CN1686890A - One-step treatment process of sol filming for preparing toughening self-cleaning glass with film of titanium dioxide - Google Patents
One-step treatment process of sol filming for preparing toughening self-cleaning glass with film of titanium dioxide Download PDFInfo
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- CN1686890A CN1686890A CN 200510018520 CN200510018520A CN1686890A CN 1686890 A CN1686890 A CN 1686890A CN 200510018520 CN200510018520 CN 200510018520 CN 200510018520 A CN200510018520 A CN 200510018520A CN 1686890 A CN1686890 A CN 1686890A
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Abstract
The present invention relates to a method for preparing tempered anti-bacterial self-cleaning glass. Said method utilizes one-step heat treatment process to make the titanium dioxide base film coated or plated on the glass surface be sintered and converted into anatase crystal type to implement glass tempering so as to obtain the transparent tempered bacteria-killing self-cleaning glass product with good photocatalytic activity photosuperhydrophilicity and anti-bacterial function. Besides, said invention also provides its application range.
Description
Technical field
The present invention be a kind of with sheet glass immersion plating or spraying go up the TiO 2 sol film, to be dried be converted into gel film after, one step thermal treatment is sintered to the titanium deoxid film with one deck anatase crystal with it, forms the method for antibiotic transparent toughening self-cleaning glass.
Background technology
Along with the development of modern society and the raising of people's quality of life, environmental purification and Comfortable Housing Project are subject to people's attention day by day.Science and technology and industrial expansion have improved people's quality of life on the one hand, and the development of Chi Xuing has caused the deterioration of environment for human survival on the other hand, and particularly people produce, pollution, the destruction of the space environment of work activities and living quarter environment.Brought influence to people are healthy, an urgent demand improves environmental quality, and the protection and preventing the pollution of the environment of going into overdrive purifies the room and the environment of an activation in the life and work.Indoor building material is that people produce, use the widest material articles for use of contact at most in the life activity, as glass curtain wall, indoor door and window, dividing plate, cabinet etc., require these materials that high intensity, high shock resistance are arranged on the one hand, good light transmission also requires to have from cleaning, can decompose the purification function of air stink oil smoke, obnoxious flavour and the goods of sterilization anti-microbial property simultaneously.
After finding that anatase titanium dioxide has photocatalysis characteristic, people utilize it to make the photocatalytic self-cleaning material, the clean glass of Photocatalystic self-cleaning TiO 2 occurred, concerning indoor material, expect that also this material is at the low light level or do not have under the light state and also can use.But the present titanium dioxide self-cleaning glass of reporting still is difficult to satisfy people's consumers demand.Subject matter is: the self-cleaning net work energy of (1) glass and the wear resisting property of film are difficult to satisfactory to both parties; (2) present self-cleaning glass must just have good self-cleaning net work energy and anti-microbial property having under sufficient sunlight or the UV-irradiation; (3) preparation of present titanium dioxide self-cleaning glass normally will be coated with the glass of TiO 2 sol film 500 ℃ of left and right sides thermal treatments 30 minutes to 2 hours, add and heat up and the refrigerative time, the manufacturing cycle of self-cleaning glass reaches 4～8 hours, cause the production cost height, energy dissipation is serious.
On the other hand, if be coated with the toughening self-cleaning glass of titanium deoxid film with the traditional method preparation, elder generation's immersion plating titania coated film burnt till to having the anatase titanium dioxide film of photochemical catalysis feature with 30～60 minutes about 500 ℃, and can produce following problem then when 650～750 ℃ of high-temperature steels change into type: (1) can make anatase titanium dioxide partially or completely be converted into the rutile titanium dioxide of no photocatalysis performance; (2) film of glass surface can be damaged, and the outward appearance light transmission degenerates.(3) twice thermal treatment meeting prolong complicated operating process, production cycle, facility investment increases, expend the energy, increase cost.
If earlier with glass tempering, burn till behind the immersion plating TiO 2 sol and be converted into the anatase titanium dioxide film and then following problem can occur: (1) twice thermal treatment meeting makes complicated operating process, and facility investment increases, and expends the energy, increases cost.(2) the more important thing is to make and have the glass finished product forfeiture tempering characteristic of tempering performance.
