CN1128187C - Reversible double-superaffinity film and its preparing process and application - Google Patents

Abstract

The invention particularly relates to a reversible super-amphiphilic thin film and its preparation method and application. Add 0.5-32 mol of metal salt to 70-98 mol of organic solvent, disperse evenly by ultrasonic wave, add 0.1-6 mol of stabilizer and 0.01-1.63 mol of catalyst to prepare transparent sol, apply it on the surface of the substrate, and place it at 550-720 In the muffler furnace at ℃, keep it warm for 0.05-1.5 hours to obtain a transparent film, and after 10 minutes to 5 hours of external field induction, obtain _TiO2 nanoparticles with a molar content of 80-98% and metal oxide nanoparticles with a molar content of 2-20%. The composed reversible super-amphiphilic thin film will lose the super-amphiphilic property after being induced by an external field that eliminates the super-amphiphilic effect.

Description

Reversible super amphiphilic thin film and its preparation method and application

Technical field

The invention belongs to the technical field of functional materials, and in particular relates to a reversible super-amphiphilic (super-hydrophilic, super-oleophilic) film and its preparation method and application.

Background technique

PCT patent WO9629375A (International Publication Date September 26, 1996) proposes to firstly synthesize a colloid by adding acid hydrolysis to titanate, and then use this colloid to prepare a super-hydrophilic _TiO2 film excited by ultraviolet light irradiation. Superhydrophilicity means that the contact angle of water on the solid surface tends to zero. However, the superhydrophilic effect lasts for a short time and its performance is unstable. The superhydrophilic film reported in the literature can only maintain its superhydrophilicity in the dark for more than ten hours after leaving the ultraviolet light source. When the time of storage in the dark is further prolonged, the water on the surface of the superhydrophilic film As the contact angle gradually increases, the superhydrophilic effect will gradually be lost. Chinese invention patent (Application No.: 98124417.3; Publication No.: CN1224036A) once proposed a titanium sol-gel coating with nano-inorganic compound particles, and the titanium dioxide film material prepared by using the titanium sol-gel can reach Highly hydrophilic, it can be used for anti-fogging and self-cleaning on surfaces such as glass and ceramics. Among them, the inorganic compound nanoparticles are directly added to the titanium sol. Since the nanoparticles all have the common characteristics of high surface energy and large specific surface area, the nanoparticles are very prone to coagulation or agglomeration, which in turn causes the nanoparticles to form in the titanium sol. - Problems with uneven dispersion and settling in gel coats.

Utilize the common problem that the film that above-mentioned prior art makes exists is:

(1) It only has superhydrophilicity, but not superlipophilicity, so it does not have superamphiphilicity. Super-amphiphilicity means that the contact angles of water and oil (with hexadecane as the standard) on the solid surface tend to be zero, that is, the surface of the film has both superhydrophilicity and superlipophilicity.

(2) The induction method is single, and there are few applicable occasions. The induction and excitation methods of superhydrophilic films reported in the literature are limited to ultraviolet light irradiation, but in the process of ultraviolet light irradiation, ultraviolet light will cause damage to the human body, and it is not suitable to use ultraviolet light irradiation in many applications. Therefore, The superhydrophilic films in the literature are applicable to few occasions.

(3) The superhydrophilicity is uncontrollable and can only be eliminated naturally. In the existing literature reports, after ultraviolet light irradiation makes the surface of titanium dioxide achieve super-hydrophilic effect, the super-hydrophilic effect can only be gradually lost after being placed in a dark place for more than ten hours. In this way, the superhydrophilic film can only be limited to occasions where continuous superhydrophilicity is required on the surface, but cannot be applied to occasions where intermittent superhydrophilicity is required.

(4) The heat treatment temperature for superhydrophilic films is low, all below 550°C, and in the existing glass production line, the temperature of the process steps suitable for modifying superhydrophilic films is all higher than 630°C, therefore, existing The preparation process of the super-hydrophilic film is not suitable for the existing glass production line, and the strength of the obtained super-hydrophilic film is low.

Contents of Invention

One of the purposes of the present invention is to overcome the problems of unstable performance, single induction method, low heat treatment temperature and extremely easy condensation or aggregation of nanoparticles in the superhydrophilic film in the prior art, and provide a method that can be used in multiple induction methods. A reversible super-amphiphilic thin film with excitation, stable performance and high temperature treatment.

Another object of the present invention is to prepare reversible super-amphiphilic thin film of metal oxide by sol-gel method and its application.

The reversible super-amphiphilic thin film of the present invention is composed of _TiO2 nanoparticles with a molar content of 80-98% and metal oxide nanoparticles with 2-20%, and the particle diameter of the nanoparticles is 50-80nm; The film has superhydrophilicity and superlipophilicity simultaneously, that is, the contact angles of water and oil (n-hexadecane) on the surface of the film all tend to zero; The contact angle of water and oil (n-hexadecane) on the surface of the film can be rapidly and reversibly changed under the alternating induction of the external field that eliminates the super-amphiphilic effect.

The metal oxide nanoparticles are selected from SnO ₂ , ZnO, WO ₃ , Al ₂ O ₃ , SrTiO ₃ , In ₂ O ₃ , MoO ₃ , Nb ₂ O ₃ , SiO ₂ , ZrO ₂ or mixtures thereof.

The metal oxide nanoparticles are preferably composed of 3 to 6 different metal oxide nanoparticles in any proportion.

The preparation method of the reversible super amphiphilic thin film of the present invention is as follows:

(1) At room temperature, add 0.5 to 32 mol of metal salt into 70 to 98 mol of organic solvent, wherein the metal salt is made of titanium salt with a molar content of 80 to 98% and 2 to 20% of other metal salts Composition, the metal salt is uniformly dispersed in the organic solvent by ultrasonic waves, and a transparent solution is obtained;

(2) Add 0.1 to 6 mol of stabilizer to the above transparent solution, slowly add 0.01 to 1.63 mol of catalyst dropwise under strong stirring at room temperature, and continue stirring for about 0.1 to 8 hours after the dropwise addition to form a part containing Mixtures of hydrolyzed metal salts;

(3) aging the above mixture for 3 to 8 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Spin-coat, spray or dip-coat the above-mentioned transparent sol on the surface of the substrate, dry it at room temperature, place it in a muffle furnace at 550-720°C, and keep it warm for 0.05-1.5 hours to obtain a transparent film;

(5) After the transparent film is subjected to an external field that causes a super-amphiphilic effect for 10 minutes to 5 hours, a reversible super-amphiphilic film is obtained.

After step (5), further have the step that makes gained ultra-amphiphilic thin film eliminate super-amphiphilic effect fast:

(6) After the above-mentioned super-amphiphilic film is induced by an external field to eliminate the super-amphiphilic effect, the film will lose the super-amphiphilic effect. The external field induction time can be determined according to actual needs.

The metal salt is preferably composed of 3 to 6 different metal salts in any proportion.

The titanium salts include tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, tetra(2-ethylhexyl) titanate, tetra(heptadecane) titanate, diisopropoxy - Titanium diacetylacetonate, titanium di-n-butoxy-bis(triethanolamine), titanium dihydroxy-dilactate, or titanium tetraoctene glycolate; other metal salts include tin tetrachloride, tin acetate, zinc chloride, acetic acid Zinc, zinc nitrate hexahydrate, zinc carbonate, tungsten hexahydrate, tungsten dichloride, basic aluminum acetate dihydrate, anhydrous aluminum chloride, aluminum isopropoxide, strontium dichloride hexahydrate, strontium carbonate, Indium trichloride, indium nitrate pentahydrate, indium acetate, ammonium molybdate, niobium pentachloride, tetrachlorosilane, tetrabromosilane, tetraethyl silicate, tetrabutyl silicate, dimethoxydiethoxy Silane, dimethyldichlorosilane, zirconium tetrachloride, zirconium nitrate pentahydrate or zirconium hypochlorite;

The organic solvent can be selected from ethanol, propanol, isopropanol, n-butanol, isobutanol, acetone, chloroform, n-hexane, benzene, toluene or carbon tetrachloride;

Described stabilizer can select ethylene glycol, diethylene glycol, triethylene glycol, glycerol or 1,3-propanediol for use;

The catalyst can be selected concentrated hydrochloric acid, acetic acid, concentrated nitric acid, concentrated sulfuric acid or concentrated ammonia water.

The method of external field induction leading to the super-amphiphilic effect includes ultraviolet light irradiation, plasma excitation, laser irradiation, 400-500nm visible light irradiation, argon ion bombardment or microwave excitation.

