CN107434360B - Super-hydrophilic agent, preparation method and super-hydrophilic vehicle window glass - Google Patents
Super-hydrophilic agent, preparation method and super-hydrophilic vehicle window glass Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/445—Organic continuous phases
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
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Abstract
The invention relates to the technical field of hydrophilic glass, in particular to a super-hydrophilic agent which is characterized by comprising the following components: 0.08-0.33 wt% of tin dioxide nanoparticles, 2-5 wt% of carbon nanotube powder, 0.2-0.8 wt% of polyvinyl alcohol and the balance of dispersion liquid; the carbon nano tube powder is a powdery single-wall or multi-wall carbon nano tube, and the tin dioxide nano particles are attached to the surface of the carbon nano tube. The invention also provides a preparation method of the super-hydrophilic agent and super-hydrophilic vehicle window glass provided with the super-hydrophilic coating formed by the super-hydrophilic agent. Has the advantages that: the visible light has high transmittance, can absorb infrared radiation and still has good super-hydrophilic characteristic under the non-illumination condition.
Description
The technical field is as follows:
the invention relates to the technical field of hydrophilic glass, in particular to a super-hydrophilic agent, a preparation method of the super-hydrophilic agent and super-hydrophilic vehicle window glass provided with a super-hydrophilic coating.
Background art:
the wettability of the surface of the material is always a focus of attention in academia and industry, and super-hydrophilicity and super-hydrophobicity are two extremely special wetting phenomena, which attract the wide research of domestic and foreign scholars in recent years. Generally, a superhydrophobic surface refers to a surface having a solid-liquid contact angle of greater than 150 °. Conversely, a superhydrophilic surface refers to a surface where the liquid is able to spread completely and result in a contact angle equal to or close to 0 °. Compared with super-hydrophobic research, research on super-hydrophilicity is less, but due to the unique wetting characteristic of the super-hydrophilic surface, the super-hydrophilic surface has the advantages of self-cleaning, high-efficiency heat conduction and the like. It was first discovered that the superhydrophilic properties were based on the photocatalytic properties of titanium dioxide, and that after exposure to ultraviolet light, water contacted the titanium dioxide semiconductor film and the contact angle rapidly decreased to 0 ± 1 °. The principle is that the bridge oxygen on the surface of titanium dioxide is excited by ultraviolet light to generate active oxygen free radicals, the active oxygen free radicals react with holes to generate oxygen-based holes, and water is absorbed in the oxygen-based holes to become chemically absorbed water, so that uniformly distributed nano-scale hydrophilic micro-regions are formed on the surface. The super-hydrophilic property has important application in antifogging glass and self-cleaning glass.
However, the significant disadvantages of titanium dioxide films for self-cleaning glass are manifested in two ways: the super-hydrophilic property can be exerted only under the condition of illumination, namely, the condition of light irradiation is required; secondly, the light transmission of the titanium dioxide coating is poor, and the titanium dioxide coating is not suitable for being directly used for a glass coating.
In comparison, the tin dioxide with the same photocatalytic property is an n-type semiconductor transparent conductive material with a wide energy gap, the visible light transmittance and the infrared transmittance can reach 80%, the light refractive index is greater than 2, the extinction coefficient tends to 0, the tin dioxide has a good bonding effect with hard materials such as glass, ceramic and the like, and the bonding force can reach 20 MPa. Meanwhile, the coating has good chemical stability under water environment, and is very suitable for being used as a self-cleaning coating on the surface of transparent glass. Nevertheless, continuous light conditions are also required to fully develop the above excellent properties of tin dioxide.