Summary of the invention
The objective of the invention is problem such as to grow, wear no resistance, can not round-the-clockly use for the preparation cycle that solves above-mentioned self-cleaning glass, provide a kind of architectural decoration have photochemical catalysis, from the glass of clean, antibiotic, transparent, shock-resistant and wear-resisting functions, this is with short production cycle, save the energy, cost is low, and the preparation method that can finish with a step thermal treatment.
A kind of method that is used to make the clean glass of tempering antibiosis and self-cleaning of the present invention, with sheet glass is matrix, with the TiO 2 sol gel method plated film that lifts or spray, and carry out tempering and handle the transparent toughened glass goods that obtain to have the photocatalysis antibacterial self-cleaning property, it is characterized in that preparation process is as follows:
1st, glass substrate is cut, edging shaping, cleaning, drying;
2nd, the TiO 2 sol of preparation TiO 2 sol and doping antimicrobial additive, titanate concentration is 0.01～1mol/L;
3rd,, and carry out drying treatment with the TiO 2 sol employing dip-coating method or the spray method plated film of the dried glass substrate of step 1 with step 2 preparation TiO 2 sol or doping antimicrobial additive;
4th, step 3 has been plated the TiO 2 sol film, or plated the dried glass of TiO 2 sol film of doping antimicrobial additive, carry out disposable typing thermal treatment, make the titanium dioxide film of its titanium dioxide porous membrane that changes the anatase octahedrite crystal type into or doping antiseptic-germicide, and make and become toughened glass;
5th, the toughened glass concentration of the titanium dioxide film of titanium dioxide porous membrane that step 4 is obtained or doping antiseptic-germicide is that hydrochloric acid, nitric acid or the sulphuric acid soln of 0.5～1.5mol/L carries out acid treatment, washing then, hot-air dry promptly makes the transparent toughened glass with self-cleaning property or has germ resistance and the transparent toughened glass of self-cleaning property.
Described acid treatment is with soaking 1 hour in hydrochloric acid, nitric acid or the sulphuric acid soln of concentration 1mol/L.
Described sheet glass size and dimension color is set according to service requirements.
The TiO that described transparent toughened glass is plated
2Film thickness is between 50～300 nanometers.
Wherein when adopting dip-coating method to prepare the TiO 2 sol plated film of TiO 2 sol or doping antiseptic-germicide, the lowering speed of dipping is 20～50cm/min, and the pull rate behind the dipping is 10～40cm/min.Glass substrate is wanted vertical hanging after adopting dip-coating method plating TiO 2 sol film, in air or adopt hot blast and infrared rays to carry out thorough drying.
Described disposable thermal is handled method for shaping: after glass substrate adopts dip-coating method or spray method plated film drying with TiO 2 sol, directly glass is placed in 620～760 ℃ of the high temperature by room temperature and heated 1～6 minute, with thickness of glass, vary in size and set, use high wind to blow then, make it carry out the chilling tempering to room temperature at 2～5 minutes internal cooling.Heating is that the organism in filming is decomposed, and is converted into Detitanium-ore-type TiO
2Make its crystallization typing and tempering by quench.
Above-mentioned TiO 2 sol is prepared by the titanate hydrolysis method, titanate is positive butyl (tetra) titanate, one or both combinations of isopropyl titanate, titanate concentration is 0.01～1mol/L, solvent for use is that ethanol is or/and Virahol, added the complexing stablizer in the TiO 2 sol, stable sol also plays the viscosity modifier effect, the complexing stablizer is a diethanolamine, trolamine, in methyl ethyl diketone and the Diethylene Glycol one or both the combination, its add-on be in the colloidal sol titanium dioxide quality 0.05～10%.
Described additive silver salt or mantoquita mixture with sterilization anti-microbial effect, silver salt uses Silver Nitrate, mantoquita uses cupric nitrate or copper sulfate, complex silver salts or copper salt solution are that silver salt or mantoquita are dissolved in the water, add diethanolamine, levulinic cave, one or both complexing stablizers in the Diethylene Glycol, add in the colloidal sol plating bath after rare with ethanol, its add-on is that silver salt or mantoquita concentration are 1～10 * 10 in the colloidal sol plating bath again
-5Mol/L.Being made into complex liquid could add, and to avoid precipitation and destroys coating colloidal sol mother liquor.
Embodiment:
The preparation of glass substrate: glass substrate is by pre-sizing, and size shape is ready to, edging, washing drying for standby.
