CN104876646A - Anti-bacterial glaze and preparation method thereof - Google Patents
Anti-bacterial glaze and preparation method thereof Download PDFInfo
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- CN104876646A CN104876646A CN201510273287.XA CN201510273287A CN104876646A CN 104876646 A CN104876646 A CN 104876646A CN 201510273287 A CN201510273287 A CN 201510273287A CN 104876646 A CN104876646 A CN 104876646A
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Abstract
The invention discloses an anti-bacterial glaze and a preparation method thereof. The glaze comprises the following raw materials in parts by mass: 40-50 parts of titanium dioxide, 0.5-0.8 part of zinc nitrate, 0.5-0.8 part of cerous nitrate, 3-5 parts of glacial acetic acid, 8-12 parts of distilled water, 30-40 parts of absolute ethyl alcohol, 0.2-0.3 part of a surfactant and 800-1200 parts of granite. The preparation method comprises the following steps: preparing an antibacterial agent, mixing for preparing glaze slip and sintering at a high temperature, so as to obtain the anti-bacterial glaze. According to the ceramic glaze with an anti-bacterial function, provided by the invention, by modifying titanium dioxide and doping titanium dioxide with related metal elements, a visible region of the titanium dioxide is enabled to have an antibacterial property; moreover, the ratio of all components is scientific and reasonable, a glaze surface is smooth, uniform color, good dispersity, high acid resistance and high alkali resistance are realized and the application range is wider.
Description
Technical field
The present invention relates to silicates arts, be specifically related to a kind of antibacterial glaze and preparation method thereof.
Background technology
China is Production of Ceramics and consumption big country, current architectural pottery annual production reaches more than 6.5 hundred million square metres, ceramic sanitary appliance about 6,000 ten thousand, along with the progress of social civilization, with the change of environment, people have been not content with the general utility functions such as attractive in appearance, durable of traditional ceramics, more wish to have the functions such as sterilization, sterilization, deodorizing.
Traditional ceramics is based on white, and glaze paint only adopts zirconium silicate to play white effect, there is no other functions, and traditional ceramics glaze paint is rough under magnifying glass, makes dirt, bacterium is easy to hide, breed; Afterwards, after traditional ceramics fires finished product, add later stage film thermal treatment, not through high-temperature firing, film poor stability, easily peels off, and finally loses antifouling and antibiosis effect, therefore needs to introduce anti-biotic material.
Prior art purposes is inorganic antibacterial material the most widely, and inorganic antibacterial material is divided into again metal ion type inorganic antibacterial material, photocatalyst-type inorganic antibacterial material; Metal ion type inorganic antibacterial material generally uses Ag
+ion is as antibacterial carrier, but Ag is as one of precious metal, and the high and easily variable color of Ag ion cost, therefore the application of Ag ion is very restricted.
And photocatalyst-type anti-biotic agent is having under light activated condition, produce active oxygen and indirectly bacterium is killed the inorganic antibacterial material reaching antibacterial effect.Photocatalysis antibacterial material is the photocatalyst material of the non-dissolving type of a based semiconductor compound, under the irradiation of UV-light, has well suppress and killing action various common pathogenic bacterium, it by photochemical catalytic oxidation by CO
x, SO
xthe organic pollutants such as waste gas, muriate and You Ji Pity decompose, and reach innoxious.Photocatalyst-type inorganic antiseptic is generally with TiO
2be main.Using titanium dioxide to be direct interpolation in prior art, without respective physical change in mixture, is the equal of " pure " titanium dioxide, but, find that " pure " titanium dioxide is without germ resistance under visible light according to the study.
Therefore need a new making method badly, add a kind of new titanium dioxide in glaze, make the glaze produced also have germ resistance under visible light.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of antibacterial glaze containing titanium dioxide, solve the limitation of above-mentioned technology.
For achieving the above object, technical scheme of the present invention is: a kind of antibacterial glaze, and raw material comprises antiseptic-germicide and granite, and antiseptic-germicide comprises titanium dioxide, zinc nitrate, cerous nitrate, Glacial acetic acid, distilled water, dehydrated alcohol, tensio-active agent; By massfraction: titanium dioxide 40 ~ 50 parts, zinc nitrate 0.5 ~ 0.8 part, cerous nitrate 0.5 ~ 0.8 part, 3 ~ 5 parts, Glacial acetic acid, distilled water 8 ~ 12 parts, dehydrated alcohol 30 ~ 40 parts, 0.2 ~ 0.3 part, tensio-active agent, granite 800 ~ 1200 parts;
A making method for antibacterial glaze, comprises the steps: that antiseptic-germicide is prepared separately, comprises the steps:
The preparation of a, antiseptic-germicide: Glacial acetic acid and distilled water are added in dehydrated alcohol simultaneously, add zinc nitrate and cerous nitrate again, add tensio-active agent afterwards, make electricity consumption agitator vigorous stirring, stirring velocity is greater than 200r/min, obtain mixing solutions, adding titanium dioxide while stirring can obtain antiseptic-germicide;
B, mixed pulp: first granite is carried out fragmentation, be mixed in proportion with antiseptic-germicide afterwards, carries out wet ball grinding afterwards, and the granite after ball milling sieves the removal of impurity, makes glaze slip;
C, high temperature burn till: glaze slip is made frit, and temperature is at 800 ~ 1200 DEG C; Firing time is 3 ~ 5h, is incubated 10 ~ 30min afterwards, cool to room temperature, can obtain antibacterial glaze.
