CN1872758A - Antifogging self-cleaning glass, and preparation method - Google Patents
Antifogging self-cleaning glass, and preparation method Download PDFInfo
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- CN1872758A CN1872758A CNA2006100193387A CN200610019338A CN1872758A CN 1872758 A CN1872758 A CN 1872758A CN A2006100193387 A CNA2006100193387 A CN A2006100193387A CN 200610019338 A CN200610019338 A CN 200610019338A CN 1872758 A CN1872758 A CN 1872758A
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Abstract
This invention provides a method for mass production of fog-proof and self-cleaning glass. The method comprises: coating TiO2 and SiO2 onto a cleaned glass substrate by DC reactive magnetron sputtering technology and radiofrequency magnetron sputtering technology using pure titanium target and pure silicon dioxide (quartz) target respectively, thus obtaining TiO2/SiO2 double-layer fog-proof and self-cleaning glass or SiO2/TiO2/SiO2 triple-layer fog-proof and self-cleaning glass. The obtained product has better hydrophilicity, lower initial wetting angle, and longer maintaining time after stopping UV radiation than those of TiO2 single-layer glass, and overcomes the shortcoming of strong dependence on environment of present fog-proof and self-cleaning glasses.
Description
Technical field
What the present invention relates to is a kind of antifogging self-cleaning glass and preparation method thereof, particularly industrial mass production has a kind of method of special glasss such as antifogging self-cleaning effect windshield, high building cladding glass, belongs to fields such as building glass, vehicle glass, ambetti.
Background technology
Growing along with material conditions, high buildings and large mansions squama thatch is placed closely side by side in the city, and there is a heavy traffic in the street, and the demand of various building glasses and vehicle glass is also at double growth.The cleaning problem of the glass surface of Yin Faing is puzzlement people's a difficult problem all the time all the time therefrom.People attempt ining all sorts of ways and prepare the glass with automatically cleaning effect, and attempt solves this difficult problem.Be to be coated with nano-titanium dioxide film by a kind of method that the public accepted extensively now at glass surface.This self-cleaning film has following characteristic:
1, the super hydrophile function of self-cleaning nanometer: treated glass surface has super hydrophilicity.This characteristic can make complete the sprawling at glass surface equably of moisture come, and simultaneously, fully soaks into glass and pollutent, and final gravity by water will be attached to pollutent on glass and carry away.Thereby reach the automatically cleaning effect, and keep the long-term cleaning of glass.Simple glass then can form the globule from the teeth outwards, adheres to dust,
2, the photo-catalysis function of decomposing organic matter: under the irradiation of sunlight or UV-light, the self-cleaning nona thin-film material can have the intensive Decomposition to organism.Experiment shows; Utilize this photocatalytic activity, degradation production is CO
2, H
2Other innocuous gas such as O.
3, the super hydrophile function of the nanometer of antifogging action: treated glass surface has super hydrophilicity, because moisture can't form the globule at substrate surface, but forms uniform moisture film, thereby can be used for the antifog of glass surface.
Above characteristic makes this self-cleaning glass can be widely used in following field:
1, building glass: building curtain wall glass, building doors and windows glass, architectural decorative glass.
2, vehicle glass: windshield, automobile window glass, automotive rear-view mirror glass.
3, antifog glass series: the bathroom antifog glass, decorate antifog glass.
Existing automatic cleaning coating, the preparation of more use sol-gel method, the characteristics of this method are, and are less demanding to production unit, but exist adhesive force poor, with shortcomings such as traditional glass coating technology are incompatible; In addition, also there is the magnetron sputtering technique of employing to be coated with single TiO
2The research of self-cleaning film, the good and traditional glass coating process compatibility of energy, but this single TiO
2The result of use of film is stronger according to patience to the ultraviolet light irradiation condition, thereby has limited its range of application and result of use.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, propose the method for a kind of antifogging self-cleaning glass and industrial mass preparation thereof, make its can overcome existing antifogging self-cleaning glass to environment according to the strong shortcoming of patience.
