CN1583636A - Sterilizing and self-cleaning glass with zinc doped titanium dioxide coating - Google Patents

Abstract

A zinc-doped titanium dioxide photocatalytic, antibacterial and bactericidal air-purifying film and a preparation method thereof. Titanate or titanate with a concentration of 5%-35% by weight; 0.1%-10% nanoparticles of zinc-containing compounds; 40%-99% diluent; 0.1%-10% hydrolysis catalyst; 0.1 %-5% stabilizer composition. It can be used to prepare multifunctional titanium dioxide composite thin film materials with photocatalytic degradation and light induction to quickly achieve high hydrophilicity. With soda calcium silicate glass as the carrier, it has the functions of high photocatalytic degradation of harmful gases, antifouling and self-cleaning, antibacterial and sterilizing, etc. .

Description

The glass of sterilization of a kind of energy and the titanium deoxid film that is coated with doping zinc that oneself is clean

Technical field the present invention relates to be coated in the lip-deep a kind of optically catalytic TiO 2 of soda lime glass, antibiotic, sterilizing and air-cleaning film and preparation method thereof, belongs to glass surface treatment conductor photocatalysis technology and antibiotic, sterilization field.

The challenge of the maximum that the background technology 21 century mankind face---environmental pollution and energy shortage have become the Damokers sharp sword of uphanging on the human crown.Atmospheric pollution, bacterium wreak havoc becomes the most serious problem that people face.The exhaust gas emission of a large amount of vehicles, the discharging of domestic refuse have caused comprehensive deterioration of Air quality.Show that through investigation China city resident is extremely serious by the indoor pollution that house fitting-up causes: objectionable impurities has kind more than 500, wherein volatile organic matter reaches kind more than 300, even carcinogenic substance just has kind more than 20, and many objectionable impuritiess are to be released gradually, need the several years just can be harmless fully.

So very easily human body is caused damage, serious room air pollution has caused the increase of China resident various diseases sickness rate, and existing many methods also may cause secondary pollution, cure the symptoms, not the disease.Human after having experienced " smoke pollution " and " photochemical pollution " that the Industrial Revolution causes, entered " indoor pollution " the 3rd pollution period for indicating.Implement the strategy of sustainable development, coordinate the relation of Man ﹠ Nature, the requirement of curbing environmental pollution is arisen at the historic moment the environmentally conscious materials science, becomes the focus of modern social science research, and the photocatalysis antibacterial material of keeping a public place clean just becomes the heat of pining for.Especially after SARS wreaked havoc whole Divine Land, people more paid close attention to it.Anti-biotic material substantially can be divided into inorganic antiseptic and organic antibacterial agent, and traditional inorganic antiseptic is poisonous mostly or be corrosive, and poor stability, has limited the use of inorganic antiseptic.Organic antibacterial agent obtain the market favor, but organic anti-bacterial has certain harm can not satisfy market demands because biological degradability is poor to human body and environment because of its efficient sterilization idiocratic fast, begins restriction and uses; The novel inorganic anti-biotic material has overcome the shortcoming of traditional inorganic antiseptic,, wide spectrum nontoxic, long-acting, do not produce resistance, particularly its excellent thermotolerance, chemical stability with it, obtained people's approval, it is numerous and kill function and cost is low that bacterium, mould are had a good resistance.The photocatalysis titanium dioxide antiseptic-germicide is wherein a kind of.Preparation has the film of high catalytic efficiency on sheet glass, can keep cleaning glass, can purify air again, and the gas defence sterilization is that the light catalysis degradation antimicrobial technology is applied to the simplest and the most direct the most direct approach in the daily life, and application prospect is boundless.

It is to plate the simple glass of titanium oxide film layer with magnetron sputtering method that Chinese patent 00115361.7 provides a kind of self-cleaning glass and method for making thereof, Chinese patent 0021712.7 provides a kind of self-cleaning glass, also be to plate titanium oxide film layer with magnetron sputtering method, ability with good hydrophilicity and decomposing organic matter, Chinese patent 01128058.1 provides self-cleaning nano glass and production technique, prepares SiO with sol-gel method at glass surface ₂/ TiO ₂Rete, Chinese patent 01128306.8 provides the method that improves titanium dioxide film self-cleaning glass photocatalytic activity that coated surface is carried out acid treatment, improve photocatalytic activity, Chinese patent 02150721.X provides a kind of nano titanium oxide automatically cleaning low temperature preparation method, at room temperature dry, curing are perhaps handled the back naturally cooling under less than 300 ℃ of temperature.

