CN1424282A - Titania nano film containing rare earth and silica and production thereof - Google Patents
Titania nano film containing rare earth and silica and production thereof Download PDFInfo
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- CN1424282A CN1424282A CN 03114751 CN03114751A CN1424282A CN 1424282 A CN1424282 A CN 1424282A CN 03114751 CN03114751 CN 03114751 CN 03114751 A CN03114751 A CN 03114751A CN 1424282 A CN1424282 A CN 1424282A
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- rare earth
- tio
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Abstract
A nano-class TiO2 film containing RE and SiO2 for higher photocatalytic activity and hydrophilicity is disclosed. Said composite TiO2/SiO2/RE film features less content of SiO2, and durable hydrophilicity.
Description
Technical field
The present invention relates to a kind of titanium dioxide nano-film and method for making thereof, particularly a kind of in adulterated nano thin-film of titanium dioxide nano-film and method for making thereof.
Background technology
Titanium dioxide (TiO
2) film surface has photocatalytic degradation organic dirt and two kinds of functions of wetting ability, because the ultraviolet ray in nature or the lighting source can be kept TiO
2Therefore the hydrophilicity of film plates TiO at glass surfaces such as window, mirrors
2Film just can play transparent antifog, self-cleaning effect.
But TiO
2Film surface in the dark or lose photocatalytic activity and wetting ability very soon when not having uviolizing, it is big to show as the very fast change in hydrophilic angle, needs continuous ultraviolet ray or solar radiation, this brings to practical application can difficulty.People are to TiO for this reason
2Film carries out doping treatment to improve the super hydrophilic effect of film, as TiO
2With SiO
2Laminated film can effectively improve TiO
2The hydrophilic time length of film.
TiO
2Film itself has photocatalytic activity and two kinds of functions of wetting ability, and these two kinds of functions take place simultaneously, and the two interacts.Surface hydrophilicity has transparent antifog, self-cleaning effect, and organic dirts such as photochemical catalysis degradable dust help keeping the automatically cleaning effect on surface.SiO
2Film has the highest photocatalytic activity when adding 10～20% left and right sides, but SiO
2Add 40%～50% o'clock hydrophilic persistency effects and just obviously increase SiO
2The hydrophilic persistency effects of film was because SiO when content was very high
2This is as due to the water-storage material.SiO
2Be isolator, itself does not have photocatalytic activity, so SiO
2Increase and reduced TiO
2Useful area, this moment, hydrophilic persistency effects increased, but photocatalytic activity reduces, and is unfavorable for keeping and the transparency of surperficial automatically cleaning effect.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of titanium dioxide nano-film that contains rare earth and silicon-dioxide, to overcome the above-mentioned defective that prior art exists;
Another technical problem that the present invention need solve provides the preparation method of above-mentioned film;
Technical conceive of the present invention makes such:
Thereby the rare earth doped physical properties that changes Nano semiconductor can increase substantially its photocatalytic activity and wetting ability.Add trace rare-earth element and just can improve TiO
2Photocatalytic activity and wetting ability, and do not resemble SiO
2Can influence TiO like that
2Useful area.Because photocatalytic activity and wetting ability are closely related, cooperate for making the two reach optimum, the contriver has designed TiO
2/ SiO
2/ rare earth laminated film is with SiO
2Reduce to 10～20%, add trace rare-earth element simultaneously, photocatalytic activity and wetting ability are increased synchronously, make the hydrophilic time length can keep the longer time darkling simultaneously.
The component and the mole percent level of film of the present invention comprise:
TiO
2 80～89.97％
SiO
2 10～19.97％
Rare earth oxide 0.03～0.06%
Said rare earth element comprises cerium or lanthanum.
Preferred mole percent level comprises:
TiO
2 80～84.97％
SiO
2 15～19.97％
Rare earth oxide 0.03～0.04%.
TiO provided by the invention
2/ SiO
2/ rare earth laminated film photocatalytic activity and Superhydrophilic are increased synchronously, and Superhydrophilic can be kept the long period darkling.
