CN102503548A - Stone slab with self-cleaning function and preparation method thereof - Google Patents
Stone slab with self-cleaning function and preparation method thereof Download PDFInfo
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- CN102503548A CN102503548A CN2011103224392A CN201110322439A CN102503548A CN 102503548 A CN102503548 A CN 102503548A CN 2011103224392 A CN2011103224392 A CN 2011103224392A CN 201110322439 A CN201110322439 A CN 201110322439A CN 102503548 A CN102503548 A CN 102503548A
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Abstract
The invention discloses a stone slab with a self-cleaning function and a preparation method thereof. The preparation method comprises the steps of: taking the stone slab as a research target and titanium tetrachloride, ammonia water and hydrochloric acid as primary raw materials; and preparing the stone slab which has the self-cleaning function and is loaded with nanometer scaled titanium dioxide by using in-situ hydrolysis technology. The stone slab has good functions of purifying air, inhibiting bacteria, sterilizing and self-cleaning and excellent weather resistance. The preparation method is simple and convenient, with remarkable economic and social benefits.
Description
Technical field
The present invention is specifically related to a kind of self-cleaning function stone slab and preparation method thereof, belongs to material science.
Background technology
Along with advancing by leaps and bounds of national urban construction, people improve constantly the requirement of producing and living environment is beautified, and are described as finishing material---the stone material of " ancient and green for a long time, traditional and modish ", receive people's favor deeply.The interior wall face and the ground of landmark buildings such as many building, shop institute, square, park have all adopted stone material to decorate.In recent years; The titanium oxide optical tech is widely used in environmental improvement fields such as purifying air, wastewater treatments, and people have developed such as multiduty optically catalytic TiO 2 products such as automatically cleaning and antibiotic ceramic tile, automatically cleaning fog resistant glass, photocatalysis air purifying devices.The titanium oxide that how will have photocatalysis performance is incorporated in the marble, develops the cleaning function marble that has automatically cleaning and anti-microbial property, can degradable organic pollutant.It has important practical significance.
Summary of the invention
The object of the present invention is to provide a kind of self-cleaning function stone slab and preparation method thereof, this stone slab have good purify air, antibacterial, sterilization and self-cleaning function and good weathering resistance.The preparation method is easy, has remarkable economical and social benefit.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
Adopt the in-situ hydrolysis technology to make load TiO
2The stone slab with self-cleaning function.Concrete preparation process is following:
(1) after stone material plate (marble slabs or granite plates, big or small 20*20cm, thickness 2-3cm) cleans up with zero(ppm) water, puts into box retort furnace or baking box, 150-400 ℃ of baking 30-180min;
(2) in hydrolytic tank, add zero(ppm) water, dripping concentration is the hydrochloric acid adjusting pH to 3-5 of 0.05-0.2mol/L; Drip the TiCl of 20-50mL then while stirring
4, stirring makes it to react 10-60min and gets reaction solution after dripping; Described stirring velocity is 150-200r/min;
(3) dipping 10-50min is immersed in the described reaction solution of step (2) in the described stone slab taking-up of step (1) immediately;
(4) temperature with hydrolytic tank rises to 70 ~ 90 ℃, and the pH value that drips the strong aqua regulator solution is to 7-8, standing and reacting 20-60min;
(5) stone slab in the hydrolytic tank is taken out, dry the stone slab surface-moisture, and put into retort furnace or baking box; In air atmosphere, be warming up to 200-400 ℃ with the speed of 10-30 ℃/min, insulation 1-3h; Naturally cool to room temperature, promptly make described self-cleaning function stone slab.
Remarkable advantage of the present invention is: stone slab of the present invention have good purify air, antibacterial, sterilization and self-cleaning function and good weathering resistance.Organism such as indoor formaldehyde, benzene, phenol had decomposition, purification function as as indoor hardware fitting the time; As outdoor wall decoration material the time, adherent pollutent is had good decomposition and dirt-removing functions, and can play antibacterial, sterilization functions; During as square or road surface tile work material adherent pollutent had the function that is eliminated more easily.The preparation method is easy, has remarkable economical and social benefit.
Embodiment
Embodiment 1
Adopt the in-situ hydrolysis technology to make load TiO
2The stone slab with self-cleaning function.Concrete preparation process is following:
(1) after stone material plate (marble slabs or granite plates, big or small 20*20cm, thickness 2-3cm) cleans up with zero(ppm) water, puts into box retort furnace or baking box, 150 ℃ of baking 180min;
(2) in hydrolytic tank, add zero(ppm) water, dripping concentration is the hydrochloric acid adjusting pH to 5 of 0.05mol/L; Drip the TiCl of 20mL then while stirring
4, stirring makes it to react 10min and gets reaction solution after dripping; Described stirring velocity is 150r/min;
(3) dipping 10min is immersed in the described reaction solution of step (2) in the described stone slab taking-up of step (1) immediately;
(4) temperature with hydrolytic tank rises to 70 ℃, and drips the pH value to 7 of strong aqua regulator solution, standing and reacting 20min;
(5) stone slab in the hydrolytic tank is taken out, dry the stone slab surface-moisture, and put into retort furnace or baking box; In air atmosphere, be warming up to 200 ℃ with the speed of 10 ℃/min, insulation 1h; Naturally cool to room temperature, promptly make described self-cleaning function stone slab.