The external field for eliminating the super-amphiphilic effect is ultrasonic wave or weak acid environment with pH=4-6.

The reversible super-amphiphilic film prepared by the present invention is used for surface modification of objects, and has good uses in many aspects:

(1) Coating the reversible super-amphiphilic film material on the surface of glass, metal, ceramics and other substrates to form a reversible super-amphiphilic film can make the surface of these substrates self-cleaning. For example, it is used for interior decoration materials, bathroom and toilet equipment, shop counters and surface decoration of tableware, so that they can be easily washed with water and remove oil stains; it can also be used to modify road signs, road lights, and roadside advertisements Signs, residential exterior walls, outdoor sculptures, car paint and car lights, etc. These modified objects can use rainfall to achieve the self-cleaning effect of removing mud;

(2) Coating the reversible super-amphiphilic thin film material on the glass and mirror surface to form a reversible super-amphiphilic thin film, which can prevent the glass and mirror surface from fogging. It can prevent fogging on roadside reflectors, bathroom mirrors, vanity mirrors, refrigerator doors, aircraft and car windshields, car reflectors, interior mirrors, etc.;

(3) Coating the reversible super-amphiphilic thin film material on the glass and mirror surface to form a reversible super-amphiphilic thin film, which can prevent the formation of water droplets on the glass and mirror surface. It can be used for surface modification of roadside reflectors, aircraft and car windshields, preventing the formation of water droplets on the surface of these modified objects, and improving light transmission;

(4) Lubrication and drag reduction. Applying the reversible super-amphiphilic thin film to the bearing surface modification of precision instruments can make the lubricating oil spread highly on the bearing surface and greatly improve the lubrication efficiency.

(5) Modification of column chromatography filler. Since the super-amphiphilicity of the film of the present invention can be induced by an external field to rapidly lose the super-amphipathic function, the interface material with the super-amphiphilic effect-modified column chromatography filler can be used for efficient organic synthesis separation, biochemical separation, and After separation, an external field is used to induce the modified filler to lose its super-amphiphilic effect, and the adsorbed component is quickly resolved from the surface of the filler.

The reversible super-amphiphilic film of the present invention has the following advantages and effects:

(1) Due to the uniform dispersion of nanoparticles in the sol used in the present invention, there is no agglomeration; in the preparation method, various metal oxides are all made by the sol-gel method, which avoids directly adding metal oxide nanoparticles in the titanium sol. particles, avoiding the agglomeration of nanoparticles. Therefore, the transparent sol used in the present invention can maintain no deterioration and no sedimentation for more than half a year under airtight conditions, and can be taken at any time to prepare a reversible super-amphiphilic film.

(2) The particle size of the metal oxide forming the reversible super-amphiphilic film is uniform, and the flatness of the film is good. Figure 1 is an AFM image of the surface morphology of the reversible super-amphiphilic film prepared in Example 1 of the present invention. It can be seen from the figure that the film is composed of spherical particles with a particle size of 50-80nm, and the surface of the film has little fluctuation.

(3) The anti-fog effect is good. Coat half of a piece of glass with the prepared reversible super-amphiphilic film material to form a reversible super-amphiphilic film, put the glass in hot steam, and observe that the half coated with the reversible super-amphiphilic film material Can maintain good transparency. The other half, which was not painted, soon became foggy, making it impossible to see the image on the back of the glass. Fig. 2 is the anti-fog effect of Example 8 of the present invention having a reversible super-amphiphilic film formed on half a piece of glass.

(4) It has self-cleaning effect. The reversible super-amphiphilic thin film material of Example 20 of the present invention is coated on building exterior wall tiles to form a reversible super-amphiphilic thin film. Since the reversible super-amphiphilic film on the surface of the exterior wall tile is induced by sunlight, that is, simultaneously induced by ultraviolet light and visible light, the super-amphiphilicity of the surface of the exterior wall tile can be maintained for a long time. The rainwater is completely spread on the surface, and the dust and other pollutants adhering to the surface of the outer wall can be washed away by the rainwater to achieve a good self-cleaning effect.

(5) Good transparency. Fig. 3 is the transmission spectrum test of the reversible super-amphiphilic film prepared in Example 29 of the present invention. The results show that, in the visible light region (300-1100nm), the transmittance of the film with the reversible super-amphiphilic film on the front and back made by the dip-coating method is greater than 75%. %. In practical applications, only a single layer of film is often required, so its transmittance will be further improved. This kind of good transparency is completely suitable for anti-fog of transparent materials.

(6) There are various methods of induction and excitation, and there are many applicable occasions, and the time required for external field induction is very short. The thin film prepared by the present invention can be induced and excited in various ways after the surface contact angle is gradually increased. According to different induction modes, it can achieve a very good super-amphiphilic effect within 10 minutes to 5 hours.

(7) The performance is stable, and the super-amphipathic effect lasts for a long time. Table 1 and Figure 4 are the surface water and oil contact angle changes of the reversible super-amphiphilic film prepared in Example 6 of the present invention stored in the dark (the contact angle measurement accuracy of the present invention is ±1°). As can be seen from Table 1 and Figure 4, when the ultra-amphiphilic film of the present invention is stored in a dark place within 30 days, the contact angle of water and oil on it can be maintained at 0°, and the anti-fog and self-cleaning effects are good. When it is stored in a dark place for 31-50 days, but the contact angle of water on it gradually rises to 1-4°, and the anti-fog and self-cleaning effects decrease. The contact angle of oil on its surface is all reduced to 0°. When the storage time in the dark continues to prolong, the contact angle of water on it will gradually increase. When the storage time in the dark reaches 90 days, the contact angle of the amphiphile surface can rise to 32-36°. However, the surface of the amphiphilic film can quickly recover to the super-amphiphilic effect within 10 minutes to 5 hours after being induced and excited by an external field.

(8) The rapid reversibility of the contact angle change on the superamphiphilic film surface is controllable by an external field. The present invention can induce the peculiar super-amphiphilic effect with various external fields, and at the same time, can induce the super-amphiphilic effect to disappear rapidly by other external fields. This feature facilitates adsorption and desorption in separation operations. The external field that can eliminate the super-amphiphilic effect is ultrasonic or weak acid environment (pH=4-6). Figure 5(a) shows the rapid and reversible change of the surface contact angle of the super-amphiphilic film of Example 40 of the present invention under the alternating induction of ultrasonic waves and ultraviolet light. Ultrasonic treatment for 30 minutes can increase the contact angle of water from zero to 18-20°, and at this time, irradiating with ultraviolet light for 30 minutes can quickly return the contact angle of water to 0°. Similarly, Fig. 5(b) shows that the super-amphiphilic film of Example 45 of the present invention is induced by alternating weak acid at pH=4 and heating at 300°C, and the contact angle of water also changes reversibly. Therefore, the superamphiphilic interface material of the present invention can be used in the occasion of adsorption and analysis reversible operation.

(9) The reversible super-amphiphilic film prepared by the present invention has a high heat treatment temperature and is more suitable for the existing glass production process.

Description of drawings

The technical solutions of the present invention will be further described below in conjunction with the drawings and embodiments.

Fig. 1. has the AFM image of the super-amphiphilic film surface topography of reversibility of the present invention;

Fig. 2. the anti-fog effect that the reversible super amphiphilic thin film of the present invention is coated on the half piece of glass;

Fig. 3. the transmission spectrum of the super amphiphilic film with reversibility of the present invention;

Fig. 4. the change of the surface water contact angle of the reversible super amphiphilic thin film of the present invention preserved in a dark place;

●water, n-hexadecane

Fig. 5. the reversibility of the contact angle of the super amphiphilic film water with reversibility of the present invention;

(a) The reversible change of the water contact angle of the ultra-amphiphilic film under the alternating induction of ultrasonic and ultraviolet light,

(b) The reversible change of the water contact angle of the superamphiphile film is induced by alternating weak acid at pH = 4 and heating at 300 °C.

Detailed ways

Example 1.

(1) At room temperature, 1.6 mol of tetrabutyl titanate, 0.1 mol of tin tetrachloride, 0.2 mol of zinc chloride, and 0.1 mol of tungsten hexachloride (at this moment, tetrabutyl titanate accounts for 80% of the total metal salt ), joined in the ethanol solvent of 97.3mol, after the metal salt was dispersed evenly with ultrasonic waves, a transparent sol was obtained;

(2) Add 0.1 mol of stabilizer glycerin to the obtained transparent sol, slowly add 35% of 0.06 mol concentrated hydrochloric acid catalyst dropwise under strong stirring, and continue stirring for about 0.1 hour to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Spin-coat the above-mentioned transparent sol on a glass sheet to make a film, dry it at room temperature, place it in a muffler furnace at 550° C., and keep it warm for 1.5 hours to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by irradiating the transparent film with an ultraviolet lamp for 0.5 hour.

When the reversible super-amphiphilic film is stored in a dark place, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

The reversible super-amphiphilic film was observed under an atomic force microscope, and the surface morphology shown in Figure 1 was obtained.

Example 2.

(1) At room temperature, add 9 mol of tetrabutyl titanate, 0.7 mol of zinc acetate, 0.2 mol of strontium dichloride hexahydrate, and 0.1 mol of ammonium molybdate (at this time, tetrabutyl titanate accounts for 90% of the total metal salt) , was added to 88.1mol of acetone solvent, and the metal salt was uniformly dispersed by ultrasonic waves to obtain a transparent sol;

(2) Add 1.8 mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 0.1 mol of acetic acid catalyst dropwise under strong stirring, and continue to stir for about 0.5 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 4 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a thin film, and after drying at room temperature, it is placed in a muffler furnace at 600° C. and kept for 0.3 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with a 532nm laser for 20 minutes.

When the reversible super-amphiphilic film is stored in a dark place, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 3.

(1) At room temperature, add 27.71 mol of tetrabutyl titanate, 2 mol of tin acetate, 1 mol of basic aluminum acetate dihydrate, 0.89 mol of ammonium molybdate, and 1 mol of niobium pentachloride (at this time, tetrabutyl titanate accounts for the total amount of metal salt) 85% of the amount), was added in the ethanol solvent of 60.4mol, and after the metal salt was dispersed uniformly by ultrasonic waves, a transparent sol was obtained;

(2)) Add 5.4mol of 1,3-propanediol stabilizer to the obtained transparent sol, slowly add 35% of 1.63mol of concentrated hydrochloric acid catalyst dropwise under vigorous stirring, and continue stirring for about 1 hour to form a partially hydrolyzed mixtures of metal salts;

(3) aging the above mixture for 3.5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, and after drying at room temperature, it is placed in a muffler furnace at 600° C. and kept for 0.2 hours to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by irradiating the transparent film with visible light of 400-500 nm for 4 hours.

When the reversible super-amphiphilic film is stored in a dark place, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 4.

(1) At room temperature, add 3.2 mol of tetrabutyl titanate, 0.6 mol of zinc nitrate hexahydrate, and 0.2 mol of tungsten dichloride (at this time, tetrabutyl titanate accounts for 80% of the total amount of metal salts), add to 95.02 mol n-hexane solvent, after the metal salt is uniformly dispersed by ultrasonic waves, a transparent sol is obtained;

(2) Add 0.9 mol of diethylene glycol stabilizer to the obtained transparent sol, slowly add 0.08 mol of concentrated nitric acid catalyst dropwise under strong stirring, and continue stirring for about 1.5 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 650° C., and kept warm for 0.05 hours to obtain a transparent film;

(5) Excite the transparent film with plasma for 10 minutes to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in a dark place, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 5.

(1) At room temperature, mix 14.58mol of tetrabutyl titanate, 2.42mol of zinc carbonate, 0.2mol of aluminum isopropoxide, and 0.8mol of indium trichloride (at this time, tetrabutyl titanate accounts for 81% of the total metal salt ), joined in the benzene solvent of 80.6mol, after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.7 mol of glycerin stabilizer to the obtained transparent sol, slowly add 0.72 mol of sulfuric acid catalyst dropwise under strong stirring, and continue stirring for about 4 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 3.5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 550° C., and kept warm for 0.6 hours to obtain a transparent film;

(5) Excite the transparent film with plasma for 10 minutes to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in a dark place, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 6.

(1) At room temperature, mix 20.47 mol of tetraethyl titanate, 0.53 mol of tungsten dichloride, 1 mol of strontium carbonate, 0.5 mol of tetrachlorosilane, and 0.5 mol of zirconium tetrachloride (at this time, tetraethyl titanate occupies the metal salt 89% of the total amount), was added in the ethanol solvent of 73.0mol, and after the metal salt was dispersed uniformly by ultrasonic waves, a transparent sol was obtained;

(2) The ethylene glycol stabilizer of 3.1mol is joined in the transparent sol that obtains, and the 0.81mol concentrated hydrochloric acid catalyst of 35% is slowly added dropwise under strong stirring, continues to stir about 8 hours, generates the metal salt that contains part hydrolysis mixture;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 650°C, and kept warm for 0.1 hour to obtain a transparent film;

(5) Excite the transparent film with plasma for 20 minutes to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in a dark place, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

The film was placed in the dark for 90 days, and the tracking test results of the changes in the contact angles of water and oil on its surface are shown in Table 1.

Example 7.

(1) At room temperature, add 2.46mol of tetraethyl titanate, 0.04mol of tungsten hexachloride, 0.2mol of strontium dichloride hexahydrate, and 0.3mol of niobium pentachloride (at this time, tetraethyl titanate accounts for the total amount of metal salts) 82%), join in the carbon tetrachloride solvent of 96.4mol, after metal salt is dispersed evenly with ultrasonic wave, obtain transparent sol;

(2) The triethylene glycol stabilizer of 0.5mol is joined in the transparent sol that obtains, and the 0.12mol concentrated hydrochloric acid catalyst of 35% is slowly added dropwise under vigorous stirring, continues to stir for about 2.5 hours, generates and contains partially hydrolyzed Mixtures of metal salts;

(3) aging the above mixture for 6 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on an aluminum sheet to make a film, and after drying at room temperature, place it in a muffler furnace at 650° C., and keep it warm for 0.05 hours to obtain a transparent film;

(5) Excite the transparent film with plasma for 0.5 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 8.

(1) At room temperature, mix 5.67 mol of tetraethyl titanate, 0.8 mol of zinc carbonate, 0.03 mol of basic aluminum acetate dihydrate, 0.2 mol of indium nitrate pentahydrate, and 0.3 mol of ammonium molybdate (at this time tetraethyl titanate accounts for 81% of the total amount of the metal salt), was added in the isopropanol solvent of 91.3mol, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 1.5 mol of glycerin stabilizer to the obtained transparent sol, slowly add 0.18 mol of concentrated sulfuric acid catalyst dropwise under strong stirring, and continue stirring for about 7 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is sprayed on half a piece of glass to make a film, and after drying at room temperature, it is placed in a muffler furnace at 600° C. and kept for 0.5 hours to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by irradiating the transparent film with a 1064 nm laser for 0.5 hour.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Putting the reversible film in a hot steam atmosphere can have an obvious anti-fog effect, as shown in Figure 2.

Example 9.

(1) At room temperature, mix 9.96 mol of tetraethyl titanate, 0.04 mol of tungsten dichloride, 1 mol of strontium dichloride hexahydrate, 0.7 mol of niobium pentachloride, and 0.3 mol of zirconium nitrate pentahydrate (at this time titanate Tetraethyl ester accounts for 83% of metal salt total amount), joins in the propanol solvent of 85.6mol, after metal salt is dispersed evenly with ultrasonic wave, obtains transparent sol;

(2) Add 1.9 mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 0.54 mol of acetic acid catalyst dropwise under strong stirring, and continue to stir for about 6.5 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 3.5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Dip-coat the above-mentioned transparent sol on the lens to make a film, dry it at room temperature, place it in a muffle furnace at 550°C, and keep it warm for 0.1 hour to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with ultraviolet light for 1 hour.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Lenses coated with a reversible super-amphiphilic film can maintain a good anti-fog effect when placed in the bathroom.

Example 10.

(1) At room temperature, add 29.4 mol of tetraethyl titanate, 0.2 mol of zinc acetate, 0.1 mol of ammonium molybdate, and 0.3 mol of tetrabutyl silicate (at this time, tetraethyl titanate accounts for 98% of the total metal salt) , was added to 63.5mol ethanol solvent, and the metal salt was uniformly dispersed by ultrasonic waves to obtain a transparent sol;

(2) Add 5.0 mol of diethylene glycol stabilizer to the obtained transparent sol, slowly add 35% of 1.5 mol of concentrated hydrochloric acid catalyst dropwise under strong stirring, continue to stir for about 4 hours, and generate a compound containing partially hydrolyzed a mixture of metal salts;

(3) aging the above mixture for 4 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Dip-coat the above-mentioned transparent sol on a porcelain bowl to form a film, dry it at room temperature, place it in a muffle furnace at 720°C, and keep it warm for 1 hour to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by treating the transparent film with microwave for 25 minutes.

The reversible super-amphiphilic film has a unique self-cleaning effect. Rinse the porcelain bowl coated with a reversible super-amphiphilic film to remove grease stains after eating.

Example 11.

At room temperature, 15.2 mol of tetraisopropyl titanate, 0.1 mol of tin tetrachloride, 0.1 mol of tungsten dichloride, 0.2 mol of basic aluminum acetate dihydrate, 0.3 mol of strontium carbonate, and 0.1 mol of indium trichloride ( At this time, tetraisopropyl titanate accounts for 95% of the total amount of the metal salt), was added to 82.7 mol of ethanol solvent, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.8mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 0.51mol of concentrated sulfuric acid catalyst dropwise under strong stirring, and continue to stir for about 4.5 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a stainless steel sheet to form a film, and after drying at room temperature, it is placed in a muffler furnace at 700° C. and kept for 0.05 hours to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by irradiating the transparent film with sunlight for 0.5 hour.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Putting the stainless steel sheet coated with a reversible super-amphiphilic film outdoors can maintain a good self-cleaning effect, and the dust and other pollutants adhering to the surface can be washed away by rainwater.

Example 12.

At room temperature, 23 mol of tetraisopropyl titanate, tetra(2-ethylhexyl) titanate, 1 mol of zinc nitrate hexahydrate, 0.2 mol of tungsten hexachloride, 0.2 mol of ammonium molybdate, and 0.6 mol of tetrabromosilane ( At this time, tetraisopropyl titanate accounted for 92% of the total amount of the metal salt), was added to 69.7 mol of acetone solvent, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 4.8mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 0.48mol of concentrated ammonia catalyst dropwise under strong stirring, and continue to stir for about 3 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 5.5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a ceramic sheet to form a film, dried at room temperature, placed in a muffle furnace at 720°C, and kept warm for 0.05 hours to obtain a transparent film;

(5) The transparent film is irradiated with 400-500nm visible light for 2 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Placing the ceramic sheet coated with a reversible super-amphiphilic film outdoors can maintain a good self-cleaning effect, and the dust and other pollutants adhering to the surface can be washed away by rainwater.

Example 13.

At room temperature, mix 2.35 mol of tetraisopropyl titanate, 0.02 mol of tin acetate, 0.07 mol of aluminum isopropoxide, 0.01 mol of indium acetate, and 0.05 mol of niobium pentachloride (at this time, tetraisopropyl titanate occupies the metal salt 94% of the total amount), joined in the isopropanol solvent of 96.8mol, after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.6 mol of triethylene glycol stabilizer to the obtained transparent sol, slowly add 0.1 mol of concentrated sulfuric acid catalyst dropwise under strong stirring, and continue stirring for about 5 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 4 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 550°C, and kept warm for 1 hour to obtain a transparent film;

(5) After irradiating the transparent film with ultraviolet light for 2 hours, a reversible super-amphiphilic film can be obtained.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

The reversible super-amphiphilic film in the initial state is alternately induced by placing it in a weakly acidic environment (pH=4.8) and in a microwave oven, and the contact angle of water on its surface can be rapidly and reversibly changed between 45° and 0°. That is, in step (6), when the reversible super-amphiphilic film is placed in a weakly acidic environment (pH=4.8) for 30 minutes, the contact angle of water becomes 45°; and then it is treated with microwaves for 30 minutes, and the water The contact angle becomes 0° again.

Example 14.

At room temperature, mix 5.16 mol of tetraisopropyl titanate, 0.5 mol of tin acetate, 0.04 mol of tungsten dichloride, 0.2 mol of strontium carbonate, and 0.1 mol of ammonium molybdate (at this time, tetraisopropyl titanate accounts for the total amount of metal salt) 86% of the amount), was added in the isopropanol solvent of 92.5mol, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 1.2 mol of glycerin stabilizer to the obtained transparent sol, slowly add 0.29 mol of concentrated sulfuric acid catalyst dropwise under strong stirring, and continue stirring for about 1.5 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 6 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 580°C, and kept warm for 0.5 hours to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by irradiating the transparent film with a 514nm laser for 20 minutes.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

The glass sheet coated with the reversible superamphiphilic film was placed outdoors, and no water droplets formed on the surface in rainy weather.

Example 15.

At room temperature, mix 7.44mol of tetraisopropyl titanate, 0.4mol of zinc carbonate, 0.04mol of tungsten hexachloride, 0.09mol of indium nitrate pentahydrate, and 0.03mol of zirconium hypochlorite (at this time tetraisopropyl titanate occupies the metal 93% of the total amount of salt), was added in the chloroform solvent of 90.3mol, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 1.4 mol of glycerin stabilizer to the obtained transparent sol, slowly add 0.27 mol of concentrated nitric acid catalyst dropwise under strong stirring, and continue stirring for about 2 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 560°C, and kept for 1 hour to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with ultraviolet light for 2 hours.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 16.

At room temperature, 29.76 mol of tetra(2-ethylhexyl) titanate, 1 mol of tin acetate, 0.04 mol of ammonium molybdate, 0.1 mol of niobium pentachloride, and 0.1 mol of tetraethyl silicate (at this time tetra(titanate) 2-Ethylhexyl) ester accounts for 96% of the total amount of metal salt), was added in the n-hexane solvent of 62.6mol, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 6.0 mol of diethylene glycol stabilizer to the obtained transparent sol, slowly add 0.37 mol of concentrated ammonia catalyst dropwise under strong stirring, and continue stirring for about 4 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Dip-coat the above-mentioned transparent sol on a ceramic sheet to make a film, dry it at room temperature, place it in a muffle furnace at 620° C., and keep it warm for 0.08 hours to obtain a transparent film;

(5) Excite the transparent film with plasma for 20 minutes to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Placing the ceramic sheet coated with a reversible super-amphiphilic film outdoors can maintain a good self-cleaning effect, and the dust and other pollutants adhering to the surface can be washed away by rainwater.

Example 17.

At room temperature, 20.16 mol of tetra(2-ethylhexyl) titanate, 2 mol of zinc acetate, 0.04 mol of tungsten hexachloride, 0.8 mol of strontium dichloride hexahydrate, 1 mol of tetrabutyl silicate (at this time titanate Tetra(2-ethylhexyl) ester accounts for 84% of the metal salt total amount), joins in the carbon tetrachloride solvent of 69.6mol, after metal salt is dispersed evenly with ultrasonic wave, obtains transparent sol;

(2) Add 5.3 mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 35% 1.06 mol of concentrated hydrochloric acid catalyst dropwise under strong stirring, and continue stirring for about 6 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 4 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Spray the above-mentioned transparent sol on a glass sheet to make a film, dry it at room temperature, place it in a muffler furnace at 600°C, and keep it warm for 0.1 hour to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by bombarding the transparent film with argon ions for 20 minutes.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 18.

At room temperature, 13.05 mol of tetra(2-ethylhexyl) titanate, 0.05 mol of tungsten dichloride, 0.9 mol of niobium pentachloride, 0.5 mol of dimethoxydiethoxysilane, zirconium hypochlorite 0.5 mol (at this time, tetra(2-ethylhexyl) titanate accounts for 87% of the total amount of the metal salt), was added to 82.5 mol of acetone solvent, and after the metal salt was uniformly dispersed by ultrasonic waves, a transparent sol was obtained;

(2) Add 5.3 mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 35% of 0.39 mol concentrated hydrochloric acid catalyst dropwise under strong stirring, and continue stirring for about 2 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, and after drying at room temperature, it is placed in a muffler furnace at 630° C. and kept for 0.05 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with sunlight for 2 hours.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 19.

At room temperature, add 4.75 mol of tetra(2-ethylhexyl) titanate, 0.1 mol of zinc nitrate hexahydrate, 0.05 mol of tungsten dichloride, 0.04 mol of anhydrous aluminum chloride, and 0.06 mol of strontium dichloride hexahydrate (Tetra(2-ethylhexyl) titanate accounts for 95% of the total amount of the metal salt at this time), adding it to 93.3 mol of benzene solvent, and dispersing the metal salt evenly with ultrasonic waves to obtain a transparent sol;

(2) Add 1.5 mol of diethylene glycol stabilizer to the obtained transparent sol, slowly add 0.18 mol of concentrated sulfuric acid catalyst dropwise under strong stirring, and continue stirring for about 2 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Dip-coat the above-mentioned transparent sol on a glass sheet to form a film, dry it at room temperature, place it in a muffle furnace at 670° C., and keep it warm for 0.05 hours to obtain a transparent film;

(5) The transparent film is irradiated with 400-500nm visible light for 5 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 20.