The preparation method of film of the present invention comprises the steps:
According to aforementioned ratio, with C
2～C
4Metatitanic acid fat, C
1～C
2Silicic acid fat, rare-earth salts, solvent and the colloidal sol that constitutes of acidic substance coat hard objects, as glass surface or ornamental brick surface, carry out sintering at 600 ℃～1000 ℃, sintering time is 0.5～3 hour, promptly makes film of the present invention.
According to the present invention, before sintering, preferably carry out 250 ℃ of oven dry earlier, bake out temperature is 200～350 ℃.
Acidic substance are used for hydrolyst, and its add-on is so that the pH value of colloidal sol is 2～4 for suitable;
Preferred metatitanic acid fat is metatitanic acid fourth fat;
Preferred silicic acid fat is the silicic acid formicester;
Preferred rare-earth salts is for being cerium salt or lanthanum salt, as cerous nitrate or lanthanum nitrate;
Said solvent comprises ethanol;
By above step---film-dry-the thermal treatment repetitive operation can obtain the film of the different numbers of plies and thickness.
Embodiment
Embodiment 1～2
Get the 100ml tetrabutyl titanate, added 900ml dehydrated alcohol magnetic agitation 30 minutes, as A liquid;
Get 10ml tetraethoxy (TEOS), add 400～500ml dehydrated alcohol and 0.35ml hydrochloric acid magnetic agitation 30min respectively, as B liquid;
B liquid is added in the A liquid, add 16mg cerous nitrate or 4mg lanthanum nitrate then, 4ml hydrochloric acid stirred 2 hours, can obtain the colloidal sol of homogeneous transparent after a period of stabilisation;
With dip coating colloidal sol is coated with glass surface, the glass of cleaning is vertically put into colloidal sol, at the uniform velocity vertically lift up then, be dried to gel-film under the normal temperature;
Film is 250 ℃ of oven dry, puts into resistance furnace then and is heated to 600 ℃ and be incubated 1h with the rate of heating of 2 ℃/min, and furnace cooling just can obtain corresponding film at glass surface to room temperature then.
By above step----600 ℃ of heating repetitive operations of filming-dry obtain 2 layer films.
The TiO that is obtained
2/ SiO
2/ rare earth laminated film photocatalytic activity and Superhydrophilic are increased synchronously, and Superhydrophilic can be kept the long period darkling.
The wetting ability experiment is adopted by the method for drop diameter measurement calculating contact angle and is undertaken.Utilize the water droplet of microsyringe 1 μ L on film surface, under reading microscope, measure the diameter of water droplet.If water droplet is spherical on the surface, can calculate the contact angle of water droplet and film surface by the spherical crown cubature formula.
Table 1 film surface hydrophilic film kind TiO
2TiO
2/ SiO
2TiO
2/ SiO
2/ Ce
2O
3TiO
2/ SiO
2/ La
2O
3The water droplet contact angle/(°) 16 933 UV-irradiation 30min water droplet contact angles/(°) water droplet contact angle behind 10 833 UV-irradiation, 60 min/(°) 30 15 68 deposit 24h in the dark after
Embodiment 3～4
Adopt identical method and the condition of embodiment, replace tetrabutyl titanate, replace tetraethoxy, the TiO that is obtained with tetramethoxysilance with titanium ethanolate
2/ SiO
2/ rare earth laminated film photocatalytic activity and Superhydrophilic are increased synchronously, and Superhydrophilic can be kept the long period darkling.
Table 2 film surface hydrophilic film kind TiO
2TiO
2/ SiO
2TiO
2/ SiO
2/ Ce
2O
3TiO
2/ SiO
2/ La
2O
3The water droplet contact angle/(°) water droplet contact angle behind the 18 11 55 UV-irradiation 30min/(°) water droplet contact angle behind the 10 733 UV-irradiation 60min/(°) 38 16 88 deposit 24h in the dark after
Claims (10)
1. contain the titanium dioxide nano-film of rare earth and silicon-dioxide, it is characterized in that, component and mole percent level comprise:
TiO
2 80～89.97％
SiO
2 10～19.97％
Rare earth oxide 0.03～0.06%.
2. film according to claim 1 is characterized in that mole percent level comprises:
TiO
2 80～84.97％
SiO
2 15～19.97％
Rare earth oxide 0.03～0.04%.