On the other hand, the glass widely used at present, such as automobile glass, architectural glass and the like, is made of silicate materials, and particularly, the sandwich type silicate glass is generally adopted for the front windshield of an automobile to improve the impact strength of the glass. However, such silicate laminated glass has high light transmittance, and especially in a high-temperature period in summer, high-intensity visible light penetrates through the automobile front windshield laminated glass, so that the sight of a driver is obstructed, visual fatigue is caused, binocular dizzy is caused, the driving risk is increased, the temperature in an automobile is increased by strong infrared heat radiation, the power load brought by an on-vehicle air conditioner is increased, and the sustainable development of the automobile towards the energy-saving and environment-friendly directions is not facilitated. Therefore, it is necessary to design a new type of window glass to achieve the light ray adaptive function, that is, automatically adjust the visible light transmission intensity according to the temperature difference between the inside and outside environment, and simultaneously absorb the infrared heat radiation.
The present invention has been made in view of the above problems.
The invention content is as follows:
the invention aims to solve the technical problem of the existing hydrophilic glass, and provides a super-hydrophilic agent which has no limitation on the use condition by illumination, has good super-hydrophilic characteristic, high visible light transmittance and can absorb infrared radiation. The invention also provides a preparation method of the super-hydrophilic agent and super-hydrophilic vehicle window glass with the inner surface coated with the super-hydrophilic coating.
The technical scheme adopted by the invention for solving the technical problems is as follows: the super-hydrophilic agent is characterized by comprising the following components: 0.08-0.33 wt% of tin dioxide nanoparticles, 2-5 wt% of carbon nanotube powder, 0.2-0.8 wt% of polyvinyl alcohol and the balance of dispersion liquid; the carbon nano tube powder is a powdery single-wall or multi-wall carbon nano tube, and the tin dioxide nano particles are attached to the surface of the carbon nano tube.
Further, the diameter of the tin dioxide nano-particles is 0.3-1.2 um.
Further, the diameter of the carbon nano tube is 1.5-3 nm, and the length of the carbon nano tube is 10-100 um.
Further, the number of the walls of the carbon nanotubes is 1 to 4.
Further, the dispersion liquid is composed of a dispersing agent and a dilute acid solution in a volume ratio of 4-7: 1.
Further, the dilute acid solution is dilute hydrochloric acid with the solute mass fraction lower than 20% or dilute sulfuric acid with the solute mass fraction lower than 70%.
Further, the dispersing agent is ethanol, isopropanol or n-hexanol.
Further, the tin dioxide nanoparticles are attached to the surface of the carbon nanotube to form a bead-like structure.
The invention also provides a preparation method of the super hydrophilic agent, which is characterized by comprising the following steps: step 1: preparing stannic oxide nanoparticles; step 2: mixing a dispersing agent and a dilute acid solution in a volume ratio of 4-7: 1 to form a dispersion solution, adding 2-5 wt% of carbon nano tube powder to make the pH value of the solution be 3-5, stirring at 25-30 ℃ for 1-3 h, and uniformly mixing to obtain a carbon nano tube dispersion solution; and step 3: and adding 0.08-0.33 wt% of tin dioxide nanoparticles into the carbon nano tube dispersion liquid, adding 0.2-0.8 wt% of polyvinyl alcohol, and stirring for 1-2 hours to obtain the super-hydrophilic agent.
Further, the preparation method of the tin dioxide nanoparticles comprises the following steps: adding a surfactant and an auxiliary agent in a volume ratio of 1: 3-6 into an organic solvent, wherein the concentration of the surfactant is 0.2-0.8 mol/L; and adding a high-molecular water solution consisting of 20-30 wt% of gelatin and 5-10 wt% of polyvinyl alcohol, wherein the volume ratio of the high-molecular water solution to the organic solvent is 1: 30-40 parts of; and adding a tin source dissolved by tert-butyl alcohol, wherein the volume ratio of the tin source to the organic solvent is 1: 20-40 ℃, and carrying out hydrolysis condensation reaction at 20-40 ℃ to obtain a reaction system; and demulsifying, centrifuging, washing and freeze-drying the reaction system to obtain the tin dioxide nano-particles.
