CN1417147A

CN1417147A - Low-temperature prepn process of self-cleaning nano Tio2 glass

Info

Publication number: CN1417147A
Application number: CN 02150721
Authority: CN
Inventors: 任达森; 崔晓莉; 沃松涛; 杨锡良; 章壮健
Original assignee: Fudan University
Current assignee: Fudan University
Priority date: 2002-11-26
Filing date: 2002-11-26
Publication date: 2003-05-14
Anticipated expiration: 2022-11-26
Also published as: CN1228267C

Abstract

The present invention relates to a low temperature treating process of self-cleaning TiO2 nanoglass. By using silica and anatase type nanosol as basic components and through pulling process, film is formed on the surface of glass plate. The film is dried at room temperature and cured or treated at temperature below 300 deg.c and cooled naturally. The prepared self-cleaned glass has excellent photocatalytic property, superhydrophilic property, high and homogeneous transparency. The said process is simple, low in cost and suitable for industrial production.

Description

A kind of low temperature preparation method of nano titanium oxide self-cleaning glass

Technical field

The invention belongs to chemical technology field, be specifically related to the method that a kind of low temperature prepares the nano titanium oxide self-cleaning glass.

Background technology

Found nano titanium oxide since splitting water into hydrogen and oxygen under the UV-irradiation since 1972, titanium dioxide is subjected to paying attention to very widely at material circle.In nano semiconductor material, Detitanium-ore-type TiO ₂With its photocatalysis efficiency height, good stability, nontoxic and receive very big concern.Moreover, with Detitanium-ore-type TiO ₂The film of making also has photic super hydrophilicity, has expanded its practical use more.Use Detitanium-ore-type TiO ₂The film of preparation both can be used for degradation of organic substances, sterilization and disinfection, sewage disposal, purifying air etc., as made green light catalytic materials such as self-cleaning glass, sterilization ceramic tile, sewage purification material, also can be used as antifog material, was used for occasions such as automobile rearview mirror.At present, nano-TiO ₂Research become a very active problem of nanometer novel material exploitation.

Preparation TiO ₂The method of film is a lot, and its relative merits are respectively arranged.As with physics method depositing Ti O such as direct current reaction magnetron sputterings ₂The glass of film has the good transparency, stronger photocatalysis performance and photic Superhydrophilic, film evenly, controllable thickness, but must vacuum system, the equipment price costliness, sputter rate also is a big bottleneck of its development of restriction in addition; The film of sol-gel method preparation has the purity height, reaction conditions is easy to advantages such as control, but need toast under comparatively high temps; And there is certain degree of difficulty in chemical Vapor deposition process in preparation large area film fashion.Just because of the various limitation that exist in various film-forming methods and the means, thereby seriously restricted nano-TiO ₂The practicalization of thin-film material.

Summary of the invention

The objective of the invention is to propose that a kind of equipment is simple, investment is little, be easy to suitability for industrialized production, low-temperature curable prepares the method for nano-titanium dioxide film self-cleaning glass.Self-cleaning glass with this method preparation has good photochemical catalysis and super hydrophilicity, and transmittance is higher, and evenly.

The low-temperature curing that the present invention proposes prepares nano-titanium dioxide film self-cleaning glass method, with silicon-dioxide, Detitanium-ore-type TiO ₂The colloidal sol nano material is basic composition, adopts crystal pulling method to form film at glass baseplate surface, and is at room temperature dry, solidify, or handles the back naturally cooling under less than 300 ℃ of temperature and get final product.

Among the present invention, silicon-dioxide derives from water-soluble silicon colloidal sol or tetraethoxysilance hydrolysis, Detitanium-ore-type TiO ₂Colloidal sol is by TiCl ₄Or other titanium salt hydrolysis preparation and obtaining, the relative content of each component is (is 1 unit with total volume): tetraethoxysilance or water-soluble silicon colloidal sol 0.1～10%, Detitanium-ore-type TiO ₂Colloidal sol 1～30% (TiO ₂Net content is 0.065%～1.948%), all the other are deionized water or deionized water and HCl.Membrane structure such as Fig. 1 show.

The concrete steps of preparation are: above-mentioned basic component is diluted with dehydrated alcohol, add deionized water, perhaps directly add deionized water, be stirred into colloid, glass substrate vertically is put in the colloid, at the uniform velocity lifts then, at room temperature dry, curing, or under less than 300 ℃ of temperature, handle the back naturally cooling, promptly get the nano titanium oxide self-cleaning glass.