3. film according to claim 1 and 2 is characterized in that said rare earth element comprises cerium or lanthanum.
4. according to the preparation method of claim 1,2 or 3 described films, it is characterized in that, comprise the steps:
In proportion with C
2～C
4Metatitanic acid fat, C
1～C
2Silicic acid fat, rare-earth salts, solvent and the colloidal sol that constitutes of acidic substance coat the hard objects surface and carry out sintering, promptly make film of the present invention.
5. method according to claim 4 is characterized in that, sintering temperature is 600 ℃～1000 ℃.
6. method according to claim 4 is characterized in that, sintering time is 0.5～3 hour.
7. method according to claim 4 is characterized in that, dries earlier before sintering.
8. method according to claim 4 is characterized in that, the acidic substance add-on is so that the pH value of colloidal sol is 2～4.
9. according to the described method of claim 4～8, it is characterized in that metatitanic acid fat is metatitanic acid fourth fat; Silicic acid fat is the silicic acid formicester; Rare-earth salts is cerium salt or lanthanum salt; Solvent comprises ethanol.
10. method according to claim 9 is characterized in that, rare-earth salts is cerous nitrate or lanthanum nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03114751 CN1424282A (en) | 2003-01-06 | 2003-01-06 | Titania nano film containing rare earth and silica and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03114751 CN1424282A (en) | 2003-01-06 | 2003-01-06 | Titania nano film containing rare earth and silica and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1424282A true CN1424282A (en) | 2003-06-18 |
Family
ID=4790470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03114751 Pending CN1424282A (en) | 2003-01-06 | 2003-01-06 | Titania nano film containing rare earth and silica and production thereof |
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|---|---|
| CN (1) | CN1424282A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305588C (en) * | 2005-03-21 | 2007-03-21 | 付飘敏 | Preparation method of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide |
| CN100372618C (en) * | 2004-09-10 | 2008-03-05 | 北京化工大学 | Aluminium heat exchanger and aluminium foil surface hydrophilic corrosive-resistant filming method |
| CN100428984C (en) * | 2006-11-17 | 2008-10-29 | 大连理工大学 | Composite separating membrane of Si-doped TiO2 nanotube and its preparing method and application |
| CN100438990C (en) * | 2006-08-21 | 2008-12-03 | 泉耀新材料科技（上海）有限公司 | Method for preparing nano film through a low temperature procedure |
| CN106513055A (en) * | 2016-09-06 | 2017-03-22 | 南昌大学 | Method for preparing PDMS-TiO2-SiO2 film and application of PDMS-TiO2-SiO2 film in fixed-bed photodegradation reactor |
| CN112109171A (en) * | 2020-09-02 | 2020-12-22 | 阜南县德盛隆工艺家具有限公司 | Preparation process of wicker surface nano-film |
-
2003
- 2003-01-06 CN CN 03114751 patent/CN1424282A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372618C (en) * | 2004-09-10 | 2008-03-05 | 北京化工大学 | Aluminium heat exchanger and aluminium foil surface hydrophilic corrosive-resistant filming method |
| CN1305588C (en) * | 2005-03-21 | 2007-03-21 | 付飘敏 | Preparation method of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide |
| CN100438990C (en) * | 2006-08-21 | 2008-12-03 | 泉耀新材料科技（上海）有限公司 | Method for preparing nano film through a low temperature procedure |
| CN100428984C (en) * | 2006-11-17 | 2008-10-29 | 大连理工大学 | Composite separating membrane of Si-doped TiO2 nanotube and its preparing method and application |
| CN106513055A (en) * | 2016-09-06 | 2017-03-22 | 南昌大学 | Method for preparing PDMS-TiO2-SiO2 film and application of PDMS-TiO2-SiO2 film in fixed-bed photodegradation reactor |
| CN106513055B (en) * | 2016-09-06 | 2019-01-29 | 南昌大学 | A kind of PDMS-TiO2-SiO2The preparation method of film and its application in fixed bed light degradation reactor |
| CN112109171A (en) * | 2020-09-02 | 2020-12-22 | 阜南县德盛隆工艺家具有限公司 | Preparation process of wicker surface nano-film |
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| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |