CN101333077A - Preparation of quartz tube carried nanometer titanium dioxide film at its surface and use thereof - Google Patents
Preparation of quartz tube carried nanometer titanium dioxide film at its surface and use thereof Download PDFInfo
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- CN101333077A CN101333077A CNA2007100493916A CN200710049391A CN101333077A CN 101333077 A CN101333077 A CN 101333077A CN A2007100493916 A CNA2007100493916 A CN A2007100493916A CN 200710049391 A CN200710049391 A CN 200710049391A CN 101333077 A CN101333077 A CN 101333077A
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- silica tube
- tio
- film
- quartz tube
- colloidal sol
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Abstract
The invention relates to a new method for loading TiO2 film or the TiO2 film doped with Ag+, Cu2+, Co2+ and iron oxide on the inner surface or the outer surface of a quartz tube. The method comprises the following steps: firstly, preparing TiO2 sol of different concentrations by n-butyl titanate through hydrolysis; secondly, evenly coating the TiO2 sol on the outer surface or the inner surface of the quartz tube through the czochralski method or the impregnation method; then putting the quartz tube into a muffle furnace for calcining so as to get the quartz tube with even surface coating. By controlling the sol composition and the coating thickness, the quartz tubes which are provided with significant hydrophobic effect and high weatherability and vary from colorless to purple and golden yellow can be obtained. The method can be applied to a variety of industrial quartz tubes for surface modification and coloring and can make use of the excellent photocatalytic properties of nano-TiO2 for air purification and sewage sterilization.
Description
Technical field
The present invention relates to utilize rotary pulling method or pickling process at silica tube outside surface or internal surface coated with nano TiO
2Film or doping Ag
+, Cu
2+, Co
2+And the TiO of ferric oxide
2The novel method of film is used for the surface treatment and the functions expanding of silica tube, belongs to chemical field.
Background technology
The silica tube major ingredient is SiO
2Because have that radiant ratio is stable, indeformable, the no harmful radiation of high temperature, high temperature resistant, resistance to corrosion is high, chemical stability is good, thermal inertia is little, thermal response speed is fast, thermal conversion efficiency is high, also can see through the ultraviolet ray of 190～320nm wavelength simultaneously, silica tube is in medicine equipment, water treatment, is used widely in fields such as food sanitation sterilization and far infrared heating.Silica tube without surperficial special processing is transparent color, because a certain amount of hydroxyl is contained on the surface, shows as wetting ability, and water droplet and dust influence the use of silica tube easily at surface enrichment.
TiO
2Be a kind of photocatalyst of excellence, have lot of documents to report at surface formation one deck TiO
2Film has hydrophobic and self-cleaning net work energy.Disclosing usefulness vapour deposition process (CVD) as Chinese invention patent 01129992.4 deposits on matrixes such as glass, pottery, stainless steel from method clean, the Superhydrophilic photocatalysis thin film; Matsushita Electric Industrial Co., Ltd provides a kind of surface coated to have photocatalytic activity TiO in the patent of invention 96112659.0 of China's application
2Method, can be widely used in fields such as set lights, bathroom fittings, automobile, personal belongings.
Yet in a lot of fields, as the automotive interior purifying air, laboratory water sterilization, industrial sewage processing etc., people need silica tube to have more function.Mating surface coating technique of the present invention, on the silica tube surface or inside plate one or more layers nano-TiO equably
2Film or doped Ti O
2Film can reach the silica tube surface colour, has sterilizing function from clean reaching under ultra violet lamp.
Summary of the invention
The purpose of this invention is to provide and a kind ofly evenly plate one or more layers TiO at silica tube outside surface or internal surface
2The preparation method of photocatalysis thin film, this method prepare TiO with the tetrabutyl titanate hydrolysis
2Colloidal sol uses rotary pulling method or pickling process at outside surface and internal surface plated film then, forms the surface evenly, has hydrophobic effect and high weather resisteant, and the silica tube of sterilizing function simultaneously, by the control coating film thickness, can form distinct colors on the silica tube surface.
Technical solution of the present invention is as follows:
At silica tube area load nano-TiO
2The preparation method of film is characterized in that this method comprises the steps:
(1) a certain amount of tetrabutyl titanate is added in certain dehydrated alcohol, under the constant temperature agitation condition, slowly drip moisture and HNO
3Mixed solution, obtain nattier blue TiO
2Colloidal sol;
(2) silica tube of cleaning surfaces is put into diluted acid (pH=4) solution and soaked 20 minutes, surface contaminants is removed in washing, puts into basic solution then and carries out surface active, and it is dry to put into vacuum drying oven;
(3) pretreated silica tube is immersed TiO
2In the colloidal sol, be rotated the crystal pulling method plated film with the device that designs voluntarily, the control climbing speed is 0.5～4cm/s, after the seasoning, put into retort furnace under the room temperature, 250～500 ℃ of calcining 1～3h in air atmosphere, naturally cool to room temperature, promptly plate the layer of even nano-TiO on the silica tube surface
2Film.Repeat n time, the term harmonization of each plated film can obtain the TiO of different thickness
2Film.Different thickness show distinct colors, from colourless, purple to gold;
(4) the processing inner surface of silica tube that uses the same method immerses TiO then
2In the colloidal sol,, obtain internal surface with different thickness TiO through same operation
2The silica tube of film.
