CN1174938C - Photocatalystic self-cleaning TiO2 ceramic and its prepn. - Google Patents
Photocatalystic self-cleaning TiO2 ceramic and its prepn. Download PDFInfo
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- CN1174938C CN1174938C CNB011283874A CN01128387A CN1174938C CN 1174938 C CN1174938 C CN 1174938C CN B011283874 A CNB011283874 A CN B011283874A CN 01128387 A CN01128387 A CN 01128387A CN 1174938 C CN1174938 C CN 1174938C
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Abstract
The present invention relates to photocatalystic self-cleaning titanium dioxide ceramic and a preparation method thereof. The ceramic comprises a ceramic body or a ceramic finished product. The glaze surface of the ceramic body or the ceramic finished product is tightly compounded with a photocatalysis film and low temperature glaze, wherein the photocatalysis film takes nano titanium dioxide as the main component. Quartz, limestone, borax, Zinc oxide and zircon are mixed and sintered into low temperature fritted glaze with the temperature of 950 to 1000 DEG C. Kaolin clay, water and adhesive are uniformly mixed and made into glaze slurry. The glaze slurry is sintered to the ceramic body or the glaze surface of the ceramic finished product by the exiting glazing and sintering technology and the device. Titanium oxide sol is loaded onto the ceramic glaze surface, and the required photocatalysis self-cleaning titanium oxide ceramic is sintered. The present invention has no need of using dissolvent of distilled water, acetone, etc. to clean the ceramic glaze surface, and can simplify process and reduce industrial cost. The surface of the ceramic product prepared by the present invention is smooth, beautiful and moderate, forms silvery white or silver yellow, has acid base resitance and scraping prevention, not only has the surface performance of fineness and smoothness of the traditional ceramic, but also has automatic soil removal, lasting clean keep and beautiful appearance.
Description
Technical field
The present invention relates to Photocatalystic self-cleaning TiO 2 ceramic and preparation method thereof.
Background technology
Ceramic is widely used building and ornament materials, but owing to reason atmospheric pollutions such as industrial expansion, emission of automobile wastes cause the traditional ceramics goods in use, performance deposits all contaminations and deepening gradually, dirty and influence decorative effect gradually.Need the cost great amount of manpower and material resources to clean.
Summary of the invention
Problem to be solved by this invention provide a kind of not only can keep the fine and smooth bright and clean apparent characteristic of traditional ceramics but also can automated decontamination, the beautiful Photocatalystic self-cleaning TiO 2 ceramic and preparation method thereof that keeps clean lastingly.
Technical scheme provided by the invention is: Photocatalystic self-cleaning TiO 2 ceramic, comprise ceramic body or ceramic finished product, its key is: closely being compounded with on the ceramic body or on the glaze of ceramic finished product by nano titanium oxide is the photocatalysis thin film and the low temperature glaze of main component, the glaze formula of low temperature glaze is quartzy 25-30 part, Wingdale 4-5 part, borax 28-30 part, zinc oxide 8-10 part, zircon 5-8 part, more than be mass fraction, it with above-mentioned component mixing firing temperature 950-1000 ℃ low temperature frit glaze, with above-mentioned frit 92-96 part, kaolin 4-8 part, add 50-100 part water, the water-soluble organic polymer binder of 0-2 part (being mass fraction) mixes makes glaze slip, adopts existing glazing, firing process and equipment fire on the ceramic body or the glaze of ceramic finished product on.The gained glaze is smooth, fine and smooth, gentle, attractive in appearance, is beige, and is sub-translucent, acid and alkali-resistance, tension mill.
Above-mentioned photocatalysis thin film can be with low-carbon (LC) (C
1-4) alcohol is raw material as ethanol, butanols etc., metatitanic acid fat or strong acid oxygen titanium salt, water, by 100: 5-20: the mixed of 1.5 volume percent is made TiO 2 sol, and employing dip-coating or spraying method load to TiO 2 sol on the Ceramic glaze and obtain.