The applied catalyzer of above-mentioned all kinds of patents all is the film that utilizes titanium dioxide, yet the energy gap of titanium dioxide is narrow, can only utilize the irradiation of the UV-light of certain wavelength just can make its generation effect that is stimulated, but has only the ultraviolet ray about 4% in the sunlight, so practicality is very low, and all do not relate to antibiotic, sterilizing function.

Summary of the invention the present invention metallic zinc ion that in titanium dioxide film, mixed, the light that has enlarged photocatalysis membrana like this utilizes scope, only utilize indoor weak light and sunlight just can be degraded into airborne obnoxious flavour innoxious substance and bring into play the good sterilization effect, thereby suppress the propagation of bacterium, have self-cleaning net work energy simultaneously.

The optically catalytic TiO 2 that the present invention proposes, the preparation method of antibiotic and sterilizing air-cleaning film are as follows:

At first, the carrier glass that is used to prepare film is carried out clean: at first water cleans; Then with the of short duration immersion of dilute hydrochloric acid to remove dirt and the free sodium ion on the glass substrate; Water washes down dilute hydrochloric acid; Then clean with ethanol; Send into thermostat container at last and carry out drying for inherent 100 ℃.Cleaning process is as follows:

Substrate → tap water → dilute hydrochloric acid → tap water → deionized water → ethanol → drying

Then, in the thinner that titanic acid ester or the titanate of weight percent concentration 5%-35% is dissolved in 40%-99%, the nanoparticle of the zinc compound of adding 0.1%-10% and the stablizer of 0.1%-5% after stirring for some time, the hydrolyst that adds 0.1%-10% at last, stir and leave standstill then, join collosol and gel, be rotated and film.

At last, heat-treat after the drying at a certain temperature and obtain required sample.

In above-mentioned preparation method, the coating method of use can be centrifugal rotational method or pickling process also crystal pulling method.

In above-mentioned preparation method, churning time is 2～10 hours, and time of repose is 2～20 hours.

In above-mentioned preparation method, the accompanying carrier of described film also can be metal, pottery etc. except that glass.

In above-mentioned preparation method, drying temperature is 30～100 ℃, and temperature range is 100～650 ℃ in the preparation process.

Embodiment

Embodiment 1

Adopting common sodium calcium silicon sheet glass is carrier, and its chemical ingredients (massfraction) is SiO ₂72.3%, Al ₂O ₃2.24%, Fe ₂O ₃0.22%, CaO 6.48%, MgO 3.96%, Na ₂O 14.05%, K ₂O 0.45%, SO ₃0.3%, before filming glass substrate is carried out cleaning pretreatment.

Mix the colloidal sol-coagulant liquid of zinc then in the preparing titanium dioxide, the titanium dioxide of getting 2mL adds in the ethanol of 4mL, add the 0.5mL diethanolamine again, stirring adds zinc acetate ethanolic soln and the 0.1mL water of the 0.15mol/L of the 5mL that has prepared again after half an hour, continue to stir one hour, leave standstill 2 hours after, utilize rotational method to film, drying is ten minutes under 70 ℃, obtains required sample after 550 ℃ of following thermal treatment.

Recording the film sample that makes with spectrophotometer is under the ultraviolet radiation of 260nm ± 30nm at wavelength, and the methyl orange solution that to concentration is 5mg/L is after a degraded in hour, and degradation rate can reach 72%.

Embodiment 2

Adopting common my sodium calcium silicon sheet glass is carrier, and its chemical ingredients is carried out cleaning pretreatment to glass substrate equally with example one.

Colloidal sol-the gelating soln of doping zinc in the preparing titanium dioxide, the titanium dioxide of getting 2mL adds in the ethanol of 3mL, add the diethanolamine of 1mL and the water of 0.15mL again, the zinc acetate ethanolic soln and the 0.1mL water continuation stirring of stirring the 0.15mol/L of the 6mL that adding has prepared after hour were left standstill 10 hours after one hour, utilize rotational method to film, 60 ℃ of dryings 15 minutes, after 600 ℃ of following thermal treatment, obtain required sample.

Recording the film sample that makes with spectrophotometer is under the ultraviolet radiation of 260nm ± 30nm at wavelength, and the methyl orange solution that to concentration is 5mg/L is after a degraded in hour, and degradation rate can reach 68%.

