, so that the ultraviolet aging resistance of the super-hydrophobic surface is enhanced, the super-hydrophobicity is kept good after 6000h of ultraviolet weathering test, and the contact angle loss rate is lower than 3%.
Example 5:
the present example is different from example 3 in the method for producing a structure having a superhydrophobic surface: the prepolymer solution in the step (5) does not contain SiO2Alcohol sol, only modified nano SiO is adopted2The particles are prepared to give a structure having a superhydrophobic surface.
Example 6:
the preparation method of the structure with the super-hydrophobic surface comprises the following specific steps:
(1) soaking the matrix structure in ethanol, ultrasonically cleaning for 30min, and drying to obtain a clean matrix structure;
(2) the powder with super-hydrophobicity prepared in the example 1 is dispersed in ethanol with the amount of 10 times of the weight of the powder to form a prepolymer solution, the prepolymer solution is coated on a substrate structure, and then the substrate structure is cured for 4.5 hours at the temperature of 120 ℃ to obtain the structure with the super-hydrophobic surface.
Example 7:
this example is different from example 6 in the method for producing a structure having a superhydrophobic surface: in the step (2), the powder having superhydrophobicity prepared in example 2 was used.
Test example 1:
hydrophobicity testing of different superhydrophobic surfaces
The test method comprises the following steps: taking the structural body samples prepared in the embodiments 3, 4, 6 and 7, testing the water contact angles and the rolling angles of different super-hydrophobic surfaces by adopting an SL200B type contact angle tester, controlling the size of water drops by controlling a microsyringe, dripping 5 mu L of small water drops on the surface of the coating, obtaining a contact image of the water drops on the surface by a computer, and obtaining the contact angle by a single circle cutting fitting method; when the rolling angle is measured, 5 mu L of water drops are firstly dropped on the surface, then the inclination angle of the sample table is slowly adjusted, so that the water drops roll under the action of gravity, and the included angle between the sample table and the horizontal line when the sample table starts to roll is the rolling angle; the tests were performed at different locations on the surface, 5 sets of parallel tests were performed, and the results are averaged as shown in table 1 below.
TABLE 1 contact angle and sliding angle test results for different superhydrophobic surfaces
Contact Angle/° Roll angle/°
Example 3 160.7 4.3
Example 4 161.1 3.6
Example 6 160.8 4.5
Example 7 153.2 5.3
As can be seen from the above table, the contact angles of the superhydrophobic surfaces of examples 3, 4, and 6 are all greater than 158 °, the rolling angles are all less than 5 °, and the contact angle of example 7 is less than 158 °, the rolling angle is greater than 5 °, which indicates that the superhydrophobic surface of example 7 has a low hydrophobic property and a high viscosity to water, mainly because the gain agent is added in the preparation method of other examples, the gain agent can increase the roughness of the superhydrophobic surface, so that the contact angle of the superhydrophobic surface is increased, and the hydrophobic property is more excellent; the difference between the contact angle and the rolling angle of examples 3 and 6 is not obvious, but the rolling angle of example 4 is more excellent than the two, and the rolling angle has lower viscous force to water, which shows that the addition of the binder of example 4 increases the roughness of the superhydrophobic surface due to the accelerated adhesion, thereby reducing the rolling angle and the viscous force to water of the superhydrophobic surface.
Test example 2:
abrasion resistance testing of different superhydrophobic surfaces
The test method comprises the following steps: a sample of the structures obtained in examples 3, 4, 5, 6 and 7 was taken, a 1000-mesh sandpaper was taken, the superhydrophobic surface was made to face the rough surface of the sandpaper, and the sandpaper was pressed against the sample with a force of 500g weight, and the sample was moved back and forth in the same direction by 10cm during the abrasion resistance test, and the two-time movement process was defined as one cycle of the friction test. After each rubbing test, the contact angle of the sample was tested. The results are shown in FIG. 1.
