CN1239254C - Spray coating fluid for fabricating photocatalysed antibafcterial ceramics - Google Patents
Spray coating fluid for fabricating photocatalysed antibafcterial ceramics Download PDFInfo
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- CN1239254C CN1239254C CN 03118518 CN03118518A CN1239254C CN 1239254 C CN1239254 C CN 1239254C CN 03118518 CN03118518 CN 03118518 CN 03118518 A CN03118518 A CN 03118518A CN 1239254 C CN1239254 C CN 1239254C
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- tio
- spray coating
- powder
- nano
- colloidal sol
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Abstract
The present invention relates to spray coating liquid for preparing photocatalysed antimicrobial ceramics, which belongs to the technical field of antimicrobial ceramic production. The present invention is composed of nanometer TiO2 sol and a loading type TiO2 powder catalyst of 2 to 3% weight percent of nanometer TiO2 sol, wherein the nanometer TiO2 sol is obtained from the hydrolysis reaction of tetrabutyl titanate; an aproper quantity of organic acid is added in the reaction process, and the particulate granularity of the nanometer TiO2 sol can be controlled. The loading type TiO2 powder catalyst is metal octahedrite type TiO2 powder or metal-oxide octahedrite type TiO2 powder loading one of Pt, Fe, Rh and V. Antimicrobial ceramic catalyst films formed from the spray coating liquid of the present invention are tightly combined with ceramics, and the antibacterial property is good.
Description
Technical field
The invention belongs to the anti-bacteria ceramic production technical field, particularly a kind of spray coating liquor that is used to make the photocatalysis antibacterial pottery.
Background technology
Inner-wall ceramic tile is that the most general finishing material is used in places such as kitchen, toilet, hospital ward, operating room and swimming pool.This type of place mostly is dark and damp environment, and ventilation is smooth and contain rich nutrient substances, and the utmost point is beneficial to growing, breed and propagating of bacterium, thereby is the main place of all kinds of cross-infections.Summer in 1966, the western because caused food poisoning of pathogenicity Escherichia coli (O-157) of Japan causes 1800 people to be in hospital and causes 12 people's death, causes the very big shock of Japanese all circles.Shortly after that, the research group that the Teng Dao of Tokyo University professor is led finds first, is scribbling TiO
2Be coated with 3 * 10 on the sheet glass of film
4Individual colibacillary bacteria suspension, through UV-irradiation after 1 hour, none survival of bacterium.And be not coated with TiO
2The same sample of film, illumination only have 50% bacterium to be killed after 4 hours.The sterilization research of building material surfaces such as glass, pottery is spreaded to photocatalysis in this discovery first.Then Dong Tao company will scribble TiO
2The cleaners and polishes of film are introduced to the market.But in the said goods, TiO
2Film and glass, the pottery adhesion a little less than, anti-microbial property is relatively poor.
Summary of the invention
The object of the invention is to provide a kind of spray coating liquor that is used to make the photocatalysis antibacterial pottery, and this spray coating liquor combines firmly with Ceramic glaze in the catalytic membrane that ceramic surface forms, and has Large ratio surface, high antibacterial activity.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: a kind of spray coating liquor that is used to make the photocatalysis antibacterial pottery, and by nano-TiO
2Colloidal sol and account for nano-TiO
2The loaded TiO of colloidal sol weight 2-3%
2Fine catalyst is formed.
Nano-TiO
2Colloidal sol is made by the tetrabutyl titanate hydrolysis reaction, adds an amount of organic acid control nano-TiO in the course of reaction
2The granularity of colloidal sol particulate.
Nano-TiO
2The colloidal sol preparation method is: get absolute ethyl alcohol, add butyl titanate and acrylic acid successively under stirring, reaction got A solution in 5-10 minute under the room temperature, and each component volume ratio is a butyl titanate: ethanol: acrylic acid=1: (8-15): (1-4); Get red fuming nitric acid (RFNA) and be dissolved in formation B solution in the secondary water, each component volume ratio is a nitric acid: water=1: (30-50); Under the strong agitation B solution is slowly splashed in the A solution, after 2-4 hour, still aging 12-24 hour, liquor capacity was than being A: B=1: (3-5) in 50-80 ℃ of reaction.
Loaded TiO
2Fine catalyst is to support any metal of Pt, Fe, Rh, V or the Detitanium-ore-type TiO of metal oxide
2Powder.
Loaded TiO
2Fine catalyst is Pt/TiO
2, the loading of Pt is TiO
2The 0.3-0.5% of powder weight; TiO
2The average grain diameter of powder is 0.1-0.2um.