Embodiment 2
Adopt the in-situ hydrolysis technology to make load TiO
2The stone slab with self-cleaning function.Concrete preparation process is following:
(1) after stone material plate (marble slabs or granite plates, big or small 20*20cm, thickness 2-3cm) cleans up with zero(ppm) water, puts into box retort furnace or baking box, 400 ℃ of baking 30min;
(2) in hydrolytic tank, add zero(ppm) water, dripping concentration is the hydrochloric acid adjusting pH to 3 of 0.2mol/L; The TiCl of Dropwise 5 0mL while stirring then
4, stirring makes it to react 60min and gets reaction solution after dripping; Described stirring velocity is 180r/min;
(3) dipping 50min is immersed in the described reaction solution of step (2) in the described stone slab taking-up of step (1) immediately;
(4) temperature with hydrolytic tank rises to 90 ℃, and drips the pH value to 8 of strong aqua regulator solution, standing and reacting 60min;
(5) stone slab in the hydrolytic tank is taken out, dry the stone slab surface-moisture, and put into retort furnace or baking box; In air atmosphere, be warming up to 400 ℃ with the speed of 30 ℃/min, insulation 3h; Naturally cool to room temperature, promptly make described self-cleaning function stone slab.
Embodiment 3
Adopt the in-situ hydrolysis technology to make load TiO
2The stone slab with self-cleaning function.Concrete preparation process is following:
(1) after stone material plate (marble slabs or granite plates, big or small 20*20cm, thickness 2-3cm) cleans up with zero(ppm) water, puts into box retort furnace or baking box, 325 ℃ of baking 110min;
(2) in hydrolytic tank, add zero(ppm) water, dripping concentration is the hydrochloric acid adjusting pH to 4 of 0.1mol/L; The TiCl of Dropwise 35 mL while stirring then
4, stirring makes it to react 35min and gets reaction solution after dripping; Described stirring velocity is 200r/min;
(3) dipping 30min is immersed in the described reaction solution of step (2) in the described stone slab taking-up of step (1) immediately;
(4) temperature with hydrolytic tank rises to 80 ℃, and drips the pH value to 7 of strong aqua regulator solution, standing and reacting 40min;
(5) stone slab in the hydrolytic tank is taken out, dry the stone slab surface-moisture, and put into retort furnace or baking box; In air atmosphere, be warming up to 300 ℃ with the speed of 20 ℃/min, insulation 2h; Naturally cool to room temperature, promptly make described self-cleaning function stone slab.
Embodiment 4
In the commercial house finishing of Ningde,, adopt the marble and the undressed marble flooring of this technology preparation respectively in two bedrooms that size is close.Fitted up after (t0, t1, t2) content of formaldehyde and benzene in two space airs of sample detecting respectively after a while; Find the room of the marble finishing of this technology preparation of employing, the concentration ratio of formaldehyde, benzene adopts the room concentration of untreated marble finishing low.Table 1 is for sampling detects the room concentration of formaldehyde (C of the marble finishing that adopts this technical finesse through different time
1 formaldehyde) and benzene concentration (C
1 benzene), fit up room concentration of formaldehyde (C with adopting undressed marble
0 formaldehyde) and benzene concentration (C
0 benzene) correlation data.
Two room formaldehyde of table 1 and benzene concentration contrast
Annotate: the sampling time is t0 for the first time, after t1 first sampling the 30th day; After t2 second sampling the 30th day.
Embodiment 5
Remove SO
2And NO
2Experiment: reach 1 m that surrounds with marble with glass, bottom at the top all around
3Closed cabinet in carry out SO respectively
2And NO
2Evaluation experimental.Appreciation condition is: 8 W low pressure mercury lamps (predominant wavelength 365 nm), the marble area is 1 m * 1 m, SO
2And NO
2Starting point concentration be 30ppm, temperature of reaction is a room temperature, the reaction times is 3 h, to SO
2And NO
2Clearance is seen table 2.
Table 2 couple SO
2And NO
2Clearance
Embodiment 6
The watercolor comparison of fading: the marble surface that in instance 2, makes draws mark with watercolor pencil, behind 8 W low pressure mercury lamps (predominant wavelength 365 nm) illumination 2h, and the watercolor color fade.And undressed under the same conditions Dali illumination 2h does not see the phenomenon of obviously fading.