Further, the surfactant is cetyl trimethyl ammonium chloride or cetyl trimethyl ammonium bromide, the auxiliary agent is n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol or cyclohexanol, and the organic solvent is n-pentane, n-hexane, cyclohexane or n-heptane.
Further, the demulsifier adopted in the demulsification process is methanol, ethanol or propanol; the washing agent adopted in the washing process is cyclohexane, benzene or carbon tetrachloride; the temperature of the freeze drying process is-50 to-30 ℃.
The invention also provides super-hydrophilic vehicle window glass, which is characterized in that: the super-hydrophilic coating is formed by the super-hydrophilic agent and is arranged on the surface, facing the interior of the vehicle, of the glass substrate.
Further, the thickness of super hydrophilic coating is 10 ~ 30 um.
Further, the method for forming the super-hydrophilic coating by the super-hydrophilic agent comprises the steps of coating the super-hydrophilic agent on the surface of the glass substrate through spraying or spin coating, placing the glass substrate in an oven at the temperature of 60-80 ℃ for 3-6 min, and cooling to room temperature.
Further, the method for forming the super-hydrophilic coating by the super-hydrophilic agent comprises the steps of coating the super-hydrophilic agent on the surface of the glass substrate through spraying or spin coating, placing the glass substrate in a drying oven at the temperature of 60-80 ℃ for 3-6 min, cooling to room temperature, placing the glass substrate in a heating furnace, heating to 120 ℃ at the speed of 2-4 ℃/min, preserving heat for 1-1.5 h, heating to 500 ℃ at the speed of 2-4 ℃/min, preserving heat for 2-3 h, and cooling to room temperature.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1) aiming at the limitation of illumination conditions of tin dioxide used as a coating material, the carbon nano tube is compounded with the tin dioxide nano particles to prepare the super-hydrophilic agent with a bead-type microstructure, so that the micro roughness of the coating is improved, and the tin dioxide has hydrophilic characteristics under non-illumination conditions;
2) the super-hydrophilic agent can also realize the special functions of high visible light transmittance and infrared radiation absorption by combining the good electric conductivity of the carbon nano tube and the strong absorption capacity of the carbon nano tube to infrared radiation;
3) on the inner surface of the super-hydrophilic vehicle window glass, water vapor is distributed in a concentrated manner according to the position of the tin dioxide nanoparticles, so that the transmission intensity of visible light can be adjusted in a self-adaptive manner and infrared heat radiation can be absorbed according to the temperature difference between the inner environment and the outer environment;
4) the super-hydrophilic agent and the vehicle window glass have simple manufacturing process, can be processed in a large scale, and have wide application prospect in the field of future functional glass.
Description of the drawings:
FIG. 1 is a partial schematic view of a super-hydrophilic window glass according to the present invention;
FIG. 2 is an enlarged partial schematic view of a super-hydrophilic coating according to the present invention;
reference numerals in the drawings indicate: 1 is a glass substrate, 2 is a super-hydrophilic coating, 3 is a carbon nano tube, and 4 is a tin dioxide nano particle.
The specific implementation mode is as follows:
the invention will be further explained with reference to the accompanying drawings.
The super-hydrophilic agent is characterized by comprising the following components: 0.08-0.33 wt% of tin dioxide nanoparticles, 2-5 wt% of carbon nanotube powder, 0.2-0.8 wt% of polyvinyl alcohol and the balance of dispersion liquid; the carbon nanotube powder is a powdery single-walled or multi-walled carbon nanotube, the number of walls is preferably 1-4, the tin dioxide nanoparticles 4 are attached to the surface of the carbon nanotube 3, and preferably form a bead structure, that is, the tin dioxide nanoparticles 4 are strung on the carbon nanotube 3 in a bead shape, as shown in fig. 2.