FIG. 1 is a schematic representation of the change in water contact angle of different superhydrophobic surfaces in a wear test. As can be seen from the graph, the water contact angle in example 5 decreased most rapidly, the contact angle at the end of the experiment was only 138 degrees, and the superhydrophobicity was not satisfied, indicating that SiO2Due to the addition of the alcosol, the surface has different rough structures and roughness, so that the super-hydrophobic performance is kept, the wear resistance and durability of the surface are improved, and the service life of the surface is prolonged; example 7 decreased most rapidly among the other groups, the contact angle at the end of the experiment was 148 °, examples 3 and 6 times, the contact angles at the end of the experiment were 158.2 ° and 159.1 °, respectively, the trend of the decrease was the slowest for example 4, and the contact angle at the end of the experiment was 160.1 °, stated asIt is clear that the wear-resistant durability of the superhydrophobic surface can be increased by the enhancement effect of the gain agent and the binder on the roughness of the superhydrophobic surface.
Test example 3:
high temperature resistance testing of different superhydrophobic surfaces
The test method comprises the following steps: the samples of the structures obtained in examples 6 and 7 were calcined in an air atmosphere at 80 ℃, 160 ℃, 240 ℃, 320 ℃, 400 ℃, 480 ℃, 560 ℃, 640 ℃, 720 ℃ and 800 ℃ for 3 hours, respectively. Meanwhile, in order to investigate the durability of the superhydrophobic surface at high temperature, the structure was calcined at 450 ℃ for various lengths of time, and the change in hydrophobicity of the coating before and after calcination was evaluated using a static contact angle, and the results are shown in fig. 2 and 3.
Fig. 2 is a schematic diagram of the relationship between the contact angle and the heat treatment temperature of different superhydrophobic surfaces, and fig. 3 is a schematic diagram of the durability of the contact angle of different superhydrophobic surfaces at a high temperature of 450 ℃. As can be seen from fig. 2, the contact angle of the superhydrophobic surface of example 6 begins to decrease below 150 ° after 480 ℃ and loses the superhydrophobic property, while the contact angle of the surface of example 7 decreases below 150 ° after 320 ℃ and loses the superhydrophobic property; as can be seen from FIG. 3, the superhydrophobic surface of example 6 can still maintain the superhydrophobic property of the contact angle of not less than 155 degrees after being subjected to high-temperature heat treatment at 450 ℃ for 24 hours, and the contact angle of example 7 is reduced to below 150 degrees after 18 hours, so that the superhydrophobic performance is lost; as can be seen from fig. 2 and 3, the addition of the gain agent enhances the heat resistance of the superhydrophobic surface, and enhances the high temperature stability and durability of the structure having the superhydrophobic surface.
Test example 4:
ultraviolet aging resistance test of different super-hydrophobic surfaces
The test method comprises the following steps: samples of the structures obtained in examples 3 and 4 were taken and placed in an ultraviolet aging oven for aging resistance test. The accelerated aging condition is that the temperature is 60 ℃, and the light intensity is 0.89W/m2. The evaluation standard is ISO 11507: 2007. the results are shown in FIG. 4.
FIG. 4 is a graph showing the relationship between the contact angle of different superhydrophobic surfaces and the UV aging treatment time. As can be seen from the graph, the contact angle of example 3 is reduced to below 150 ℃ after 5000h of weathering, and the superhydrophobic performance is lost, while the contact angle of example 4 is 155.5 ℃ after 6000h of weathering, the superhydrophobic performance is well maintained, and the contact angle loss rate is lower than 3%, which shows that the ultraviolet aging resistance of the superhydrophobic surface can be enhanced by adding the binder in example 4.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.