The TiO 2 sol compound method is as follows: with butyl (tetra) titanate, be dissolved in organic solvent under constantly stirring, in dehydrated alcohol, add diethanolamine or other complexing stablizer simultaneously, with the hydrolysis rate of control butyl (tetra) titanate.Stir after 2 hours the water that adds again with the titanium equimolar amount by the butyl (tetra) titanate hydrolysis, strengthen anti-microbial property as need, need to add antiseptic-germicide silver or/and the mixture of copper stirs after 30 minutes and should remove by filter impurity as becoming turbid, obtain yellow transparent colloidal sol, leave standstill after 12 hours and promptly can be used for plated film.Plated film adopts dip-coating method or spray method.The gained gel-film at air drying more than 1 hour, or about 110 ℃ dry 5～30 minutes, is directly put into exsiccant gelatin plating glass High Temperature Furnaces Heating Apparatus sintering transition and tempering under design temperature then and handled.The size of High Temperature Furnaces Heating Apparatus temperature and heat-up time and glass substrate, thickness is relevant.Whether fully and TiO temperature is 620～760 ℃, 1～6 minute heat-up time, look organic decomposition
2Crystal conversion is that the Detitanium-ore-type situation is decided.Cross low temperature and spend the short period of time the two is transformed not exclusively, temperature is too high, TiO
2Crystal formation can change rutile-type into and promptly lose photocatalytic activity, and causes glass substrate distortion and can not get predetermined result.After time to be heated arrives, glass substrate is made its typing by taking out and be cooled to room temperature with high wind in the stove.Speed of cooling should make substrate reach room temperature in 2～5 minutes.After the cooling, at room temperature carry out acid treatment again, diffuse into sodium plasma in the film to remove in the heat treatment process by glass substrate.
The toughening self-cleaning glass that adopts present method to prepare has good photocatalytic activity and photic Superhydrophilic makes glass have self-cleaning net work energy, have the good wear resistance and the transparency simultaneously, strength of glass reaches the degree of toughened glass, the coated glass that does not contain antiseptic-germicide has germ resistance having under sunlight or the UV-irradiation, the coated glass that contains antiseptic-germicide unglazed according to the time also have a good antibacterial effect.
Embodiment 1:
1, the preparation of TiO 2 sol plating bath
With the butyl (tetra) titanate is main raw material, and it is in 1: 3 the dehydrated alcohol that the butyl (tetra) titanate that calculates good amount is dissolved in volume ratio.In wherein adding entry and diethanolamine, its volume ratio is a water: butyl (tetra) titanate: diethanolamine=1: 17: 5, and being diluted with ethanol to cumulative volume at last is 100, filters then, gets faint yellow transparent clear sol, leaves standstill more than 12 hours standby;
2, the coated glass substrate is prepared: plated film is to carry out in stainless steel tank, with substrate on request size cut out and cut edging, clean, in 105～110 ℃ of dryings 10 minutes;
3, adopt the pickling process plated film, glass substrate is descended with 50cm/min speed, dipping lifted vertically upward with 24cm/min speed after 1 minute in the plating bath of step 1 gained, then 105～110 ℃ of dryings 15 minutes;
4, adopt the vertical hanging mode that coated glass is directly put into rectilinear heat treatment furnace, 720～730 ℃ of furnace temperature are incubated 2.5 minutes, shift out rapidly with high wind blast-cold method cooling 2 minutes and 30 seconds;
5, with cooled glass after concentration is to soak 1 hour in the aqueous sulfuric acid of 1mol/L, washing, air-dry promptly gets the toughening self-cleaning glass goods again.
The intensity of this toughening self-cleaning glass reaches the toughened glass standard, is reduced to below 3 ° with the wetting angle of water after 1 hour at solar irradiation, and photocatalytic degradation acetone velocity constant is 2 * 10
-2/ min reaches 100% to colibacillary killing rate.