At room temperature, 8.9 mol of tetra(2-ethylhexyl) titanate, 0.6 mol of tin tetrachloride, 0.1 mol of anhydrous aluminum chloride, strontium dichloride hexahydrate, 0.3 mol of strontium carbonate, and indium nitrate pentahydrate 0.1 mol (at this time, tetra(2-ethylhexyl) titanate accounts for 89% of the total amount of the metal salt), was added to 86.4 mol of toluene solvent, and after the metal salt was uniformly dispersed by ultrasonic waves, a transparent sol was obtained;

(2) Add 3.2 mol of diethylene glycol stabilizer to the obtained transparent sol, slowly add 0.37 mol of concentrated ammonia catalyst dropwise under strong stirring, and continue stirring for about 6 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 8 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Spray the above-mentioned transparent sol on the ceramic tiles that decorate the exterior wall of the building to make a film. After drying at room temperature, place it in a muffle furnace at 720° C. and keep it warm for 0.2 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with sunlight for 3 hours.

When the reversible super-amphiphilic film is placed in a sunny outdoor environment, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 90 days. Since the contact angle of water on the modified surface tends to be zero, the rainwater can be completely spread on the surface, and the dust and other pollutants adhering to the surface of the outer wall can be washed away by the rainwater to achieve a good self-cleaning effect.

Example 21.

At room temperature, 13.2 mol of tetra(heptadecane) titanate, 1 mol of zinc nitrate hexahydrate, 0.5 mol of niobium pentachloride, 0.3 mol of dimethyldichlorosilane, and 0.1 mol of zirconium hypochlorite (at this time, (17) ester accounts for 88% of metal salt total amount), joins in the carbon tetrachloride solvent of 97.3mol, after metal salt is dispersed evenly with ultrasonic wave, obtains transparent sol;

(2) 1.7mol of 1,3-propanediol stabilizer was added to the obtained transparent sol, and 35% of 0.63mol concentrated hydrochloric acid catalyst was slowly added dropwise under vigorous stirring, and the stirring was continued for about 4.5 hours to generate a partially hydrolyzed Mixtures of metal salts;

(3) aging the above mixture for 4 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Spray the above-mentioned transparent sol on a glass sheet to make a film, dry it at room temperature, place it in a muffler furnace at 550°C, and keep it warm for 1 hour to obtain a transparent film;

(5) Excite the transparent film with plasma for 10 minutes to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

The glass sheet coated with the reversible superamphiphilic film was placed outdoors, and no water droplets formed on the surface in rainy weather.

Example 22.

At room temperature, 18.8 mol of tetra(heptadecane) titanate, 0.6 mol of aluminum isopropoxide, 0.1 mol of indium acetate, 0.4 mol of ammonium molybdate, and 0.1 mol of zirconium hypochlorite (at this time tetra(heptadecane) titanate ) ester accounts for 94% of the total amount of the metal salt), joins in the propanol solvent of 77.0mol, after the metal salt is dispersed evenly by ultrasonic waves, a transparent sol is obtained;

(2) Add 2.4 mol of glycerin stabilizer to the obtained transparent sol, slowly add 0.56 mol of acetic acid catalyst dropwise under strong stirring, and continue stirring for about 2 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 560°C, and kept for 1.2 hours to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by irradiating the transparent film with a 670nm laser for 10 minutes.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 23.

At room temperature, 27.6 mol of tetra(heptadecane) titanate, 1 mol of zinc chloride, 1 mol of anhydrous aluminum chloride, 0.2 mol of strontium dichloride hexahydrate, and 0.2 mol of indium acetate (at this time tetra(heptadecane) titanate ) ester accounts for 92% of the total amount of metal salt), was added in the isopropanol solvent of 65.6mol, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 4.0 mol of 1,3-propanediol stabilizer to the obtained transparent sol, slowly add 0.45 mol of acetic acid catalyst dropwise under strong stirring, and continue stirring for about 8 hours to generate a mixture containing partially hydrolyzed metal salts ;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a copper sheet to form a thin film, dried at room temperature, placed in a muffler furnace at 650° C., and kept for 0.2 hours to obtain a transparent film;

(5) The transparent film was treated with microwave for 0.5 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Putting the copper sheet coated with a reversible super-amphiphilic film outdoors can maintain a good self-cleaning effect, and the dust and other pollutants adhering to the surface can be washed away by rainwater.

Example 24.

At room temperature, 23.25 mol of tetra(heptadecane) titanate, 0.7 mol of tin tetrachloride, 0.6 mol of zinc chloride, 0.05 mol of tungsten dichloride, and 0.4 mol of anhydrous aluminum chloride (at this time tetratitanate (17) ester accounts for 93% of metal salt total amount), joins in the acetone solvent of 71.6mol, after metal salt is dispersed evenly with ultrasonic wave, obtains transparent sol;

(2) 3.0mol of 1,3-propanediol stabilizer is added to the obtained transparent sol, slowly add 35% of 0.45mol concentrated hydrochloric acid catalyst dropwise under vigorous stirring, and continue to stir for about 2 hours to generate a partially hydrolyzed Mixtures of metal salts;

(3) aging the above mixture for 6 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a ceramic sheet to form a film, dried at room temperature, placed in a muffle furnace at 700°C, and kept for 1.3 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with sunlight for 1 hour.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Placing the ceramic sheet coated with a reversible super-amphiphilic film outdoors can maintain a good self-cleaning effect, and the dust and other pollutants adhering to the surface can be washed away by rainwater.

Example 25.

At room temperature, 3.52 mol of tetra(heptadecane) titanate, 0.2 mol of zinc acetate, 0.06 mol of indium nitrate pentahydrate, 0.02 mol of niobium pentachloride, and 0.2 mol of tetrabutyl silicate (at this time tetra(decyl) titanate 7) The ester accounts for 88% of the total amount of the metal salt), which is added to 95.7mol of ethanol solvent, and after the metal salt is dispersed evenly by ultrasonic waves, a transparent sol is obtained;

(2) Add 0.2mol of triethylene glycol stabilizer to the obtained transparent sol, slowly add 35% of 0.14mol of concentrated hydrochloric acid catalyst dropwise under vigorous stirring, and continue to stir for about 0.5 hours to form a compound containing partially hydrolyzed mixtures of metal salts;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a copper sheet to form a thin film, and after drying at room temperature, it is placed in a muffler furnace at 550° C. and kept for 1.5 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with sunlight for 3 hours.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 26.

At room temperature, 8.1 mol of tetra(heptadecan) titanate, 0.3 mol of tin acetate, 0.2 mol of ammonium molybdate, and 0.4 mol of zirconium nitrate pentahydrate (at this time, tetra(heptadecan) titanate accounts for 90%), joined in the ethanol solvent of 89.8mol, after the metal salt was dispersed uniformly with ultrasonic waves, a transparent sol was obtained;

(2) Add 0.9 mol of glycerin stabilizer to the obtained transparent sol, slowly add 0.27 mol of acetic acid catalyst dropwise under vigorous stirring, and continue stirring for about 2 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a stainless steel sheet to make a film, dried at room temperature, placed in a muffler furnace at 550°C, and kept for 1.5 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with laser light for 2.5 hours.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 27.

At room temperature, diisopropoxy-diacetylacetonate titanium 9.02mol, tin tetrachloride 1mol, tungsten hexachloride 0.48, indium trichloride 0.5mol (at this time diisopropoxy-diacetylacetonate titanium accounted for 82% of the total amount of the metal salt), was added in the propanol solvent of 97.9mol, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.5 mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 0.11 mol of acetic acid catalyst dropwise under strong stirring, and continue stirring for about 2.5 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 600°C, and kept warm for 0.5 hours to obtain a transparent film;

(5) The transparent film was treated with microwave for 0.5 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 28.

At room temperature, diisopropoxy-diacetylacetonate titanium 21.84mol, zinc acetate 3.3mol, tungsten hexachloride 0.86mol (now diisopropoxy-diacetylacetonate titanium accounted for 84% of the metal salt total amount ), join in the propanol solvent of 71.9mol, after metal salt is dispersed evenly with ultrasonic wave, obtain transparent sol;

(2) Add 1.8 mol of triethylene glycol stabilizer to the obtained transparent sol, slowly add 0.31 mol of concentrated sulfuric acid catalyst dropwise under strong stirring, and continue stirring for about 6 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Dip-coat the above-mentioned transparent sol on the lens to make a film, dry it at room temperature, place it in a muffle furnace at 550°C, and keep it warm for 0.5 hours to obtain a transparent film;

(5) The transparent film is irradiated with 400-500nm visible light for 3 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

The lens coated with the reversible super-amphiphilic film is placed outdoors, and no water droplets are formed on the surface in rainy days.