The present invention also provides the preparation method of above-mentioned Photocatalystic self-cleaning TiO 2 ceramic, with 25-30 part quartz, 4-5 part Wingdale, 28-30 part borax, 8-10 part zinc oxide, it is 950-1000 ℃ low temperature frit glaze that 5-8 part zircon (more than be mass fraction) mixes firing temperature, with above-mentioned frit 92-96 part, kaolin 4-8 part, add 50-100 part water, the agent of 0-2 part aforementioned adhesion mixes makes glaze slip, adopt existing glazing, firing process and equipment fire on the ceramic body or the glaze of Tao Cuihua porcelain finished product on, titanium dichloride load is compound to Ceramic glaze and adopts sol-gel technique, with metatitanic acid lipid as raw material under the acidity condition of pH=3-4, be added drop-wise to slowly hydrolysis in the ethanol, vigorous stirring prepares the titanium dioxide melten gel simultaneously, adopt dip-coating or spraying method that TiO 2 sol is loaded to Ceramic glaze, under 500-700 ℃ temperature calcination 1-3 hour, can obtain required Photocatalystic self-cleaning TiO 2 ceramic.
Above-mentioned low temperature glaze fire on the ceramic body or the glaze of ceramic finished product on, after ash is blown in cooling, carry out dip-coating or spraying TiO 2 sol immediately.To avoid Ceramic glaze to pollute TiO 2 sol is come off or pollute.This technology need not use distilled water, acetone equal solvent that Ceramic glaze is cleaned, and can simplify technology and reduce industrial cost.
The ceramic any surface finish exquisiteness attractive in appearance, gentle that the present invention is prepared is silvery white in color or the silver yellow look acid and alkali-resistance, anti-scratch mill.Under the irradiation of light, the various organism of the deposition surface of degrading have super hydrophilic simultaneously, and this specific character can make water soak into the surface better, is beneficial to the wash-out surface mass.Under normal conditions, the pollutent of ceramic surface is organism and inorganic dust granules mixture.The prepared ceramic of the present invention can be under illumination (as the sunlight incandescent light etc.), effective degraded organism wherein, and remaining inorganic dust thing is wind-force outside, and self gravitation comes off under the effects such as rain drop erosion power and the surface is kept clean lastingly.A large amount of uses are also capable of purifying air.Thereby by gained titanium dioxide self cleaning enamel of the present invention not only have the fine and smooth bright and clean apparent characteristic of traditional ceramics have again automated decontamination, lastingly keep clean attractive in appearance.
The present invention can be used for making wall, ornamental brick, sanitary china, ceramics such as household china are used for decorative constructure, communal facility, family room, lavatory, kitchen etc.
Embodiment
Embodiment 1: get 30 parts in quartz, 20 parts of feldspars, 5 parts in Wingdale, 30 parts of boraxs, 8 parts in zinc oxide, 8 parts of zircons (mass fraction), mix the back and cross 200 mesh sieves after 1000 ℃ of following fusions, hardening, fine grinding; Get 96 parts in this fritted glaze powder and 4 parts of kaolin, water 60-70 part (mass fraction), be mixed and made into flowable glaze slip and adopt existing glazing technology such as waterfall process to impose on ripe base surface, burn till stand-by at 960 ℃.
75 parts of ethanol (volume parts, down with) and 1.5 parts of redistilled waters are under agitation dripped nitric acid regulate pH=3-4, then 10 parts of positive fourth fat of metatitanic acid and 25 parts of ethanol are mixed the back and under violent stirring, be added drop-wise in the aforementioned solution, get faint yellow vitreosol.
Adopt dip-coating method of the prior art, the ceramic (need not clean) that newly burns out is vertically lifted out liquid level with the speed of 5-15cm/min; In the time of need repeatedly filming, sample at room temperature can be placed behind the 20-40min once more dipping and be lifted and film; The last dustless placement sample of room temperature is after about 12 hours, 600 ℃ of following calcinations 2 hours, cooling is taken out and promptly to be got any surface finish exquisiteness attractive in appearance, gentle, is silvery white in color or silver yellow look, acid and alkali-resistance, anti-scratch mill, self-cleaning function ceramic with characteristics such as self-cleaning decontamination, super hydrophilics.