Loaded TiO
2The fine catalyst preparation method is: get Detitanium-ore-type TiO
2Powder is in N
2In the air-flow, 500-800 ℃ preliminary treatment 2-4 hour, be cooled to again that cooling is stand-by naturally after 200-400 ℃ of constant temperature 2-4 hour; Press TiO
2The Pt of the 0.1-1% of weight supports measures H
2PtCl
66H
2O is dissolved in the secondary water and moves in the Photoreactor; TiO with above-mentioned processing
2Powder stirs down and slowly adds in the reactor, uses N again
2Purge 10-20 minute rear enclosed Photoreactor, reduction is 1-2 hour under UV-irradiation, and the gained slurry washs after filtration to there not being Cl
-The back gets the loaded TiO of Pt in 100-150 ℃ of dry 12-24h
2Fine catalyst.
Spray coating liquor of the present invention can directly be sprayed at and carry on the glaze biscuit of ceramics fired formation photocatalysis membrana.The TiO that utilizes spray coating liquor of the present invention to form
2The sterilization principle of film is: under certain wavelength light irradiation, and TiO
2It is right that the optical excitation of photochemical catalyst receipts produces high-octane electronics-hole, and this energetic charges has extremely strong redox ability, can will be adsorbed on the H of catalyst surface
2O and O
2Some activity site at catalyst surface is reduced into very active OH free radical and O
- 2Superoxide anion.OH can attack organic unsaturated bond or extract its hydrogen atom and cause cell protein variation and lipidolysis, O
- 2Also oxidation operation can be decomposed, thereby destroy the multiplication capacity of cell, reach and suppress or the purpose of kill bacteria.
Compared with prior art, available technology adopting adhesive or directly with TiO
2Fine catalyst is coated on ceramic surface, though have higher sterilizing activity, relatively poor with the ground adhesion, come off easily, and also stronger to the ground covering power, influence product quality.TiO
2Colloidal sol directly is coated on ceramic surface, and is though adhesion has improvement, active relatively poor.And the TiO that supports of the present invention
2Type fine catalyst and nano-TiO
2The spray coating liquor that colloidal sol is compound had both guaranteed the strong bonded of catalyst film and Ceramic glaze, had brought into play the advantage of the high sterilizing activity of supported catalyst again.
With the Pt loading 0.3% powder TiO
2Catalyst with press Ti (OC
4H
9)
4: C
2H
5OH: CH
2=CHCOOH: H
2O: HNO
3The nano-TiO of=1: 10: 1: 40: 1 preparation
2Colloidal sol is by the spray coating liquor that is mixed and made at 1: 50, be sprayed on year glaze biscuit of ceramics with high-pressure nozzle, after high-temperature calcination, get the antibiotic ceramic tile of finished product, test through scratching instrument, catalyst film and glaze adhesion are up to 61N, and catalytic membrane does not have obvious influence to tone, the decorative pattern of ground.
Get above-mentioned antibiotic ceramic tile sample and film carrier finished product ceramic tile (common ceramic tile) sample not, dripping concentration respectively on the surface is 10
5-10
6The staphylococcus aureus of cfu/ml (ATCC6538) and Escherichia coli (8099) bacteria suspension 0.1ml used the 8W fluorescent lamp 4 hours again.Contrast detects and shows that antibiotic ceramic tile is 90.23% to the antibiotic rate of staphylococcus aureus, is 87.03% to colibacillary antibiotic rate.
Above-mentioned antibiotic ceramic tile sample is under the condition of 13.5 ℃ and RH47%, recording ceramic tile surface with the JY-82 contact angle instrument is θ＜1 ° to the contact angle of water, do not add θ=10 ° of the ceramic tile sample of antibacterial film, illustrate that the antibiotic ceramic tile surface that makes with spray coating liquor of the present invention has self-cleaning function.
Get 12 of above-mentioned antibiotic ceramic tile 200 * 50 (mm) specifications, be evenly arranged in the airtight photo catalysis reactor of 16 liters of volumes, inject certain density NH
3, shining 6h with black light lamp, the conversion ratio of ammonia is 80.5%, shows that the antibiotic ceramic tile that makes with spray coating liquor of the present invention has certain pollution abatement function.
In addition, spray coating liquor of the present invention prepares easy, and is with low cost, good stability.Because spray coating liquor of the present invention is in a liquid state, can be sprayed on highly equably and carry on the glaze biscuit of ceramics, quality index such as the tone of finished bricks, pattern, fineness all there is not visible influences.The spraying of spray coating liquor of the present invention combines convenient with ceramic production line, need not other equipment input.
Description of drawings
Fig. 1 photo catalysis reactor structural representation.
The specific embodiment
Spray coating liquor is 0.3% powder TiO by the Pt loading among embodiment 1, the present invention
2Catalyst with press Ti (OC
4H
9)
4: C
2H
5OH: CH
2=CHCOOH: H
2O: HNO
3The nano-TiO of=1: 10: 1: 40: 1 preparation
2Colloidal sol was mixed and made into by 1: 50.This spray coating liquor is sprayed on year glaze biscuit of ceramics with high-pressure nozzle, gets the antibiotic ceramic tile of finished product after high-temperature calcination, its catalyst film and glaze adhesion are up to 61N.Antibiotic ceramic tile is 90.23% to the antibiotic rate of staphylococcus aureus, is 87.03% to colibacillary antibiotic rate, and under the condition of 13.5 ℃ and RH47%, ceramic tile surface is θ＜1 to the contact angle of water
1 is sampling head among Fig. 1, and 2 is thermometer, and 3 is reactor, and 4 is fluorescent tube, and 5 is antibiotic ceramic tile, and 6 is blower fan.