Example 29.

At room temperature, diisopropoxy-diacetylacetonate titanium 29.44mol, ammonium molybdate 0.5mol, tetrabutyl silicate 0.96mol, zirconium hypochlorite 1.1mol (at this time diisopropoxy-diacetylacetonate Titanium accounts for 92% of the total amount of the metal salt), was added to 63.1mol of n-butanol solvent, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 4.1 mol of triethylene glycol stabilizer to the obtained transparent sol, slowly add 0.83 mol of concentrated nitric acid catalyst dropwise under strong stirring, and continue stirring for about 3 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 4.5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Dip-coat the above-mentioned transparent sol on a glass sheet to form a film, dry it at room temperature, place it in a muffle furnace at 550° C., and keep it warm for 1.5 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by microwave treatment of the transparent film for 15 minutes.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

The transparency of the reversible super-amphiphilic film is good, and the glass plate coated with the reversible super-amphiphilic film on both sides has been tested for transmission spectrum. The transmittances are all in the range of 85-90%.

Example 30.

At room temperature, diisopropoxy-diacetylacetonate titanium 13.16mol, anhydrous aluminum chloride 0.2mol, indium acetate 0.1mol (at this time diisopropoxy-diacetylacetonate titanium accounted for 94% of the total metal salt %), was added in the n-butanol solvent of 85.0mol, after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.4mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 0.56mol of concentrated nitric acid catalyst dropwise under strong stirring, continue to stir for about 4 hours, and generate a mixture containing partially hydrolyzed metal salts;

(3) The above mixture was left to age for 3.5 hours to obtain a transparent sol with uniformly dispersed nanoparticles

(4) Dip-coat the above-mentioned transparent sol on a glass sheet to make a film, dry it at room temperature, place it in a muffle furnace at 610° C., and keep it warm for 0.1 hour to obtain a transparent film;

(5) Excite the transparent film with plasma for 0.5 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

The reversible super-amphiphilic film in the initial state is alternately induced by placing it in a weakly acidic environment (pH=6) and ultraviolet light irradiation, and the contact angle of water on its surface can be rapidly reversible between 23° and 0° Variety. That is, step (6), when the reversible super-amphiphilic film is placed in a weakly acidic environment (pH=6) for 30 minutes, the contact angle of water becomes 23°; and then it is irradiated with ultraviolet light for 30 minutes, The contact angle of water becomes 0° again.

Example 31.

At room temperature, diisopropoxy-titanium diacetylacetonate 11.05mol, zinc chloride 1mol, tungsten dichloride 0.05mol, aluminum isopropoxide 0.5mol, strontium carbonate 0.4mol (at this time diisopropoxy Base-titanium diacetylacetonate accounts for 85% of the total amount of the metal salt), was added in the chloroform solvent of 84.7mol, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) 2.0mol of 1,3-propanediol stabilizer is added in the obtained transparent sol, under vigorous stirring, slowly add the concentrated sulfuric acid catalyst of 0.31mol dropwise, continue to stir for about 2.5 hours, generate the metal salt containing part hydrolysis mixture;

(3) aging the above mixture for 5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on an aluminum sheet to form a thin film, and after drying at room temperature, it is placed in a muffler furnace at 550° C. and kept for 0.1 hour to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by irradiating the transparent film with ultraviolet light for 0.5 hour.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Putting the aluminum sheet coated with a reversible super-amphiphilic film outdoors can maintain a good self-cleaning effect, and the dust and other pollutants adhering to the surface can be washed away by rainwater.

Example 32.

At room temperature, 25.81mol of diisopropoxy-diacetylacetonate titanium, 0.29mol of tungsten hexachloride, 0.2mol of indium nitrate pentahydrate, 0.5mol of niobium pentachloride, and 2.2mol of zirconium hypochlorite (at this time diiso Propoxy-titanium diacetylacetonate accounts for 89% of the total amount of the metal salt), was added to 69.1mol of benzene solvent, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) The 1,3-propanediol stabilizer of 1.4mol is joined in the transparent sol that obtains, and the concentrated sulfuric acid catalyst of 0.52mol is slowly added dropwise under strong stirring, continues to stir about 3 hours, generates the metal salt containing part hydrolysis mixture;

(3) aging the above mixture for 4 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is sprayed on a glass sheet to make a film, and after drying at room temperature, it is placed in a muffler furnace at 550° C. and kept for 0.8 hours to obtain a transparent film;

(5) Excite the transparent film with plasma for 0.5 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 33.

At room temperature, di-n-butoxy-bis(triethanolamine) titanium 5.4mol, tin acetate 0.3mol, ammonium molybdate 0.1mol, tetrachlorosilane 0.2mol (at this time di-n-butoxy-bis(triethanolamine) Titanium accounts for 90% of the total amount of the metal salt), was added to 93.2mol of chloroform solvent, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.7 mol of 1,3-propanediol stabilizer to the obtained transparent sol, slowly add 0.12 mol of acetic acid catalyst dropwise under strong stirring, and continue stirring for about 1.5 hours to generate a mixture containing partially hydrolyzed metal salts ;

(3) aging the above mixture for 5.5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Dip-coat the above-mentioned transparent sol on a glass sheet to make a film, dry it at room temperature, place it in a muffle furnace at 600°C, and keep it warm for 0.2 hours to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by treating the transparent film with microwave for 10 minutes.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 34.

At room temperature, 26.46mol of di-n-butoxy-bis(triethanolamine)titanium, 0.2mol of zinc chloride, 0.2mol of basic aluminum acetate dihydrate, 0.1mol of indium nitrate pentahydrate, and 0.04mol of ammonium molybdate (at this time Di-n-butoxy-two (triethanolamine) titanium accounts for 98% of the total amount of the metal salt), joins in the carbon tetrachloride solvent of 71.3mol, and after the metal salt is dispersed evenly by ultrasonic waves, a transparent sol is obtained;

(2) The diethylene glycol stabilizer of 1.3mol is joined in the obtained transparent sol, the acetic acid catalyst of 0.38mol is slowly added dropwise under vigorous stirring, continues to stir for about 3.0 hours, generates the metal salt containing part hydrolysis mixture;

(3) The above mixture was aged for 1.5 hours to obtain a transparent sol with uniformly dispersed nanoparticles.

(4) The above-mentioned transparent sol is spin-coated on an aluminum sheet to form a thin film, and after drying at room temperature, it is placed in a muffler furnace at 550° C. and kept for 0.5 hours to obtain a transparent film;

(5) The transparent film is irradiated with 400-500nm visible light for 3 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 35.

At room temperature, di-n-butoxy-bis(triethanolamine)titanium 21.84mol, tin acetate 1.8mol, indium trichloride 0.2mol, ammonium molybdate 0.16mol (at this time di-n-butoxybis(triethanolamine) Titanium accounts for 91% of the metal salt total amount), joins in the carbon tetrachloride solvent of 74.0mol, after metal salt is dispersed evenly with ultrasonic wave, obtains transparent sol;

(2) Add 1.5 mol of diethylene glycol stabilizer to the obtained transparent sol, slowly add 35% of 0.48 mol of concentrated hydrochloric acid catalyst dropwise under strong stirring, and continue stirring for about 3 hours to form a compound containing partially hydrolyzed a mixture of metal salts;

(3) aging the above mixture for 6 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 600°C, and kept warm for 0.5 hours to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by irradiating the transparent film with a 735nm laser for 25 minutes.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 36.

At room temperature, 11.57 mol of di-n-butoxy-bis(triethanolamine) titanium, 0.7 mol of zinc nitrate hexahydrate, 0.23 mol of tungsten dioxide dichloride, 0.2 mol of indium trichloride, and 0.3 mol of zirconium tetrachloride (the Di-n-butoxyl-bis(triethanolamine)titanium accounts for 89% of the total amount of the metal salt), was added in the acetone solvent of 86.0mol, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.8 mol of glycerin stabilizer to the obtained transparent sol, slowly add 0.2 mol of concentrated sulfuric acid catalyst dropwise under strong stirring, and continue stirring for about 4.5 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) Spray the above-mentioned transparent sol on an aluminum sheet to make a film, dry it at room temperature, place it in a muffler furnace at 600°C, and keep it warm for 0.1 hour to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with sunlight for 3 hours.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 37.