Embodiment 3

When utilizing optical density(OD) to represent, at first the bacterium liquid that obtains is diluted to certain turbidity with diluent.Then with blank sample, scribble the pure titinium dioxide film sample, scribble the titanium deoxid film sample of mixing zinc and place the silica glass beaker respectively, get identical turbidity, the bacterium liquid of equal volume adds wherein, under ultraviolet ray, shine, utilize the variation of visible light-its optical density value of UV-light spectrophotometric determination, just the variation of the turbidity of bacterium liquid as can be known.Can obtain the contrast effect of sample germicidal action thus.After the UV-irradiation by certain hour, we find to place blank sample the turbidity of bacterium liquid become 0.106 by 0.125, place the pure titinium dioxide sample the turbidity of bacterium liquid become 0.095 by 0.125, and the turbidity that scribbles the bacterium liquid of the titanium deoxid film sample of mixing zinc becomes 0.084 by 0.125, clearly, scribble the titanium deoxid film sample that the present invention mixes zinc and have antibiotic preferably, bactericidal property.

Embodiment 4

When utilizing number bacterial count method, at first cultured large intestine bar being diluted to concentration with stroke-physiological saline solution is 3 * 10 ⁸The bacterium liquid of individual/mL is coated in above-mentioned bacterium liquid one transfering loop respectively on the sample (A2) and blank glass sample (A3) of the sample (A1) of the pure titinium dioxide that makes, doping zinc acetate of the present invention, and diameter is about 12mm.Placed 24 hours under room temperature, gram's staining counts at microscopically.Table 1 is three kinds and scribbles the bacterial count contrast of colibacillary sample placement after 24 hours.

Table 1 sample is placed the bacterial count after 24 hours

Sample	????A1	????A2	????A3
				Bacterial count	????188	???120	???220

Compare with blank sample, the sample that is coated with pure titinium dioxide and doping zinc acetate film of the present invention all has certain anti-microbial effect, and the anti-microbial effect of the sample behind the doping zinc acetate of the present invention will be apparently higher than the sample that only is coated with pure titinium dioxide.

Embodiment 5

Table 2 is doping the present invention 3% zinc acetate film of temperature preparation under the different heat treatment shines 40min under ultraviolet ray after, the relation of its angle of wetting and thermal treatment temp, THIN COMPOSITE after finding to mix still has good wettability, best 550 ℃ of wettabilitys, with the temperature variant trend of photocatalysis efficiency is consistent, prove also that under the photoinduction situation this sample can reach high wetting ability fast.

Sample wetting under the temperature under table 2 different heat treatment

Temperature (℃)	????450	????500	????550	????600
					Wetting angle (degree)	????24	????12	????5	????13

Claims (9)

1. A titanium sol-gel film material doped with zinc, characterized in that the components are titanate or titanate with a concentration of 5%-35% by weight; nanometers of 0.1%-10% zinc-containing compounds Particles; 40%-99% diluent; 0.1%-10% hydrolysis catalyst; 0.1%-5% stabilizer. 2. The method according to claim 1, characterized in that the nanoparticles are one or more of zinc chloride, zinc acetate, and zinc ferrite. 3. The method according to claims 1 and 2, characterized in that said nanoparticles have a particle size of 2-200 nm. 4. The method according to claim 1, characterized in that said titanate or titanate is one or more of tetrabutyl titanate, titanium tetrachloride or titanium sulfate. 5. The method according to claim 1, characterized in that the diluent is one or more of absolute ethanol, water, and absolute methanol. 6. The method according to claim 1, characterized in that the hydrolysis catalyst is one or more of hydrochloric acid, sulfuric acid, nitric acid and water. 7. The method according to claim 1, characterized in that the stabilizer is one or more of diethanolamine, acetylacetone, ammonia water or ammonia gas. 8. The method according to claim 1, characterized in that after dissolving the titanate or titanate stabilizer in the diluent, adding zinc compound nanoparticles and a hydrolysis catalyst, stirring, and then standing and aging for 30 minutes- After 20 hours, a doped titanium sol-gel solution was obtained. 9. The method according to claim 1, characterized in that coating the zinc-doped sol-gel on the surface of the carrier glass to prepare a titanium dioxide film material with photocatalytic degradation of harmful gases in the air under visible light. At the same time, it has light-induced high hydrophilicity, can be anti-fouling and self-cleaning under sunlight, and has good antibacterial and bactericidal properties.