Claims (10)

1. The preparation method of the powder with the super-hydrophobic surface comprises the following steps: with nano SiO2Respectively preparing modified nano SiO by using particles as raw materials2Particles and SiO2Alcohol sol of said SiO2The alcohol sol comprises a photocatalyst and the modified nano SiO2The particles are prepared by mixing nano SiO2The particles are prepared in the environment of a modifier and a gain agent, wherein the gain agent is diphenyl ethanone and hexahydrophthalic anhydride;
the super-hydrophobic surface prepared from the powder shows a contact angle of not less than 158 degrees and a rolling angle of less than 5 degrees.
2. The method for preparing a powder having a superhydrophobic surface according to claim 1, characterized in that: the addition amount of the modifier is nano SiO23-15% of the weight of the particles; the addition amount of the gain agent is nano SiO20.03-0.15% of the weight of the particles, and the weight ratio of the diphenyl ethanone to the hexahydrophthalic anhydride is 1: 0.5-1.5.
3. The method for preparing a powder having a superhydrophobic surface according to claim 1, characterized in that: the nano SiO2Particle preparationThe conditions are as follows: the weight ratio of the raw materials is silicon source, water, ammonia water and alcohol is 1:4-6:1-3:10-13, the reaction temperature is 40-50 ℃, and the reaction time is 4-6 h.
4. The method for preparing a powder having a superhydrophobic surface according to claim 3, characterized in that: the alcohol is absolute ethyl alcohol, and the weight fraction of the ammonia water is 20-30%; the silicon source is selected from one or more of methyl orthosilicate and ethyl orthosilicate, and preferably, the silicon source is tetraethyl orthosilicate.
5. The method for preparing a powder having a superhydrophobic surface according to claim 1, characterized in that: the amount of photocatalyst in the alcohol sol is 15-35 wt%.
6. The method for preparing a powder having a superhydrophobic surface according to claim 1, characterized in that: the SiO2The alcohol sol is prepared by the following method: taking nano SiO2Placing the particles in ethanol, adding 4-8 wt% hydrochloric acid and photocatalyst, stirring, dispersing, and aging at 35-60 deg.C for 24-48 h.
7. Use of a powder having a superhydrophobic surface prepared by the method of any one of claims 1-6 for preparing a film or surface coating having superhydrophobicity and low viscous force.
8. A method of making a structure having a superhydrophobic surface, comprising: coating a prepolymer solution on a clean matrix structure; and curing the prepolymer solution on the matrix structure to form a structure with a stable superhydrophobic surface; the solute of the prepolymer solution is the powder with super-hydrophobicity prepared by the method of any one of claims 1 to 6.
9. The method for producing a structure having a superhydrophobic surface according to claim 8, characterized in that:
the base structure is a dielectric, semiconductor, insulator or conductor structure of any shape.
10. The method for producing a structure having a superhydrophobic surface according to claim 8, characterized in that:
the curing operation conditions of the prepolymer solution are as follows: the temperature is 100-120 ℃, and the time is 2-6 h.
CN201911131973.8A 2019-11-19 2019-11-19 Method for producing structure having superhydrophobic surface Pending CN111218153A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112048202A (en) * 2020-09-14 2020-12-08 陈佳 Preparation method of steel-based corrosion-resistant super-hydrophobic coating

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Publication number Priority date Publication date Assignee Title
CN101955728A (en) * 2009-07-17 2011-01-26 黄祥道 Organic-inorganic hybrid wear-resistant transparent coating for reinforcing surface of optical plastics
CN110183880A (en) * 2019-05-21 2019-08-30 东南大学 A kind of photocatalysis super-amphiphobic coating and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101955728A (en) * 2009-07-17 2011-01-26 黄祥道 Organic-inorganic hybrid wear-resistant transparent coating for reinforcing surface of optical plastics
CN110183880A (en) * 2019-05-21 2019-08-30 东南大学 A kind of photocatalysis super-amphiphobic coating and its preparation method and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112048202A (en) * 2020-09-14 2020-12-08 陈佳 Preparation method of steel-based corrosion-resistant super-hydrophobic coating

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