At room temperature, 16.49 mol of di-n-butoxy-bis(triethanolamine) titanium, 0.2 mol of zinc chloride, 0.11 mol of strontium dichloride hexahydrate, 0.2 mol of tetrabromosilane (at this time di-n-butoxy-di (Triethanolamine) titanium accounts for 97% of the total amount of metal salt), joins in the benzene solvent of 82.1mol, after the metal salt is dispersed evenly with ultrasonic wave, obtains transparent sol;

(2) Add 0.7 mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 0.2 mol of acetic acid catalyst dropwise under strong stirring, and continue stirring for about 2 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 5.5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on the lens to form a film, and after drying at room temperature, it is placed in a muffler furnace at 550° C. and kept for 1 hour to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by bombarding the transparent film with argon ions for 10 minutes.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Lenses coated with a reversible super-amphiphilic film can maintain a good anti-fog effect when placed in the bathroom.

Example 38.

At room temperature, 10.08 mol of di-n-butoxy-bis(triethanolamine) titanium, 1 mol of tin tetrachloride, 0.12 mol of tungsten dichloride, 0.5 mol of strontium carbonate, and 0.4 mol of niobium pentachloride (at this time, Butoxyl-bis(triethanolamine)titanium accounts for 84% of the total amount of the metal salt), was added to 87.2mol of ethanol solvent, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.6mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 0.06mol of acetic acid catalyst dropwise under strong stirring, continue to stir for about 1.2 hours, and generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 5.5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is sprayed on ceramic tiles to form a film, and after drying at room temperature, it is placed in a muffler furnace at 610° C. and kept for 1 hour to obtain a transparent film;

(5) Excite the transparent film with plasma for 20 minutes to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 39.

At room temperature, 24.08 mol of titanium dihydroxy-dilactate, 2 mol of zinc acetate, 0.2 mol of indium nitrate pentahydrate, 0.22 mol of ammonium molybdate, and 1.5 mol of tetrabromosilane were used as main raw materials (at this time, titanium dihydroxy-dilactate accounted for 86% of the total amount of the metal salt), was added in the ethanol solvent of 69.2mol, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 2.2mol of 1,3-propanediol stabilizer to the obtained transparent sol, slowly add 35% of 0.644mol of acetic acid catalyst dropwise under strong stirring, and continue to stir for about 2.5 hours to generate partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 5.5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on the lens to form a film, dried at room temperature, placed in a muffler furnace at 610°C, and kept warm for 0.05 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with sunlight for 1 hour.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 40.

At room temperature, 12.48 mol of dihydroxy-dilactate titanium, 0.2 mol of tin acetate, 0.3 mol of zinc carbonate, and 0.12 mol of tungsten hexachloride (at this time, dihydroxy-dilactate titanium accounted for 96% of the total amount of the metal salt), added In 85.9mol of carbon tetrachloride solvent, after the metal salt is uniformly dispersed by ultrasonic waves, a transparent sol is obtained;

(2) Add 1.0 mol of diethylene glycol stabilizer to the obtained transparent sol, slowly add 0.13 mol of concentrated ammonia catalyst dropwise under strong stirring, and continue stirring for about 4.5 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 590° C., and kept warm for 0.8 hours to obtain a transparent film;

(5) The reversible super-amphiphilic film can be obtained by irradiating the transparent film with 810 nm laser for 10 minutes.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

The reversible super-amphiphilic thin film in the initial state is irradiated alternately with ultrasound and ultraviolet light, and the contact angle of water on its surface can be changed rapidly and reversibly. That is, step (6), ultrasonic treatment for 30 minutes can increase the contact angle of water from 0° to 18-20°; and at this time, irradiating with ultraviolet light for 30 minutes can quickly return the water contact angle to 0°.

Example 41.

At room temperature, 15.2 mol of dihydroxy-titanium dilactate, 0.4 mol of zinc nitrate hexahydrate, 0.08 mol of tungsten dichloride, 0.12 mol of strontium dichloride hexahydrate, and 0.2 mol of tetraethyl silicate (at this time dihydroxy -titanium dilactate accounts for 95% of the total amount of the metal salt), was added to 82.4mol of acetone solvent, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 1.4mol of diethylene glycol stabilizer to the obtained transparent sol, slowly add 35% of 0.22mol of concentrated hydrochloric acid catalyst dropwise under strong stirring, and continue to stir for about 3 hours to form a compound containing partially hydrolyzed a mixture of metal salts;

(3) aging the above mixture for 6 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 550° C., and kept for 1.5 hours to obtain a transparent film;

(5) The transparent film was irradiated with visible light for 3.5 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 42.

At room temperature, mix 8.3 mol of dihydroxy-titanium dilactate, 0.2 mol of zinc chloride, 0.2 mol of tungsten hexachloride, 0.1 mol of niobium pentachloride, 1 mol of tetrabromosilane, and 0.2 mol of zirconium nitrate pentahydrate (at this time, dihydroxy -titanium dilactate accounts for 83% of the total amount of the metal salt), was added to 89.7mol of ethanol solvent, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.3mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 35% of 0.01mol concentrated hydrochloric acid catalyst dropwise under strong stirring, and continue stirring for about 2.5 hours to generate a partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 4.5 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a copper sheet to form a thin film, and after drying at room temperature, it is placed in a muffler furnace at 620° C. and kept for 0.2 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with an 810 nm laser for 15 minutes.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 43.

At room temperature, mix 9.57 mol of dihydroxy-dilactate titanium, 1 mol of zinc nitrate hexahydrate, 0.2 mol of basic aluminum acetate dihydrate, 0.1 mol of indium nitrate pentahydrate, and 0.13 mol of ammonium molybdate (at this time, dihydroxy-dilactate titanium accounted for 87% of the total amount of metal salts), was added to 88.6mol of propanol solvent, and after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.2mol of ethylene glycol stabilizer to the obtained transparent sol, slowly add 0.19mol of concentrated sulfuric acid catalyst dropwise under strong stirring, continue to stir for about 4 hours, and generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 2.5 hours to obtain a transparent sol with uniformly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 600°C, and kept warm for 0.5 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with sunlight for 1.5 hours.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 44.

At room temperature, 12.75 mol of titanium tetraoctene glycolate, 0.05 mol of tungsten dichloride, 0.2 mol of strontium dichloride hexahydrate, and 2 mol of dimethyldichlorosilane (at this time, titanium tetraoctene glycolate occupies the metal salt 85% of the total amount), joined in the propanol solvent of 84.3mol, after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.5 mol of glycerin stabilizer to the obtained transparent sol, slowly add 0.24 mol of acetic acid catalyst dropwise under strong stirring, and continue stirring for about 3 hours to generate a mixture containing partially hydrolyzed metal salts;

(3) aging the above mixture for 4 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a ceramic sheet to form a thin film, dried at room temperature, placed in a muffle furnace at 720°C, and kept warm for 1 hour to obtain a transparent film;

(5) Excite the transparent film with plasma for 0.5 hours to obtain a reversible super-amphiphilic film.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Placing the ceramic sheet coated with a reversible super-amphiphilic film outdoors can maintain a good self-cleaning effect, and the dust and other pollutants adhering to the surface can be washed away by rainwater.

Example 45.

At room temperature, 7.2mol of titanium tetraoctene glycolate, 0.5mol of zinc acetate, 0.11mol of indium acetate, 0.09mol of ammonium molybdate, and 0.1mol of zirconium hypochlorite (at this time, titanium tetraoctene glycolate accounts for the total amount of metal salts) 90%), was added in the isopropanol solvent of 91.1mol, and after the metal salt was dispersed uniformly by ultrasonic waves, a transparent sol was obtained;

(2) Add 0.6 mol of glycerin stabilizer to the obtained transparent sol, slowly add 35% of 0.27 mol concentrated hydrochloric acid catalyst dropwise under strong stirring, continue stirring for about 3.5 hours, and generate a mixture containing partially hydrolyzed metal salts ;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a ceramic sheet to form a film, dried at room temperature, placed in a muffle furnace at 560°C, and kept for 1.2 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with ultraviolet light for 2 hours.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

The reversible super-amphiphilic film in the initial state is placed in a weakly acidic environment (pH=4) and exposed to ultraviolet light alternately, and the contact angle of water on its surface can be rapidly reversible between 32° and 0° Variety. That is step (6), when the reversible super-amphiphilic film is placed in a weakly acidic environment (pH=4) for 30 minutes, the contact angle of water becomes 32°; and then it is irradiated with ultraviolet light for 30 minutes, The contact angle of water becomes 0° again.