Colloidal sol of the present invention is except pure TiO
2Colloidal sol also can add the Ag of different volumes ratio inside
+, Cu
2+, Co
2+And Fe (OH)
3Colloid allows the surface colour horn of plenty more of silica tube, improves TiO
2The photocatalysis performance of film.
The surface that utilizes the present invention to prepare is coated with nano-TiO
2The silica tube of film, through 600～1000 ℃ high-temperature calcination 1h, pH=1 strong acid and pH=13 highly basic respectively soak the weather resisteant experiment of 24h, TiO
2Film can not come off and chemical transformation takes place.Along with TiO
2Rete is counted the variation of n, and silica tube can be colourless (n=1) of high transmission rate, lavender (n=2), colored (n=3), and after adding a small amount of other material, as Fe (OH)
3Colloid shows as gold, and all coating all show as water droplet and do not sprawl on the silica tube surface, is gathered into to drip, and has strong-hydrophobicity.With flat band method internal surface is plated TiO
2The silica tube of film to sewage sterilization study, under uv irradiating, the silica tube sterilizing rate obviously improves, the bacterium absolute quantity before and after the sterilization is by 9.1 * 10
3Drop to 3.5 * 10
3, reduced 50% even more than the silica tube that does not plate nano titanium dioxide film, after being repeatedly used, sterilizing rate changes little.
Embodiment:
(1) TiO
2Colloidal sol and TiO
2And Fe (OH)
3The preparation of mixed sols
10ml tetrabutyl titanate (analytical pure) adding is filled in the beaker of 200ml dehydrated alcohol, be placed on stirring at low speed on constant temperature (35～45 ℃ of the temperature) magnetic stirrer, the beaker top is that 0.5mol/L nitric acid (HNO is housed
3) acid buret, dropwise add 100ml, can obtain nattier blue TiO
2Colloidal sol.
In the beaker that 1500ml ebullient distilled water is housed, add 100g iron trichloride (FeCl
3), FeCl
3Hydrolysis generates the Fe (OH) of reddish-brown
3Colloid behind the naturally cooling, removes by filter following precipitation in air, obtain purified reddish-brown colloid.Press TiO
2Colloidal sol and Fe (OH)
3The colloidal sol different volumes as 3: 1, promptly obtains mixed sols than mixing.
(2) at silica tube outside surface plating nano thin-film or be doped with the TiO of ferric oxide
2Film
With silica tube (length 300mm, diameter 20mm) with behind washing composition and the distilled water repetitive scrubbing, put into diluted acid (pH=4) solution and soak after 20 minutes, use distilled water wash again, put into basic solution and soaked 20 minutes, allow surface active, dry with putting into vacuum drying oven behind the distilled water wash.Highly be 500mm, diameter is to contain TiO in the container of 100mm
2Colloidal sol, the lifting gear of using design voluntarily is to the silica tube plated film after handling.The speed of lifting gear is by step motor control, and the speed of lifting influences the thickness of plated film.Silica tube soaks 2 minutes in colloidal sol after, lifting speed with 1.5cm/s is taken out silica tube, behind the at room temperature natural then Rotary drying, put into the retort furnace that temperature rise rate is 8 ℃/min, 350 ℃ of calcining 2h in air atmosphere, naturally cooling can plate the layer of even nano-TiO on the silica tube surface
2Film.Repeat n time, every plating one deck is all controlled identical condition, can obtain the TiO of different thickness
2Film.When number of plies n changed, the silica tube surface presented distinct colors, as colourless (n=1), and lavender (n=2), colored (n=3).If change sol volume ratio is 3: 1 mixed sols (TiO
2Colloidal sol: Fe (OH)
3Colloidal sol), can obtain the silica tube of golden series.
(3) weather resisteant experiment and surface property test
The surface that utilizes method for preparing to go out is coated with nanometer or contains the TiO of ferric oxide
2The silica tube of film, put into temperature and be 800 ℃ retort furnace calcining 1h after, take out immediately with tap water flushing cooling, put into pH=1 strong acid then and pH=13 highly basic respectively soaks 24h, the film on surface is not seen and is come off and any chemical transformation takes place.Silica tube behind the plated film is compared with uncoated silica tube, and water droplet can not sprawled on the surface, and globulate shows good hydrophobic performance, is placed on outdoor 60 days, and the nature dirt is not seen on the surface, as dust, mildew, very strong self-cleaning net work energy is arranged.