Embodiment 2:
1, mixes the preparation of silver-colored TiO 2 sol plating bath
With the butyl (tetra) titanate is main raw material, and it is that in wherein adding entry and diethanolamine, its volume ratio is a water: butyl (tetra) titanate: diethanolamine=1: 17: 5 in 1: 3 the dehydrated alcohol that the butyl (tetra) titanate that calculates good amount is dissolved in volume ratio.Being diluted with ethanol to cumulative volume at last is 100, adds bactericidal additive silver salt mixture thereafter, and add-on is 2 * 10 of a content of titanium dioxide
-5, continue to stir 1 hour after-filtration, get faint yellow transparent clear sol, leave standstill more than 12 hours standby;
2, the coated glass substrate is prepared: plated film is to carry out in stainless steel tank, with glass substrate on request size cut out and cut edging, clean, in 105～110 ℃ of dryings 10 minutes;
3, adopt the pickling process plated film, glass substrate is descended with 50cm/min speed, dipping lifted vertically upward with 24cm/min speed after 1 minute in the plating bath of step 1 gained, then 105～110 ℃ of dryings 15 minutes;
4, adopt the vertical hanging mode that coated glass is directly put into rectilinear heat treatment furnace, 720～730 ℃ of furnace temperature are incubated 2.5 minutes, shift out rapidly with high wind blast-cold method cooling 2 minutes and 30 seconds;
5, with cooled glass after concentration is to soak 1 hour in the aqueous sulfuric acid of 1mol/l, washing, air-dry promptly gets tempering sterilization self-cleaning glass goods again.
The intensity of this tempering sterilization self-cleaning glass reaches the toughened glass standard, is reduced to below 3 ° with the wetting angle of water after 1 hour at solar irradiation, and photocatalytic degradation acetone velocity constant is 2.2 * 10
-2/ min reaches 100% to colibacillary killing rate.Unglazed according to the time, after 1 hour the killing rate of golden staphylococci reached that the killing rate to golden staphylococci reaches 99.9% after 92%, 24 hour, the killing rate of colon bacillus is reached 98%.
Embodiment 3
1, the preparation of TiO 2 sol plating bath is with embodiment 1 step 1;
2, glass substrate is prepared with embodiment 1 step 2;
3, the one-sided spraying coating method is filmed on glass substrate, adopt the colloidal sol spray method to film, TiO 2 sol is packed in the spray tank, start air pressure switch, adjust air pressure and make ejection colloidal sol reach fogging degree, glass substrate lies against on the fixed support, and support pushes the spray chamber by the transfer roller transmission mechanism, spray chamber's nozzle is located at the upper end, multiple spot distributes, and can obtain even one-sided spraying and film when substrate moves transmission;
4, a step sinter molding, the single face coated glass is placed on the transfer roller travelling belt, face up, directly be sent in the high temperature sintering chamber, agglomerating chamber comes and goes driven type for the transfer roller cycle, and temperature is set at 720～730 ℃, and the time is 3 minutes, sintering is directly sent into the cooling room cooling and shaping after finishing, and makes glass substrate be cooled to room temperature in 3 minutes;
5, with cooled glass after concentration is to soak 1 hour in the aqueous sulfuric acid of 1mol/L, washing, air-dry promptly gets the toughening self-cleaning glass goods again.
The intensity of this toughening self-cleaning glass reaches the toughened glass standard, is reduced to below 3 ° with the wetting angle of water after 1 hour at solar irradiation, and photocatalytic degradation acetone velocity constant is 2 * 10
-2/ min reaches 100% to colibacillary killing rate.
Embodiment 4:
1, TiO 2 sol steeping fluid method for making is with embodiment 1 step 1;
2, glass substrate is prepared with embodiment 1 step 2;
3, two-sided sprayed on membrane method is filmed on glass substrate, adopt the colloidal sol spray method to film, TiO 2 sol is packed in the spray tank, starts air pressure switch, adjusts pressure and makes ejection colloidal sol reach fogging degree, glass substrate vertically places on the fixed support, support pushes in the spray chamber by the transfer roller transmission mechanism, and spray nozzle is located at both sides, and multiple spot distributes, when substrate moves transmission, can obtain even double-face spray painting film;
4, a step sinter molding, two-sided coating base can not use and keep flat the transfer roller transmission, can scrape the damage face like this, can not get evenly harmless plated film.Adopt the vertical hanging method herein, directly push in the rectilinear heat treatment furnace, 720～730 ℃ of furnace temperature shift out rapidly 2 minutes and 30 seconds heat-up time then, and high wind blast-cold mode was cooled off 2 minutes and 30 seconds.
5, with cooled glass after soaking 1 hour in the aqueous hydrochloric acid that in concentration is 1mol/L, washing, air-dry promptly obtains the toughening self-cleaning glass goods again.