Embodiment 2: get 25 parts in quartz, 20 parts of feldspars, 4 parts in Wingdale, 28 parts of boraxs, 10 parts in zinc oxide, 6 parts of zircons (mass fraction), mix the back and cross 200 mesh sieves after 950 ℃ of following fusions, hardening, fine grinding; Get 92 parts in this fritted glaze powder and 8 parts of kaolin, water 60-70 part, 1 part of polyvinyl alcohol (mass fraction), be mixed and made into flowable glaze slip and adopt existing glazing technology such as waterfall process to impose on ripe base surface, burn till stand-by at 1000 ℃.
75 parts of butanols (volume parts, down with) and 1.5 parts of redistilled waters are under agitation dripped nitric acid regulate pH=3-4, then 25 parts of butanols of 15 parts of titanyl sulfates are mixed the back and under violent stirring, be added drop-wise in the aforementioned solution, faint yellow vitreosol.
Adopt dip-coating method of the prior art, the ceramic (need not clean) that newly burns out is vertically lifted out liquid level with the speed of 5-15cm/min; In the time of need repeatedly filming, sample at room temperature can be placed behind the 20-40min once more dipping and be lifted and film; The last dustless placement sample of room temperature is after about 12 hours, 500 ℃ of following calcinations 3 hours, cooling is taken out and promptly to be got any surface finish exquisiteness attractive in appearance, gentle, is silvery white in color or silver yellow look, acid and alkali-resistance, anti-scratch mill, self-cleaning function ceramic with characteristics such as self-cleaning decontamination, super hydrophilics.
Embodiment 3: get 28 parts in quartz, 18 parts of feldspars, 5 parts in Wingdale, 29 parts of boraxs, 8 parts in zinc oxide, 5 parts of zircons (mass fraction), mix the back and cross 200 mesh sieves after 980 ℃ of following fusions, hardening, fine grinding; Get 94 parts in this fritted glaze powder and 6 parts of kaolin, water 60-70 part, 1.5 parts of polyglycol (mass fraction), be mixed and made into flowable glaze slip and adopt existing glazing technology such as waterfall process to impose on ripe base surface, burn till stand-by at 980 ℃.
75 parts of methyl alcohol (volume parts, down together) are under agitation dripped nitric acid with 1.5 parts of redistilled waters regulate pH=3-4, then 5 parts of metatitanic acid second fat and 25 parts of methanol mixed evenly are added drop-wise under violent stirring in the aforementioned solution back, get faint yellow vitreosol.
Adopt dip-coating method of the prior art, the ceramic (need not clean) that newly burns out is vertically lifted out liquid level with the speed of 5-15cm/min; In the time of need repeatedly filming, sample at room temperature can be placed behind the 20-40min once more dipping and be lifted and film; The last dustless placement sample of room temperature is after about 12 hours, 700 ℃ of following calcinations 1 hour, cooling is taken out and promptly to be got any surface finish exquisiteness attractive in appearance, gentle, is silvery white in color or silver yellow look, acid and alkali-resistance, anti-scratch mill, self-cleaning function ceramic with characteristics such as self-cleaning decontamination, super hydrophilics.
Claims (3)
1. Photocatalystic self-cleaning TiO 2 ceramic, comprise ceramic body or ceramic finished product, it is characterized in that: being compounded with by nano titanium oxide on the ceramic body or on the glaze of ceramic finished product is the photocatalysis thin film of main component and the low temperature glaze that firing temperature is 950-1000 ℃, the glaze formula of low temperature glaze is quartzy 25-30 part, Wingdale 4-5 part, borax 28-30 part, zinc oxide 8-10 part, zircon 5-8 part, more than be mass fraction, it with above-mentioned component mixing firing temperature 950-1000 ℃ low temperature frit glaze, with above-mentioned frit 92-96 part, kaolin 4-8 part, 50-100 part water, the water-soluble organic polymer binder of 0-2 part mixes makes glaze slip, adopts glazing, firing process and equipment fire on the ceramic body or the glaze of ceramic finished product on; Above-mentioned photocatalysis thin film is with C
1-4Low-carbon alcohol, metatitanic acid fat or strong acid oxygen titanium salt, water be raw material, by 100: 5-20: the mixed of 1.5 volume percent is made TiO 2 sol, adopts dip-coating or spraying method that TiO 2 sol is loaded on the Ceramic glaze.