Beneficial effect of the present invention: (1) Ti02 is a kind of extraordinary photocatalysis antibacterial material, has that photocatalytic activity is high, good stability, harmless, low cost and other advantages; Zine ion has certain antibacterial effect and the low colour stable of cost, toxicity are little; Ce is one of rare earth element, and rare earth ion, due to security and broad spectrum antibacterial, is also used to anti-biotic material for a long time at field of medicaments; (2) pure titinium dioxide is under visible light without germ resistance, therefore, by doped metal ion, its photoresponse scope is extended to visible region to improve its quantum yield, makes the titanium dioxide of doping zinc and cerium possess photocatalysis performance in visible region.The present invention has the ceramic glaze of antibacterial, and by by titania modified, the metallic element that doping is relevant, makes to possess germ resistance in its visible region; Each component proportioning is scientific and reasonable simultaneously, and glaze paint is smooth, uniform color, good dispersity, and acid-fast alkali-proof, the scope of application is more extensive.
Further, granite is granite waste material, and not leaded; Granite is one of a kind of widely distributed, resourceful rock, along with the continuous increase to granite demand, a large amount of barren rock blocks, barren rock limit, waste stone dust, waste mud are also following, and this not only causes very serious pollution to environment, is in fact also a kind of wasting of resources.Granite waste material can replace feldspar and quartz raw material potting enamel, selects not leaded or after deleading process glaze economic worth higher, is also the manipulation of regeneration to resource simultaneously.
Further, titanium dioxide is that titanium waste residue obtains after removal of impurities harmless treatment, in titanium production process, produce a large amount of titanium-containing waste residues, and containing a large amount of titanium dioxide and other metal-salts in titanium waste residue, after removal of impurities and harmless treatment, be directly used in production glaze, the comprehensive utilization of Ti industry waste residue can be realized, reduce production cost, alleviate the pollution to environment, more effectively develop the limited titanium resource of China, there is great economic implications and social benefit.
Further, tensio-active agent is anion surfactant, is mainly Sulfonates, and Main Function is the Granular composite of the ceramic surface after making glazing, for improving the mechanical property of material, also can reduce the sintering temperature of pottery simultaneously.
Embodiment
Embodiment 1: a kind of antibacterial glaze and preparation method thereof, shared by the raw material of glaze, mass fraction is: titanium dioxide 40 parts, zinc nitrate 0.5 part, cerous nitrate 0.5 part, 3 parts, Glacial acetic acid, distilled water 8 parts, dehydrated alcohol 30 parts, 0.2 part, tensio-active agent, granite 800 parts.
Concrete making method is as follows: described antiseptic-germicide is prepared separately, comprises the steps:
The preparation of a, antiseptic-germicide: 3 parts of Glacial acetic acid and 8 parts of distilled water are added in 30 parts of dehydrated alcohols, then add the zinc nitrate of 0.5 part and the cerous nitrate of 0.5 part, adds 0.2 part of sulfonic acid analog anion surfactants afterwards; Main Function is the Granular composite of the ceramic surface after making glazing, for improving the mechanical property of material, also can reduce the sintering temperature of pottery simultaneously; Make electricity consumption agitator speed vigorous stirring under 200r/min, obtain mixing solutions, after 10 minutes, add 40 parts of titanium dioxide while stirring and can obtain antiseptic-germicide, until fully mix;
B, mixed pulp: first 800 parts of granites are carried out fragmentation, particle diameter, between 0.1 ~ 0.5mm, is mixed in proportion with antiseptic-germicide afterwards, then carries out wet ball grinding, and the slurry after ball milling sieves the removal of impurity, makes glaze slip;
C, high temperature burn till: glaze slip is made frit, and temperature is at 800 ~ 1000 DEG C; Firing time is 3 ~ 5h, is incubated 10 ~ 30min afterwards, cool to room temperature, can obtain antibacterial glaze.