The present invention is achieved by the following technical solutions, the present invention adopts magnetron sputtering technique, with pure titanium target and pure silicon dioxide (quartz) target is target, adopts direct current reaction magnetron sputtering and radiofrequency magnetron sputtering technology to be coated with TiO respectively in clean simple glass substrate
2And SiO
2Film forms a kind of substrate of glass+TiO
2/ SiO
2The antifogging self-cleaning glass of film, or form a kind of substrate of glass+SiO
2/ TiO
2/ SiO
2The antifogging self-cleaning glass of film.
For glass basis+TiO
2/ SiO
2The antifogging self-cleaning glass of film, its bottom TiO
2Film thickness is 200nm--500nm.Top layer Si O
2Film thickness is generally about 10nm-40nm.TiO
2Layer thickness can not be too thin, because the sodium ion in the sputter procedure in the glass substrate can spread in film, and sodium ion is unfavorable for TiO
2The photocatalytic activity of film surpasses not obvious that this effect of certain thickness film just will become.TiO
2Layer thickness can not be blocked up, blocked up TiO
2Film will directly cause the lifting of preparation cost, and photochemical catalysis of Ti Shenging and Superhydrophilic effect are then not obvious thus.
For glass basis+SiO
2/ TiO
2/ SiO
2The antifogging self-cleaning glass of film, bottom SiO
2The thickness of film is generally 10nm-40nm.Middle layer TiO
2Thickness is between the 100nm-500nm.Top layer Si O
2The thickness of film is generally about 20nm-40nm.Bottom SiO
2The introducing of film can stop in the sputter procedure sodium ion to TiO
2The diffusion of film can reduce TiO
2The thickness of film can further improve the quality of product.
Its preparation methods steps is as follows:
1, glass substrate to be coated is cleaned up.Concrete purging method can be with reference to glass cleaning (for example using the alcohol ultrasonic cleaning) commonly used, on the specimen holder of the coating chamber of then glass substrate being packed into.
2, regulate the coating chamber working parameter.Coating chamber forvacuum to 1.0 * 10
-3-1.0 * 10
-4Pa.Feed the mixed gas of argon gas and oxygen then to sputtering chamber, the content of oxygen is 10%-100%, controls the flow of argon gas and oxygen respectively with mass flowmeter, regulates the vacuum chamber main valve, make to reach the required total pressure of sputter in the coating chamber, its scope is usually between 0.1Pa-10Pa.
3, adopt the direct current reaction magnetron sputtering technology to be coated with Ti0
2Layer plated film, sputtering target material is 99.5% titanium plate, target-substrate distance 3-15cm, the Surface field intensity of titanium target plate is 200-500 Gauss, regulating sputtering voltage is-500V--800V, sputtering current is 100mA-600mA, and substrate temperature is set in 25 ℃ to 500 ℃ scopes, and depositing of thin film speed is controlled at 1nm/min to 30nm/min with the size of regulating sputtering current.Control TiO by the control sputtering time
2The thickness of layer.
4, adopt radiofrequency magnetron sputtering technology to be coated with SiO
2Film.Sputtering target material is 99.5% SiO
2Silica glass, target-substrate distance 3-15cm, radio frequency power are adjusted between the 20W-200W, depositing of thin film speed with regulate the radio-frequency sputtering watt level with rate-controlling at 1nm/min between the 10nm/min.
When if the substrate of glass temperature is lower than 200 ℃ during plated film, need after thin film deposition finishes, carry out anneal, annealing temperature generally about 500 ℃, heat treatment time 30 to 60 minutes, the TiO that obtains
2Film generally is the anatase octahedrite phase.
The experiment proved that the self-cleaning glass that is made by the present invention has good hydrophilicity, particularly than common individual layer TiO
2The wetting ability of film will be got well, and the initial contact angle that is mainly reflected in film surface water is starkly lower than individual layer TiO
2Film is stopping later the holding time also than common individual layer TiO of UV-irradiation
2Film will be grown a lot.