The tin dioxide has excellent photocatalytic property, is a transparent conductive semiconductor material with wide forbidden band, is very suitable for being used as a glass surface coating material, and enables the glass to have the functions of transparency, conductivity, self-cleaning and the like. However, the single tin dioxide coating layer is difficult to exert a hydrophilic effect under the non-illumination condition due to the illumination condition. Therefore, the carbon nano tube and the tin dioxide nano particles are compounded, and the hydrophilic capacity of the coating under the non-illumination condition is improved by improving the micro roughness of the original coating.
According to the Cassie-Baxter model, the contact between liquid and the surface is composite contact, namely, trapped liquid or air exists between liquid drops and grooved solid, and when the material has better hydrophilic performance, the capillary action is easily generated and the material is adsorbed on the surface of the hydrophilic material. The report of the literature [ Zhang et al nature Communication,2013,4:1727 ] shows that tin dioxide nanoparticles obtained after hydrolysis of a tin source are easily adsorbed on the surface of a single carbon nanotube, and here, a carbon nanotube dispersion liquid is compounded with tin dioxide to obtain a unique bead structure so as to enhance the micro roughness of a tin dioxide coating. The carbon nano tube has strong hydrophobic property, so that external moisture can be spontaneously concentrated around the tin dioxide particles under the driving of high potential energy, and the limitation of illumination conditions is avoided, thereby being beneficial to realizing the lasting super-hydrophilic characteristic of the coating.
On the other hand, the super-hydrophilic coating can realize the special functions of transmitting visible light and absorbing infrared radiation by combining the good electric conduction of the carbon nano tube and the strong absorption capacity of the carbon nano tube to the infrared radiation.
Further, the diameter of the tin dioxide nano-particles is 0.3-1.2 um, the diameter of the carbon nano-tubes is 1.5-3 nm, and the length of the carbon nano-tubes is 10-100 um.
Further, the dispersion liquid is a mixed liquid of a dispersing agent and a dilute acid solution in a volume ratio of 4-7: 1, the dilute acid solution is preferably a dilute hydrochloric acid solution with a solute mass fraction of less than 20% or a dilute sulfuric acid solution with a solute mass fraction of less than 70%, and the dispersing agent is preferably ethanol, isopropanol or n-hexanol.
The invention also provides a preparation method of the super hydrophilic agent, which is characterized by comprising the following steps:
step 1: preparing stannic oxide nanoparticles;
step 2: mixing a dispersing agent and a dilute acid solution in a volume ratio of 4-7: 1 to form a dispersion solution, adding 2-5 wt% of carbon nano tube powder to make the pH value of the solution be 3-5, stirring at 25-30 ℃ for 1-3 h, and uniformly mixing to obtain a carbon nano tube dispersion solution;
and step 3: and adding 0.08-0.33 wt% of tin dioxide nanoparticles into the carbon nano tube dispersion liquid, adding 0.2-0.8 wt% of polyvinyl alcohol, and stirring for 1-2 hours to obtain the super-hydrophilic agent. Wherein, the weight percent is weight percent, h is hour, and the weight percent of each component is the weight proportion of the super-hydrophilic agent finally prepared.
Further, the preparation method of the tin dioxide nanoparticles comprises the following steps: adding a surfactant and an auxiliary agent in a volume ratio of 1: 3-6 into an organic solvent, wherein the concentration of the surfactant is 0.2-0.8 mol/L; and adding a high-molecular water solution consisting of 20-30 wt% of gelatin and 5-10 wt% of polyvinyl alcohol, wherein the volume ratio of the high-molecular water solution to the organic solvent is 1: 30-40 parts of; and adding a tin source dissolved by tert-butyl alcohol, wherein the volume ratio of the tin source to the organic solvent is 1: 20-40 ℃, and carrying out hydrolysis condensation reaction at 20-40 ℃ to obtain a reaction system; and demulsifying, centrifuging, washing and freeze-drying the reaction system to obtain the tin dioxide nano-particles.