Embodiment 2: embodiment 1: a kind of antibacterial glaze and preparation method thereof, shared by the raw material of glaze, mass fraction is: TiO 2 sol 45 parts, zinc nitrate 0.6 part, cerous nitrate 0.6 part, 4 parts, Glacial acetic acid, distilled water 10 parts, dehydrated alcohol 35 parts, 0.25 part, tensio-active agent, granite 1000 parts.
Concrete making method is as follows: described antiseptic-germicide is prepared separately, comprises the steps:
The preparation of a, antiseptic-germicide: 4 parts of Glacial acetic acid and 10 parts of distilled water are added in 35 parts of dehydrated alcohols, then add the zinc nitrate of 0.6 part and the cerous nitrate of 0.6 part, adds 0.25 part of sulfonic acid analog anion surfactants afterwards; Main Function is the Granular composite of the ceramic surface after making glazing, for improving the mechanical property of material, also can reduce the sintering temperature of pottery simultaneously; Make electricity consumption agitator speed vigorous stirring under 200r/min, obtain mixing solutions, after 10 minutes, add 45 parts of titanium dioxide while stirring and can obtain antiseptic-germicide, until fully mix;
B, mixed pulp: first 1000 parts of granites are carried out fragmentation, particle diameter, between 0.1 ~ 0.5mm, is mixed in proportion with antiseptic-germicide afterwards, then carries out wet ball grinding, and the slurry after ball milling sieves the removal of impurity, makes glaze slip;
C, high temperature burn till: glaze slip is made frit, and temperature is at 800 ~ 1000 DEG C; Firing time is 3 ~ 5h, is incubated 10 ~ 30min afterwards, cool to room temperature, can obtain antibacterial glaze.
Embodiment 3: embodiment 1: a kind of antibacterial glaze and preparation method thereof, shared by the raw material of glaze, mass fraction is: titanium dioxide 50 parts, zinc nitrate 0.8 part, cerous nitrate 0.8 part, 5 parts, Glacial acetic acid, distilled water 12 parts, dehydrated alcohol 40 parts, 0.3 part, tensio-active agent, granite 1200 parts.
Concrete making method is as follows: described antiseptic-germicide is prepared separately, comprises the steps:
The preparation of a, antiseptic-germicide: 5 parts of Glacial acetic acid and 12 parts of distilled water are added in 40 parts of dehydrated alcohols, then add the zinc nitrate of 0.8 part and the cerous nitrate of 0.8 part, adds 0.3 part of sulfonic acid analog anion surfactants afterwards; Main Function is the Granular composite of the ceramic surface after making glazing, for improving the mechanical property of material, also can reduce the sintering temperature of pottery simultaneously; Make electricity consumption agitator speed vigorous stirring under 200r/min, obtain mixing solutions, after 10 minutes, add 50 parts of titanium dioxide while stirring and can obtain antiseptic-germicide, until fully mix;
B, mixed pulp: first 1200 parts of granites are carried out fragmentation, particle diameter, between 0.1 ~ 0.5mm, is mixed in proportion with antiseptic-germicide afterwards, then carries out wet ball grinding, and the slurry after ball milling sieves the removal of impurity, makes glaze slip;
C, high temperature burn till: glaze slip is made frit, and temperature is at 800 ~ 1000 DEG C; Firing time is 3 ~ 5h, is incubated 10 ~ 30min afterwards, cool to room temperature, can obtain antibacterial glaze.
Above-described is only the preferred embodiment of the present invention; should be understood that; for a person skilled in the art; under the prerequisite not departing from structure of the present invention; some distortion and improvement can also be made; these also should be considered as protection scope of the present invention, and these all can not affect effect of the invention process and practical applicability.
Claims (5)
1. an antibacterial glaze, raw material comprises antiseptic-germicide and granite, it is characterized in that: described antiseptic-germicide comprises titanium dioxide, zinc nitrate, cerous nitrate, Glacial acetic acid, distilled water, dehydrated alcohol, tensio-active agent; By massfraction: titanium dioxide 40 ~ 50 parts, zinc nitrate 0.5 ~ 0.8 part, cerous nitrate 0.5 ~ 0.8 part, 3 ~ 5 parts, Glacial acetic acid, distilled water 8 ~ 12 parts, dehydrated alcohol 30 ~ 40 parts, 0.2 ~ 0.3 part, tensio-active agent, granite 600 ~ 1200 parts.