2. the preparation method of the described pottery of claim 1, with mass fraction is that 25-30 part quartz, 4-5 part Wingdale, 28-30 part borax, 8-10 part zinc oxide, 5-8 part zircon mixing firing temperature are 950-1000 ℃ low temperature frit glaze, with above-mentioned frit 92-96 part, kaolin 4-8 part add 50-100 part water, the water-soluble organic polymer binder of 0-2 part mixes and makes glaze slip, adopt glazing, firing process and equipment is fired on the ceramic body or the glaze of ceramic finished product on; Titanium dichloride load is compound to Ceramic glaze and adopts sol-gel technique, with metatitanic acid fat or strong acid oxygen titanium salt as raw material under the acidity condition of pH=3-4, be added drop-wise to C
1-4Low-carbon alcohol in slowly hydrolysis, vigorous stirring prepares the titanium dioxide melten gel simultaneously, adopt dip-coating or spraying method that TiO 2 sol is loaded to Ceramic glaze, under 500-700 ℃ temperature calcination 1-3 hour, can obtain required Photocatalystic self-cleaning TiO 2 ceramic.
3. preparation method according to claim 2 is characterized in that: low temperature glaze fire on the ceramic body or the glaze of ceramic finished product on, after ash is blown in cooling, carry out dip-coating or spraying TiO 2 sol immediately.
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CNB011283874A CN1174938C (en) | 2001-08-30 | 2001-08-30 | Photocatalystic self-cleaning TiO2 ceramic and its prepn. |
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CNB011283874A CN1174938C (en) | 2001-08-30 | 2001-08-30 | Photocatalystic self-cleaning TiO2 ceramic and its prepn. |
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CN1174938C true CN1174938C (en) | 2004-11-10 |
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Families Citing this family (15)
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CN1297519C (en) * | 2003-10-24 | 2007-01-31 | 蔡日馨 | Nanometer glaze with far infrared radiating function and its application |
CN1304126C (en) * | 2005-04-28 | 2007-03-14 | 湖南泰鑫瓷业有限公司 | Method for manufacturing nano TiO2 composite antibacterial membrane |
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WO2008152154A1 (en) * | 2007-06-14 | 2008-12-18 | Cerámica La Escandella, S.A. | Ceramic glaze, method for obtaining age-resistant glazed tiles and resulting tile |
CN101417893B (en) * | 2008-11-28 | 2011-08-31 | 河北理工大学 | Nano phase separation self-cleaning glaze of sanitary ware |
CN101786794B (en) * | 2010-01-26 | 2012-08-08 | 福建省水产研究所 | Nano-titanium energy-saving radiation layer, energy saver and manufacturing methods thereof |
CN104513066B (en) * | 2013-09-30 | 2017-02-08 | 佛山市克里普斯科技有限公司 | Low temperature ceramic glaze manufacturing method |
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CN104446667B (en) * | 2014-10-30 | 2017-01-25 | 四川省达州质量技术监督检验测试中心 | Method and device for producing surface self-cleaning tiles |
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CN107903025A (en) * | 2017-11-24 | 2018-04-13 | 任合超 | It is a kind of except pottery product of formaldehyde and preparation method thereof |
CN111233325A (en) * | 2020-02-27 | 2020-06-05 | 福建省德化县华瓷新材料科技有限公司 | Nano TiO (titanium dioxide)2Self-cleaning functional ceramic and preparation method and application thereof |
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CN114573232A (en) * | 2022-04-06 | 2022-06-03 | 福建省漳州瑞成陶瓷有限公司 | Tile-splitting glaze for ceramic tiles and method for preparing ceramic tiles |
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