Embodiment 7
Sterilization experiment: pipette 100 mL intestinal bacteria bacteria suspensions under the same conditions respectively and pour in the container that surrounds with marble, under 8 W low pressure mercury lamps (predominant wavelength 365 nm) irradiation, whenever get once appearance, measure the bacteria living rate through the method for plate culture count at a distance from 1 h.
Table 3 pair colibacillary germ-killing efficiency
The above is merely preferred embodiment of the present invention, and all equalizations of doing according to claim of the present invention change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. self-cleaning function stone slab is characterized in that: said stone slab is the load TiO that adopts the in-situ hydrolysis technology to make
2The stone slab with self-cleaning function.
2. the preparation method of a self-cleaning function stone slab as claimed in claim 1, it is characterized in that: said preparing method's step is following:
(1) after the stone material plate cleans up with zero(ppm) water, puts into box retort furnace or baking box, 150-400 ℃ of baking 30-180min;
(2) in hydrolytic tank, add zero(ppm) water, dripping hydrochloric acid is regulated pH to 3-5; Drip the TiCl of 20-50mL then while stirring
4, stirring makes it to react 10-60min and gets reaction solution after dripping;
(3) dipping 10-50min is immersed in the described reaction solution of step (2) in the described stone slab taking-up of step (1) immediately;
(4) temperature with hydrolytic tank rises to 70 ~ 90 ℃, and the pH value that drips the strong aqua regulator solution is to 7-8, standing and reacting 20-60min;
(5) stone slab in the hydrolytic tank is taken out, dry, put into retort furnace or oven for baking, take out, naturally cool to room temperature, promptly make described self-cleaning function stone slab.
3. the preparation method of self-cleaning function stone slab according to claim 2 is characterized in that: the described stone material plate of step (1) is a kind of in marble slabs or the granite plates.
4. the preparation method of self-cleaning function stone slab according to claim 2 is characterized in that: the concentration of the described hydrochloric acid of step (2) is 0.05-0.2mol/L.
5. the preparation method of self-cleaning function stone slab according to claim 2 is characterized in that: the stirring velocity of the described stirring of step (2) is 150-200r/min.
6. the preparation method of self-cleaning function stone slab according to claim 2 is characterized in that: the described baking of step (5) is in air atmosphere, is warming up to 200-400 ℃ with the speed of 10-30 ℃/min, insulation 1-3h.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102785275A (en) * | 2012-08-15 | 2012-11-21 | 福建农林大学 | Wood slab with self-cleaning functions and preparation method for wood slab |
CN104446667A (en) * | 2014-10-30 | 2015-03-25 | 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 |
CN109384947A (en) * | 2018-12-04 | 2019-02-26 | 哈尔滨工业大学 | A kind of preparation method of topological structure titanium dioxide super hydrophobic material |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1149588A (en) * | 1997-07-31 | 1999-02-23 | Kawai Musical Instr Mfg Co Ltd | Natural stone with photocatalyst and its production |
JP2000256079A (en) * | 1999-03-08 | 2000-09-19 | Toomikku:Kk | Production of antimicrobial stone |
CN1662465A (en) * | 2002-04-17 | 2005-08-31 | 法国圣戈班玻璃厂 | Substrate with a self-cleaning coating |
CN101293787A (en) * | 2008-05-28 | 2008-10-29 | 上海金博石材建设有限公司 | Modification method for nano-titanium dioxide on natural stone surface |
-
2011
- 2011-10-21 CN CN 201110322439 patent/CN102503548B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1149588A (en) * | 1997-07-31 | 1999-02-23 | Kawai Musical Instr Mfg Co Ltd | Natural stone with photocatalyst and its production |
JP2000256079A (en) * | 1999-03-08 | 2000-09-19 | Toomikku:Kk | Production of antimicrobial stone |
CN1662465A (en) * | 2002-04-17 | 2005-08-31 | 法国圣戈班玻璃厂 | Substrate with a self-cleaning coating |
CN101293787A (en) * | 2008-05-28 | 2008-10-29 | 上海金博石材建设有限公司 | Modification method for nano-titanium dioxide on natural stone surface |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102785275A (en) * | 2012-08-15 | 2012-11-21 | 福建农林大学 | Wood slab with self-cleaning functions and preparation method for wood slab |
CN104446667A (en) * | 2014-10-30 | 2015-03-25 | 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 |
CN109384947A (en) * | 2018-12-04 | 2019-02-26 | 哈尔滨工业大学 | A kind of preparation method of topological structure titanium dioxide super hydrophobic material |
CN109384947B (en) * | 2018-12-04 | 2021-07-13 | 哈尔滨工业大学 | Preparation method of titanium dioxide super-hydrophobic material with topological structure |
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