Example 46.

At room temperature, 17.48 mol of titanium tetraoctene glycolate, 0.9 mol of tin acetate, 0.32 mol of basic aluminum acetate dihydrate, 0.2 mol of strontium carbonate, and 0.1 mol of zirconium nitrate pentahydrate (at this time, titanium tetraoctene glycolate occupies the metal 92% of the total amount of salt), joined in the n-butanol solvent of 79.8mol, after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 1.0 mol of triethylene glycol stabilizer to the obtained transparent sol, slowly add 35% of 0.23 mol concentrated hydrochloric acid catalyst dropwise under strong stirring, and continue stirring for about 3 hours to form a compound containing partially hydrolyzed mixtures of metal salts;

(3) aging the above mixture for 8 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a stainless steel sheet to make a film, dried at room temperature, placed in a muffle furnace at 580° C., and kept warm for 0.5 hours to obtain a transparent film;

(5) The reversible superamphiphilic film can be obtained by irradiating the transparent film with visible light of 400-500 nm for 4.5 hours.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 47.

At room temperature, 23.04mol of titanium tetraoctene glycolate, 0.3mol of tin tetrachloride, 0.5mol of zinc nitrate hexahydrate, 0.06mol of tungsten hexachloride, and 0.1mol of dichlorodioxydimethyldichlorosilane (at this time Tetraoctene glycol titanium accounts for 96% of the total amount of the metal salt), joins in the chloroform solvent of 73.5mol, after the metal salt is dispersed evenly by ultrasonic waves, a transparent sol is obtained;

(2) The triethylene glycol stabilizer of 1.9mol is joined in the transparent sol that obtains, and the acetic acid catalyst of 0.58mol is slowly added dropwise under strong stirring, continues to stir about 2.5 hours, generates the metal salt that contains part hydrolysis mixture;

(3) aging the above mixture for 6 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on a glass sheet to form a film, dried at room temperature, placed in a muffle furnace at 570°C, and kept warm for 0.3 hours to obtain a transparent film;

(5) A reversible super-amphiphilic film can be obtained by irradiating the transparent film with sunlight for 1 hour.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Example 48.

At room temperature, 27.44mol of titanium tetraoctene glycolate, 0.2mol of tin tetrachloride, 0.11mol of anhydrous aluminum chloride, 0.16mol of ammonium molybdate, and 0.09mol of zirconium tetrachloride (at this time, titanium tetraoctene glycolate Accounting for 98% of the total amount of the metal salt), added to 69.2mol of ethanol solvent, after the metal salt was dispersed evenly by ultrasonic waves, a transparent sol was obtained;

(2) Add 2.3 mol of 1,3-propanediol 2.3 mol stabilizer to the obtained transparent sol, slowly add 0.50 mol of concentrated ammonia catalyst dropwise under strong stirring, and continue stirring for about 5 hours to generate partially hydrolyzed metal salt mixture;

(3) aging the above mixture for 3 hours to obtain a transparent sol with evenly dispersed nanoparticles;

(4) The above-mentioned transparent sol is spin-coated on an aluminum sheet to form a thin film, and after drying at room temperature, it is placed in a muffler furnace at 550° C. and kept for 0.1 hour to obtain a transparent film;

(5) A reversible superamphiphilic film can be obtained by irradiating the transparent film with a 532 nm laser for 0.5 hour.

When the reversible super-amphiphilic film is stored in the dark, it can keep the contact angles of water and oil (n-hexadecane) on the film at 0° within 30 days.

Table 1 Surface water and oil contact angle changes of reversible superamphiphilic films stored in the dark Storage time in dark place (days) Water contact angle (degrees) Oil contact angle (degrees) 0 0 0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 10 0 0 15 0 0 20 0 0 25 0 0 30 0 0 32 1 0 34 2 0 36 2 0 38 3 0 40 4 0 42 5 0 44 5 0 46 6 1 48 6 0 50 7 1 52 9 2 54 12 2 56 13 3 60 15 2 62 17 4 64 20 5 66 twenty two 4 68 twenty three 6 70 twenty two 7 72 25 7 74 twenty four 8 76 26 9 78 28 9 80 30 10 82 30 13 84 32 14 86 34 15 88 35 14 90 36 15

Claims (7)

1. a kind of preparation method with reversible super amphiphilic thin film is characterized in that: the preparation step of thin film is: (1) At room temperature, add 0.5 to 32 mol of metal salt into 70 to 98 mol of organic solvent, wherein the metal salt is made of titanium salt with a molar content of 80 to 98% and 2 to 20% of other metal salts Composition, the metal salt is uniformly dispersed in the organic solvent by ultrasonic waves, and a transparent solution is obtained; (2) Add 0.1 to 6 mol of stabilizer to the above transparent solution, slowly add 0.01 to 1.63 mol of catalyst dropwise under strong stirring at room temperature, and continue stirring for about 0.1 to 8 hours after the dropwise addition to form a part containing Mixtures of hydrolyzed metal salts; (3) aging the above mixture for 3 to 8 hours to obtain a transparent sol with evenly dispersed nanoparticles; (4) Spin-coat, spray or dip-coat the above-mentioned transparent sol on the surface of the substrate, dry it at room temperature, place it in a muffle furnace at 550-720°C, and keep it warm for 0.05-1.5 hours to obtain a transparent film; (5) After the transparent film is exposed to an external field that causes a super-amphiphilic effect for 10 minutes to 5 hours, a reversible super-amphiphilic film is obtained; The titanium salt is tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, tetra(2-ethylhexyl) titanate, tetra(heptadecane) titanate, diisopropoxy - titanium diacetylacetonate, di-n-butoxy-di(triethanolamine) titanium, dihydroxy-dilactate or titanium tetraoctene glycolate; other metal salts are tin tetrachloride, tin acetate, zinc chloride, acetic acid Zinc, zinc nitrate hexahydrate, zinc carbonate, tungsten hexahydrate, tungsten dichloride, basic aluminum acetate dihydrate, anhydrous aluminum chloride, aluminum isopropoxide, strontium dichloride hexahydrate, strontium carbonate, Indium trichloride, indium nitrate pentahydrate, indium acetate, ammonium molybdate, niobium pentachloride, tetrachlorosilane, tetrabromosilane, tetraethyl silicate, tetrabutyl silicate, dimethoxydiethoxy Silane, dimethyldichlorosilane, zirconium tetrachloride, zirconium nitrate pentahydrate or zirconium hypochlorite; The stabilizer is ethylene glycol, diethylene glycol, triethylene glycol, glycerol or 1,3-propanediol; The catalyst is concentrated hydrochloric acid, acetic acid, concentrated nitric acid, concentrated sulfuric acid or concentrated ammonia water. 2. the preparation method of the super amphiphilic film with reversibility as claimed in claim 1, is characterized in that: after step (5), further comprises step (6): the super amphiphilic film with reversibility is eliminated super amphiphilic film Field induction of amphipathic effects. 3. the preparation method of the super-amphiphilic film with reversibility as claimed in claim 1 is characterized in that: described organic solvent is ethanol, propanol, Virahol, n-butanol, isobutanol, acetone, chloroform , n-hexane, benzene, toluene or carbon tetrachloride. 4. The method for preparing a reversible super-amphiphilic thin film as claimed in claim 1, characterized in that: the external field induction that causes the super-amphiphilic effect is ultraviolet light irradiation, plasma excitation, laser irradiation, 400-500nm Visible light irradiation, argon ion bombardment or microwave excitation. 5. The method for preparing a reversible super-amphiphilic thin film according to claim 1, characterized in that: the external field induction for eliminating the super-amphiphilic effect is ultrasonic waves or a weak acid environment with a pH of 4-6. 6. The reversible super-amphiphilic thin film prepared by the method according to any one of claims 1 to 5, characterized in that: the thin film is made of TiO with a molar content of 80 to 98% Nanoparticles and ₂ to 20 % metal oxide nanoparticles, the particle size of the nanoparticles is 50-80nm; The metal oxide nanoparticles are selected from SnO ₂ , ZnO, WO ₃ , Al ₂ O ₃ , SrTiO ₃ , In ₂ O ₃ , MoO ₃ , Nb ₂ O ₃ , SiO ₂ , ZrO ₂ or mixtures thereof. 7. the purposes of the reversible super amphiphilic film as claimed in claim 6, is characterized in that: described film is used for the antifogging or self-cleaning of the substrate surface of glass, mirror surface, metal or pottery; Surface modification of bearings of precision instruments; modification of column chromatography fillers.

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