(3) photo-catalyst of sewage is tested
Earlier all instruments that will use and apparatus are sterilized in the high pressure steam pot with moist heat sterilization, sterilization time is 20～30min, and temperature is 121.3～128 ℃.Respectively the fresh sanitary sewage of taking is injected and do not plate TiO
2Film, be coated with one deck, two layers and three layers of TiO
2In each 3 of the silica tubes of film, 12 altogether, silica tube seals in order to avoid caused the result inaccurate by airborne bacterial contamination with the sterilization cotton.Is the silica tube power that sanitary sewage is housed 350W, and distance is the ultra violet lamp sterilization of 0.5m, and the time is 20min.Former water is diluted to 10
-6, be diluted to 10 through germ-resistant water sample
-2, adopt then and mix bacterium method mensuration bacteria content.Former hydromining is with 10
-4, 10
-5, 10
-6Three concentration gradients are respectively fallen three flat boards; Do not plate TiO
2The water sample of film adopts 10
-2Concentration is respectively fallen three flat boards; Be coated with one deck TiO
2Film, be coated with two layers of TiO
2Film, be coated with three layers of TiO
2Film adopts 10
-2The water determination bacteria content respectively falls three flat boards; Pour beef-protein medium into a flat board again and do blank assay.In 37 ℃ incubator, cultivated 24 hours the observed and recorded bacterial number.Get wherein partial results and list table 1 in.
The variation of the former water bacteria number of table 1 different treatment mode
Sterilization experiment shows that internal surface is coated with nano-TiO
2The sterilization effect of the silica tube of film is more obvious than uncoated silica tube sterilization effect, be more than doubled, but at internal surface plated film repeatedly, influence is not clearly to sterilization effect, because we are in sterilization experiment, UV-light is shone from the outside, and the silica tube of certain volume depends on the surface TiO that contacts with light fully to the absorption of light
2Film thickness.
Claims (3)
1. in the preparation method of silica tube outside surface or internal surface plating nano titanium dioxide film, it is characterized in that coating material is industrial widely used various silica tubes, with TiO
2Colloidal sol or the mixed sols that contains other colloidal sol are plating bath, are rotated crystal pulling method or pickling process at silica tube outside surface or internal surface coated with nano TiO by automatic gear
2Film and other metal ion that mixes, Ag
+, Cu
2+, Co
2+Or the method for ferric oxide, carry out the surface treatment of silica tube.TiO is passed through on the silica tube surface that obtains
2Film and dopant ion thereof or oxide compound obtain different surface colors, and have self-cleaning net work energy and hydrophobic performance; At internal surface plating TiO
2The silica tube of film has sterilizing function.
2. according to claim 1, the base material quartz pipe is characterised in that all size that uses on the market and the silica tube of shape, and plating bath is TiO
2Colloidal sol, or contain the Ag of certain volume
+, Cu
2+, Co
2+And Fe (OH)
3Mixed sols.
3. contain the silica tube of nano titanium dioxide film and titania-doped film thereof according to the surface of claim 1 and 2 preparations, Application Areas comprises the surface colour of silica tube, self-cleaning clean functionalization and photocatalysis apparatus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100493916A CN101333077A (en) | 2007-06-26 | 2007-06-26 | Preparation of quartz tube carried nanometer titanium dioxide film at its surface and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100493916A CN101333077A (en) | 2007-06-26 | 2007-06-26 | Preparation of quartz tube carried nanometer titanium dioxide film at its surface and use thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101333077A true CN101333077A (en) | 2008-12-31 |
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ID=40195999
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100493916A Pending CN101333077A (en) | 2007-06-26 | 2007-06-26 | Preparation of quartz tube carried nanometer titanium dioxide film at its surface and use thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972671A (en) * | 2010-09-21 | 2011-02-16 | 南京工业大学 | Surface hydrophobically modified TiO2 catalyst and preparation method and application thereof |
| CN105800917A (en) * | 2016-04-21 | 2016-07-27 | 太仓市建兴石英玻璃厂 | Preparation method of quartz tube with sterilization effect |
| CN106555178A (en) * | 2016-11-17 | 2017-04-05 | 榆林学院 | One kind mixes ferrum titanium oxide hydrophobic film and preparation method thereof |
-
2007
- 2007-06-26 CN CNA2007100493916A patent/CN101333077A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972671A (en) * | 2010-09-21 | 2011-02-16 | 南京工业大学 | Surface hydrophobically modified TiO2 catalyst and preparation method and application thereof |
| CN101972671B (en) * | 2010-09-21 | 2012-05-30 | 南京工业大学 | Surface hydrophobically modified TiO2 catalyst and preparation method and application thereof |
| CN105800917A (en) * | 2016-04-21 | 2016-07-27 | 太仓市建兴石英玻璃厂 | Preparation method of quartz tube with sterilization effect |
| CN106555178A (en) * | 2016-11-17 | 2017-04-05 | 榆林学院 | One kind mixes ferrum titanium oxide hydrophobic film and preparation method thereof |
| CN106555178B (en) * | 2016-11-17 | 2019-03-08 | 榆林学院 | One kind mixing iron titanium oxide hydrophobic film and preparation method thereof |
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Open date: 20081231 |