2. a making method for antibacterial glaze, is characterized in that: described antiseptic-germicide is prepared separately, comprises the steps:
The preparation of a, antiseptic-germicide: Glacial acetic acid and distilled water are added in dehydrated alcohol, then add zinc nitrate and cerous nitrate, add tensio-active agent afterwards, make electricity consumption agitator vigorous stirring, obtain mixing solutions, adding titanium dioxide while stirring can obtain antiseptic-germicide;
B, mixed pulp: first granite is carried out fragmentation, be mixed in proportion with antiseptic-germicide afterwards, carries out wet ball grinding afterwards, and the slurry after ball milling sieves the removal of impurity, makes glaze slip;
C, high temperature burn till: glaze slip is made frit, and temperature is at 800 ~ 1200 DEG C; Firing time is 3 ~ 5h, is incubated 10 ~ 30min afterwards, cool to room temperature, can obtain antibacterial glaze.
3. a kind of antibacterial glaze according to claim 1, is characterized in that: described granite is granite waste material, and not leaded.
4. a kind of antibacterial glaze according to claim 1, is characterized in that: described titanium dioxide is that titanium waste residue obtains after removal of impurities harmless treatment.
5. a kind of antibacterial glaze according to claim 1, is characterized in that: described tensio-active agent is anion surfactant.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669035A (en) * | 2016-02-02 | 2016-06-15 | 大埔漳联瓷业发展有限公司 | Self-cleaning and antibacterial ceramic glaze and preparation method thereof |
| CN107265860A (en) * | 2017-07-21 | 2017-10-20 | 龙泉市宏鑫瓷业有限公司 | A kind of celadon antibacterial glaze water and preparation method thereof |
| CN107265842A (en) * | 2017-07-21 | 2017-10-20 | 龙泉市宏盛科技咨询服务有限公司 | A kind of antibacterial additives of celadon glaze water and preparation method thereof |
| CN110759642A (en) * | 2018-07-03 | 2020-02-07 | 佛山欧神诺陶瓷有限公司 | Rare earth antibacterial ceramic glaze |
| CN111689689A (en) * | 2020-06-11 | 2020-09-22 | 内蒙古华宸再生资源科技有限公司 | Antibacterial ceramic raw glaze and preparation method thereof |
| CN111718124A (en) * | 2020-06-11 | 2020-09-29 | 内蒙古华宸再生资源科技有限公司 | Antibacterial lead-free ceramic fritted glaze and preparation method thereof |
| CN112939458A (en) * | 2020-05-07 | 2021-06-11 | 佛山市利德嘉陶瓷制釉有限公司 | Antibacterial ceramic glaze for wall and floor tiles and application method of glaze |
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| CN1785502A (en) * | 2005-11-02 | 2006-06-14 | 刘应希 | Nano-composite composite material and its preparation method |
| CN1843995A (en) * | 2006-05-12 | 2006-10-11 | 丁文战 | Antibacterial enamel and preparation method thereof |
| CN101326133B (en) * | 2005-12-12 | 2011-12-28 | 秦皇岛易鹏特种玻璃有限公司 | Antimicrobial sol-gel plating solution and preparation method thereof, antimicrobial product as well as method and apparatus for preparing the antimicrobial product |
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Patent Citations (4)
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| CN1785502A (en) * | 2005-11-02 | 2006-06-14 | 刘应希 | Nano-composite composite material and its preparation method |
| CN101326133B (en) * | 2005-12-12 | 2011-12-28 | 秦皇岛易鹏特种玻璃有限公司 | Antimicrobial sol-gel plating solution and preparation method thereof, antimicrobial product as well as method and apparatus for preparing the antimicrobial product |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669035A (en) * | 2016-02-02 | 2016-06-15 | 大埔漳联瓷业发展有限公司 | Self-cleaning and antibacterial ceramic glaze and preparation method thereof |
| CN107265860A (en) * | 2017-07-21 | 2017-10-20 | 龙泉市宏鑫瓷业有限公司 | A kind of celadon antibacterial glaze water and preparation method thereof |
| CN107265842A (en) * | 2017-07-21 | 2017-10-20 | 龙泉市宏盛科技咨询服务有限公司 | A kind of antibacterial additives of celadon glaze water and preparation method thereof |
| CN110759642A (en) * | 2018-07-03 | 2020-02-07 | 佛山欧神诺陶瓷有限公司 | Rare earth antibacterial ceramic glaze |
| CN112939458A (en) * | 2020-05-07 | 2021-06-11 | 佛山市利德嘉陶瓷制釉有限公司 | Antibacterial ceramic glaze for wall and floor tiles and application method of glaze |
| CN111689689A (en) * | 2020-06-11 | 2020-09-22 | 内蒙古华宸再生资源科技有限公司 | Antibacterial ceramic raw glaze and preparation method thereof |
| CN111718124A (en) * | 2020-06-11 | 2020-09-29 | 内蒙古华宸再生资源科技有限公司 | Antibacterial lead-free ceramic fritted glaze and preparation method thereof |
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Application publication date: 20150902 |