Experiment showed, that the self-cleaning glass by the present invention's preparation has good Superhydrophilic and photocatalysis performance:

1. wetting ability experiment.In power density is 200 μ W/cm2, and wavelength is to shine under the UV-light of 254nm, measures the variation of the contact angle of water droplet (1 μ l) and film surface with the UV-irradiation time.Through after the irradiation of 40min time, contact angle is less than 1 degree, as shown in Figure 2.Has good anti-fog function.

2. photochemical catalysis experiment.Be about 100 μ W/cm2 in power density, wavelength is to shine under the UV-light of 254nm, to the decomposition of dyestuff methylene blue, as shown in Figure 3.

With half glass that is coated with nano-titanium dioxide film on March 26th, 2002 to being positioned between 10 days November in 2002 on outdoor windowsill, after water dashes as a result, this nano-TiO is arranged ₂The part of film cleaning is bright, and the part dirt that does not have a film is still on its surface.

The inventive method, equipment is simple, invests for a short time, is easy to suitability for industrialized production.

This self-cleaning glass can be widely used in the window glass of buildings, auto mirror etc.

Description of drawings

Fig. 1 is this nano titanium oxide self-cleaning glass membrane structure diagram.

Fig. 2 is in the hydrophilic experiment, the diagram that contact angle changed with the UV-irradiation time.Wherein, Fig. 2 (a) is (6 °) diagram before the illumination, and Fig. 2 (b) illustrates for (0 °) after the illumination, and Fig. 2 (c) is a change curve.

Fig. 3 is in the photochemical catalysis experiment, to the decomposition diagram of dyestuff methylene blue.

Number in the figure: 1 is glass substrate, and 2 is film.

Embodiment

The invention is further illustrated by the following examples.

Embodiment 1: with 9.2ml Detitanium-ore-type TiO ₂Colloid, 3ml water-soluble silicon colloidal sol and 47.8ml deionized water mix and stir; The glass substrate of previously prepd cleaning is vertically put into colloid, then it is at the uniform velocity lifted, place clean environment, and at room temperature dry, solidify or handling the back naturally cooling down smaller or equal to 300 ℃.Zhi Bei self-cleaning glass is that 254nm, optical power density are 200 μ W/cm at wavelength thus ²UV-light under the irradiation 40 minutes after, contact angle is reduced to below 1 ° by 54 °, approaches 0 °, has tangible anti-fog function.

Embodiment 2: the tetraethoxysilance of 4ml was mixed stirring after 4 hours with 50ml dehydrated alcohol (〉=99.7%), add the mixed solution of deionized water (4ml) and HCl (0.12ml), and stirred 2 hours; Again will be with the Detitanium-ore-type TiO of dehydrated alcohol (50ml) dilution ₂Colloid (20ml) adds wherein, mixes with ultrasonic device.The clean glass substrate of previously prepd is inserted wherein, and vertically at the uniform velocity lift, place it in seasoning in the clean environment, curing or descending processing back naturally cooling getting final product smaller or equal to 300 ℃.Zhi Bei self-cleaning glass is that 254nm, optical power density are 160 μ W/cm at wavelength thus ²UV-light under the irradiation 40 minutes after, the contact angle of water is reduced to below 1 ° by 13 °.

Claims

1, a kind of nano titanium oxide self-cleaning glass low temperature preparation method is characterized in that with silicon-dioxide and Detitanium-ore-type TiO ₂Nano material is basic composition, makes colloid, adopts crystal pulling method to form film at glass baseplate surface, at room temperature dry, curing, or under less than 300 ℃ temperature, handle cooling then.

2, preparation method according to claim 1 is characterized in that silicon-dioxide derives from water-soluble silicon colloidal sol or tetraethoxy, Detitanium-ore-type TiO ₂Colloidal sol is by TiCl ₄Or other titanium salt hydrolysis preparation and obtaining.

3, preparation method according to claim 2, the content that it is characterized in that each component in the colloid is tetraethoxy or water-soluble silicon colloidal sol 0.1-10%, Detitanium-ore-type TiO ₂Colloidal sol 1-30%, Detitanium-ore-type TiO ₂Middle TiO ₂Molten net content is 0.065-1.948%.

4, preparation method according to claim 3, it is characterized in that the concrete steps that prepare are as follows: basic component is diluted with dehydrated alcohol, add deionized water again, perhaps directly add ionized water, be stirred into colloid, glass substrate vertically is put in the colloid, at the uniform velocity lift then, at room temperature dry, curing are perhaps handled the back naturally cooling under less than 300 ℃ of temperature.