Claims (5)
1, a kind of spray coating liquor that is used to make the photocatalysis antibacterial pottery is characterized in that, by nano-TiO
2Colloidal sol and account for nano-TiO
2The loaded TiO of colloidal sol weight 2-3%
2Fine catalyst is formed, loaded TiO
2Fine catalyst is to support any metal of Pt, Fe, Rh, V or the Detitanium-ore-type TiO of metal oxide
2Powder, TiO
2The powder average grain diameter is 0.1-0.2 μ m.
2, spray coating liquor as claimed in claim 1 is characterized in that, nano-TiO
2Colloidal sol is made by the tetrabutyl titanate hydrolysis reaction, adds an amount of organic acid control nano-TiO in the course of reaction
2The granularity of colloidal sol particulate.
3, spray coating liquor as claimed in claim 2 is characterized in that, nano-TiO
2The colloidal sol preparation method is: get absolute ethyl alcohol, add butyl titanate and acrylic acid successively under stirring, reaction got A solution in 5-10 minute under the room temperature, and each component volume ratio is a butyl titanate: ethanol: acrylic acid=1: (8-15): (1-4); Get red fuming nitric acid (RFNA) and be dissolved in formation B solution in the secondary water, each component volume ratio is a nitric acid: water=1: (30-50); Under the strong agitation B solution is slowly splashed in the A solution, after 2-4 hour, still aging 12-24 hour, liquor capacity was than being A: B=1: (3-5) in 50-80 ℃ of reaction.
As claim 1,2 or 3 described spray coating liquors, it is characterized in that 4, loaded TiO2 fine catalyst is Pt/TiO
2, the loading of Pt is TiO
2The 0.3-0.5% of powder weight.
5, spray coating liquor as claimed in claim 4 is characterized in that, loaded TiO
2The fine catalyst preparation method is: get Detitanium-ore-type TiO
2Powder is in N
2In the air-flow, 500-800 ℃ preliminary treatment 2-4 hour, be cooled to again that cooling is stand-by naturally after 200-400 ℃ of constant temperature 2-4 hour; Press TiO
2The Pt of the 0.1-1% of weight supports measures H
2PtCl
66H
2O is dissolved in the secondary water and moves in the Photoreactor; TiO with above-mentioned processing
2Powder stirs down and slowly adds in the reactor, uses N again
2Purge 10-20 minute rear enclosed Photoreactor, reduction is 1-2 hour under UV-irradiation, and the gained slurry washs after filtration to there not being C1
-The back gets the loaded TiO of Pt in 100-150 ℃ of dry 12-24h
2Fine catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03118518 CN1239254C (en) | 2003-01-22 | 2003-01-22 | Spray coating fluid for fabricating photocatalysed antibafcterial ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03118518 CN1239254C (en) | 2003-01-22 | 2003-01-22 | Spray coating fluid for fabricating photocatalysed antibafcterial ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1519051A CN1519051A (en) | 2004-08-11 |
| CN1239254C true CN1239254C (en) | 2006-02-01 |
Family
ID=34284907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03118518 Expired - Fee Related CN1239254C (en) | 2003-01-22 | 2003-01-22 | Spray coating fluid for fabricating photocatalysed antibafcterial ceramics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1239254C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307265C (en) * | 2004-10-15 | 2007-03-28 | 朱克勤 | Nano-antibacterial inorganic composite coloured metal coating layer material |
| CN102174293B (en) * | 2011-01-22 | 2013-06-05 | 广东三圆微晶玻璃科技有限公司 | Golden spraying liquid and production method for preparing golden glass ceramic from same |
| CN106607015B (en) * | 2016-12-07 | 2019-03-29 | 广州市逸都环保科技有限公司 | A kind of nano titanium dioxide photocatalyst and preparation method thereof of double particle diameter distributions |
| CN111205108A (en) * | 2020-01-19 | 2020-05-29 | 唐勇 | Spraying liquid for manufacturing photocatalytic antibacterial ceramic |
| CN112645740B (en) * | 2020-12-23 | 2022-09-09 | 甄崇礼 | Preparation method of anti-skid antibacterial ceramic tile |
| CN115636694B (en) * | 2022-12-26 | 2023-03-14 | 佛山市陶莹新型材料有限公司 | Nano self-cleaning ceramic glaze and preparation method thereof |
-
2003
- 2003-01-22 CN CN 03118518 patent/CN1239254C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1519051A (en) | 2004-08-11 |
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