Further, the surfactant is cetyl trimethyl ammonium chloride or cetyl trimethyl ammonium bromide, the auxiliary agent is n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol or cyclohexanol, and the organic solvent is n-pentane, n-hexane, cyclohexane or n-heptane; the demulsifier adopted in the demulsification process is methanol, ethanol or propanol; the washing agent adopted in the washing process is cyclohexane, benzene or carbon tetrachloride; the temperature of the freeze drying process is-50 to-30 ℃.
As shown in fig. 1, the present invention also provides a super-hydrophilic vehicle window glass, which is characterized in that: including glass substrate 1 and by above super hydrophilic coating 2 that super hydrophilic agent formed, super hydrophilic coating 2 sets up on glass substrate's the interior surface in the car, super hydrophilic coating 2's thickness is preferred 10 ~ 30 um.
In the present invention, the window glass may be a single sheet of glass, a laminated glass, a vacuum glass, a hollow glass or a combination thereof. The material of the vehicle window pane can be selected from flat glass, float glass, quartz glass, borosilicate glass, soda-lime glass or plastics, in particular rigid plastics, preferably polyethylene, polypropylene, polycarbonate, polymethyl methacrylate, polystyrene, polyamide, polyester, polyvinyl chloride and/or mixtures thereof.
In the invention, the super-hydrophilic agent can be coated on the surface of the glass substrate by spraying, spin coating, magnetron sputtering and other modes, and then the glass substrate is placed in an oven at the temperature of 60-80 ℃ for 3-6 min and is naturally cooled. For temperature-resistant glass materials, such as silicates, heat treatment can be continued to enhance the bonding force between the super-hydrophilic coating and the glass substrate. The heat treatment comprises the following specific processes: and (3) placing the glass coated with the super-hydrophilic agent in a heating furnace, heating to 120 ℃ at the speed of 2-4 ℃/min, preserving heat for 1-1.5 h, heating to 500 ℃ at the speed of 2-4 ℃/min, preserving heat for 2-3 h, and cooling to room temperature. Wherein h is hour and min is minute.
The vehicle window glass structure coated with the super-hydrophilic coating is very suitable for being used as automobile front windshield glass, and has the functions of transparency, conductivity, self-cleaning and infrared radiation prevention, and the visible light transmission intensity can be adaptively adjusted according to the temperature difference between the inside and the outside of a vehicle. The working principle is that water vapor is intensively distributed along the nano particles due to the bead-string type special microstructure of the inner coating. In high-temperature weather in summer, the air conditioner is started in the vehicle, the temperature difference between the inside and the outside is large, so that the water vapor content on the surface of the inner layer is high, and visible light can be refracted by the water vapor for multiple times when passing through the surface of the inner layer, so that the transmitted illumination intensity can be greatly weakened; in winter or cloudy days, the temperature difference between the inside and the outside of the vehicle is low, and the water vapor content of the inner surface is low, so that the visible light basically maintains normal transmission intensity, and the normal driving of a driver is not influenced.
The present invention is described in more detail below with reference to specific examples.
The first embodiment is as follows: preparation of super-hydrophilic agent
(1) And preparing the tin dioxide nano particles. Adding 3g of hexadecyl trimethyl ammonium chloride into 10ml of n-pentane, then adding 5ml of n-pentanol, stirring and heating to 60 ℃ to completely dissolve the hexadecyl trimethyl ammonium chloride, then adding 0.3ml of 6 wt% polyvinyl alcohol aqueous solution, and cooling to 30 ℃. Then 0.5ml of 8 wt% tin tert-butoxide/tert-butanol solution is added dropwise, reaction is carried out for 2h at 30 ℃, 12ml of ethanol is added for demulsification, ultrasonic treatment is carried out for 2min, and centrifugation is carried out for 10min at the rotating speed of 5000 rpm. After the centrifugation is finished, washing the solid with 6.5ml of carbon tetrachloride, centrifuging, and freeze-drying at-45 ℃ for 6h to obtain the product.