The intensity of this toughening self-cleaning glass meets or exceeds the toughened glass standard, is reduced to below 3 ° with the wetting angle of water after 1 hour at solar irradiation, and photocatalytic degradation acetone velocity constant is 2 * 10
-2/ min reaches 100% to colibacillary killing rate.
Claims (7)
1, a kind of method that is used to make the clean glass of tempering antibiosis and self-cleaning, with sheet glass is matrix, with the TiO 2 sol gel method plated film that lifts or spray, and carry out tempering and handle the transparent toughened glass goods that obtain to have the photocatalysis antibacterial self-cleaning property, it is characterized in that preparation process is as follows:
1st, glass substrate is cut, edging shaping, cleaning, drying;
2nd, the TiO 2 sol of preparation TiO 2 sol and doping antimicrobial additive, titanate concentration is 0.01～1mol/L;
3rd,, and carry out drying treatment with the TiO 2 sol employing dip-coating method or the spray method plated film of the dried glass substrate of step 1 with step 2 preparation TiO 2 sol or doping antimicrobial additive;
4th, step 3 has been plated the TiO 2 sol film, or plated the dried glass of TiO 2 sol film of doping antimicrobial additive, carry out disposable typing thermal treatment, make the titanium dioxide film of its titanium dioxide porous membrane that changes the anatase octahedrite crystal type into or doping antiseptic-germicide, and make and become toughened glass;
5th, the toughened glass concentration of the titanium dioxide film of titanium dioxide porous membrane that step 4 is obtained or doping antiseptic-germicide is that hydrochloric acid, nitric acid or the sulphuric acid soln of 0.5～1.5mol/L handled, washing then, hot-air dry promptly makes the transparent toughened glass with self-cleaning property or has germ resistance and the transparent toughened glass of self-cleaning property.
2,, it is characterized in that TiO2 film thickness that described transparent toughened glass plates is between 50～300 nanometers by the described method of claim 1.
3, by the described method of claim 1, during the TiO 2 sol plated film that it is characterized in that adopting dip-coating method to prepare TiO 2 sol or doping antiseptic-germicide, the lowering speed of dipping is 20～50cm/min, and the pull rate behind the dipping is 10～40cm/min.
4,, it is characterized in that wanting vertical hanging, thorough drying after glass substrate adopts dip-coating method plating TiO 2 sol film by the described method of claim 1.
5, by the described method of claim 1, it is characterized in that described disposable thermal processing method for shaping is: after glass substrate adopts dip-coating method or spray method plated film drying with TiO 2 sol, directly glass is placed in 620～760 ℃ of the high temperature by room temperature and heated 1～6 minute, use high wind to blow then, make it carry out the chilling tempering to room temperature at 2～5 minutes internal cooling.
6, by the described method of claim 1, it is characterized in that TiO 2 sol is to use butyl (tetra) titanate or/and isopropyl titanate, with ethanol or/and Virahol be mixed with as solvent, and added the complexing stablizer, the complexing stablizer is a diethanolamine, the levulinic cave, one or both in the Diethylene Glycol, the complexing consistent dose be in the colloidal sol titanium dioxide quality 0.05～10%.
7, by the described method of claim 6, it is characterized in that in TiO 2 sol, having added additive silver salt or mantoquita mixture with sterilization anti-microbial effect, silver salt uses Silver Nitrate, mantoquita uses cupric nitrate or copper sulfate, complex silver salts or copper salt solution are that silver salt or mantoquita are dissolved in the water, add diethanolamine, the levulinic cave, one or both complexing stablizers in the Diethylene Glycol, add in the colloidal sol plating bath after rare with ethanol, add-on is that silver salt or mantoquita concentration are 1～10 * 10 in the colloidal sol plating bath again
-5Mol/L.
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| KR100365663B1 (en) * | 1994-10-31 | 2003-02-25 | 카나가와 아카데미 오브 사이언스 앤드 테크놀로지 | Titanium oxide photocatalyst structure and its manufacturing method |
| US5811192A (en) * | 1996-01-12 | 1998-09-22 | Matsushita Electric Works, Ltd. | Titanium dioxide film having photocatalytic activity and substrate having the same |
| CN1197803C (en) * | 2001-07-31 | 2005-04-20 | 武汉理工大学 | Method for preparing high-activity titanium dioxide film self-cleaning glass material |
| CN1189412C (en) * | 2001-07-31 | 2005-02-16 | 武汉理工大学 | Method for raising titanium dioxide film self-cleaning glass photocatalytic activity |
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