In the step of preparing the tin dioxide nanoparticles, the specific preparation method refers to the "preparation method of tin dioxide nanoparticles" disclosed in chinese patent CN 105819497A. In order to meet the technical requirements of the invention, the invention carries out experimental verification on the basis of the published patent method and further optimizes the parameters. For the sake of brevity, this is incorporated herein by reference, and all technical disclosure of the above-mentioned applications should be considered as part of the technical disclosure of the present application.
(2) Preparing a carbon nanotube dispersion. Adding 2ml of dilute sulfuric acid into 10ml of ethanol to prepare a dispersion, adding 2g of multi-walled carbon nanotube powder, then slowly dropwise adding the dilute sulfuric acid while testing the pH value of the solution until the pH value of the solution is adjusted to be 4, and then magnetically stirring for 2 hours at 25 ℃ to uniformly mix the solution.
(3) And preparing the tin dioxide/carbon nano tube coating liquid. And slowly adding 0.1g of the tin dioxide nanoparticles prepared in the steps into the carbon nanotube dispersion liquid, adding 0.5 wt% of polyvinyl alcohol 0.5ml, and stirring for 2 hours to obtain the super-hydrophilic agent.
Example two: production of super-hydrophilic glass
(1) And (5) cleaning. And (2) taking a glass substrate, cleaning the glass substrate by using a detergent and deionized water, then sequentially cleaning the glass substrate by using acetone, ethanol and water for 10min, then cleaning the glass substrate by using the deionized water, and drying the glass substrate to obtain a clean glass substrate.
(2) And spin-coating the super-hydrophilic coating prepared in the first embodiment on the surface of the glass substrate. 0.3ml of super-hydrophilic agent is dripped into the center of the glass, spin-coated for 2min at the rotating speed of 2000rpm, placed in a 60 ℃ oven for 5min, and then naturally cooled. And then placing the glass substrate in a heating furnace, heating to 120 ℃ at the speed of 2 ℃/min, preserving heat for 1h, heating to 500 ℃ at the speed of 4 ℃/min, preserving heat for 2h, and naturally cooling to room temperature to obtain the super-hydrophilic glass.
The above description specifically describes the super-hydrophilic agent, the preparation method and the super-hydrophilic vehicle window glass, but the present invention is not limited by the above description, and therefore, any improvements, equivalent modifications, substitutions and the like performed according to the technical gist of the present invention are within the scope of the present invention.
Claims (13)
1. The super-hydrophilic agent is characterized by comprising the following components: 0.08-0.33 wt% of tin dioxide nanoparticles, 2-5 wt% of carbon nanotube powder, 0.2-0.8 wt% of polyvinyl alcohol and the balance of dispersion liquid; the carbon nano tube powder is a powdery single-walled or multi-walled carbon nano tube, the tin dioxide nano particles are attached to the surface of the carbon nano tube, and the tin dioxide nano particles are attached to the surface of the carbon nano tube to form a bead-string type structure; the diameter of the tin dioxide nano-particles is 0.3-1.2 mu m, the diameter of the carbon nano-tubes is 1.5-3 nm, and the length of the carbon nano-tubes is 10-100 mu m.
2. A superhydrophilic agent according to claim 1, characterized in that: the number of walls of the carbon nanotube is 1 to 4.
3. A superhydrophilic agent according to claim 1, characterized in that: the dispersion liquid is composed of a dispersing agent and a dilute acid solution in a volume ratio of 4-7: 1.
4. A superhydrophilic agent according to claim 3, characterized in that: the dilute acid solution is dilute hydrochloric acid with the solute mass fraction lower than 20% or dilute sulfuric acid with the solute mass fraction lower than 70%.
5. A superhydrophilic agent according to claim 3, characterized in that: the dispersing agent is ethanol, isopropanol or n-hexanol.
6. A preparation method of the super hydrophilic agent as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
step 1: preparing stannic oxide nanoparticles;
step 2: mixing a dispersing agent and a dilute acid solution in a volume ratio of 4-7: 1 to form a dispersion liquid, then adding 2-5 wt% of carbon nano tube powder to enable the pH value of the solution to be 3-5, stirring at 25-30 ℃ for 1-3 hours, and uniformly mixing to obtain a carbon nano tube dispersion liquid;
and step 3: and adding 0.08-0.33 wt% of tin dioxide nanoparticles into the carbon nano tube dispersion liquid, adding 0.2-0.8 wt% of polyvinyl alcohol, and stirring for 1-2 hours to obtain the super-hydrophilic agent.
7. The method of claim 6, wherein: the preparation method of the tin dioxide nano-particles comprises the following steps: adding a surfactant and an auxiliary agent in a volume ratio of 1: 3-6 into an organic solvent, wherein the concentration of the surfactant is 0.2-0.8 mol/L; and adding a high-molecular water solution consisting of 20-30 wt% of gelatin and 5-10 wt% of polyvinyl alcohol, wherein the volume ratio of the high-molecular water solution to the organic solvent is 1: 30-40 parts of; and adding a tin source dissolved by tert-butyl alcohol, wherein the volume ratio of the tin source to the organic solvent is 1: 20-40 ℃, and carrying out hydrolysis condensation reaction at 20-40 ℃ to obtain a reaction system; and demulsifying, centrifuging, washing and freeze-drying the reaction system to obtain the tin dioxide nano-particles.
8. The method of claim 7, wherein: the surfactant is cetyl trimethyl ammonium chloride or cetyl trimethyl ammonium bromide, the auxiliary agent is n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol or cyclohexanol, and the organic solvent is n-pentane, n-hexane, cyclohexane or n-heptane.
9. The method of claim 7, wherein: the demulsifier adopted in the demulsification process is methanol, ethanol or propanol; the washing agent adopted in the washing process is cyclohexane, benzene or carbon tetrachloride; the temperature of the freeze drying process is-50 to-30 ℃.
10. The super-hydrophilic vehicle window glass is characterized in that: the automobile interior decoration super-hydrophilic coating comprises a glass substrate and a super-hydrophilic coating formed by the super-hydrophilic agent as claimed in any one of claims 1 to 8, wherein the super-hydrophilic coating is arranged on the surface, facing the automobile, of the glass substrate.
11. The superhydrophilic glazing of claim 10, wherein: the thickness of the super-hydrophilic coating is 10-30 mu m.
12. The superhydrophilic glazing of claim 10, wherein: the method for forming the super-hydrophilic coating by the super-hydrophilic agent comprises the steps of coating the super-hydrophilic agent on the surface of the glass substrate through spraying or spin coating, placing the glass substrate in an oven at the temperature of 60-80 ℃ for 3-6 min, and cooling to room temperature.
13. The superhydrophilic glazing of claim 10, wherein: the method for forming the super-hydrophilic coating by the super-hydrophilic agent comprises the steps of coating the super-hydrophilic agent on the surface of a glass substrate through spraying or spin coating, then placing the glass substrate in a drying oven at the temperature of 60-80 ℃ for 3-6 min, cooling to room temperature, then placing the glass substrate in a heating furnace, heating to 120 ℃ at the speed of 2-4 ℃/min, preserving heat for 1-1.5 h, then heating to 500 ℃ at the speed of 2-4 ℃/min, preserving heat for 2-3 h, and cooling to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710738869.XA CN107434360B (en) | 2017-08-25 | 2017-08-25 | Super-hydrophilic agent, preparation method and super-hydrophilic vehicle window glass |
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| KR101398971B1 (en) * | 2013-07-19 | 2014-05-27 | 주식회사 케이닉스공사 | Coated film with high-hydrophilic and ir shield characteristic, and preparing method thereof |
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