Embodiment
The present invention is further described with embodiment below.
Embodiment 1: selecting purity for use is that 99.5% titanium plate is a sputtering target material, and the adjusting target-substrate distance is 5.5cm, and the sputtering chamber base vacuum is evacuated to 2.0 * 10
-4Pa is the substrate deposition film with the simple glass that cleans up.Before formal sputtering,, treat to prepare when aura becomes blueness by pink to regulate every sputtering parameter to set(ting)value earlier with argon gas build-up of luminance sputtered titanium target.Glass substrate is heated to 200 ℃, and the flow of controlling argon gas and oxygen by mass flowmeter respectively is 29.5sccm and 10.5sccm, regulates the sputtering chamber main valve and makes the sputtering chamber operating air pressure be stabilized in 0.5Pa.Regulating sputtering voltage is-470V, and this moment, corresponding sputtering current was 440mA by the reometer reading, was converted into the about 207W of power.Depositing of thin film speed is 11.4nm/min under this sputtering condition, and the control sputtering time obtains the TiO of the about 400nm of thickness at 35min
2Film.And then, be coated with TiO
2Be coated with the SiO of different thickness on the glass substrate of film with radiofrequency magnetron sputtering technology
2Film.With purity is that 99.996 silica glass is a sputtering target material, and the adjusting target-substrate distance is 6.5cm, is 30sccm by mass flowmeter control argon flow amount, regulates operating air pressure to 0.5Pa, and radio frequency power is 50W.Depositing of thin film speed is 2nm/min under this sputtering condition, controls SiO respectively
2Layer sputtering time is 0min, 5min, 10min, 15min, 20min and 25min, obtains SiO
2Top layer thickness is respectively the TiO of 0nm, 10nm, 20nm, 30nm, 40nm and 50nm
2/ SiO
2Two membranes, their wetting ability is as shown in table 1.
The different SiO of table 1
2The wetting ability of the two-layer film configuration of top layer thickness
| Top layer Si O 2Thickness (nm) | 0 | 10 | 20 | 30 | 40 | 50 |
| Initially | 78 | 17 | 10 | 8 | 9 | 7 |
| 30min | 27 | 6 | 4 | 6 | 8 | 7 |
| 60min | 8 | 0 | 0 | 4 | 7 | 7 |
Embodiment 2: be coated with SiO on glass substrate
2/ TiO
2/ SiO
2Trilamellar membrane.Wherein, bottom SiO
2Gauge control is at 10nm, middle TiO
2Layer thickness is controlled at 250nm, top layer Si O
2Gauge control is at 20nm.Other various sputtering parameters are with embodiment 1.The wetting ability of trilamellar membrane sample is as shown in table 2.Show bottom SiO
2Introducing, can be in the middle of suitably reducing TiO
2The thickness (reducing production costs) of layer is taken into account the wetting ability effect of film simultaneously.
The wetting ability of table 2 trilamellar membrane
| Irradiation time | Initially | 30min | 60min |
| Contact angle | 11 | 5 | 0 |
In centre wavelength is 365nm, and power density is that the UV-light of 7.9mW is carried out irradiation to the film sample surface, adopts quiet contact angle of JC 2000A type/stalagmometry instrument to measure the change procedure of the contact angle of different irradiation time film surface water.The result shows does not have SiO
2The TiO of top layer
2The hydrophilicity of film far has been worse than SiO
2The film of top layer, by finding that relatively top layer thickness is about 20nm the time, the wetting ability of film is best in addition.
Claims (4)
1, a kind of antifogging self-cleaning glass is a substrate with the simple glass, it is characterized in that being coated with TiO by direct current reaction magnetron sputtering and rf magnetron sputtering on this glass substrate
2/ SiO
2The antifogging self-cleaning glass of double-layer films, perhaps SiO
2/ TiO
2/ SiO
2The antifogging self-cleaning glass of three-layer thin-film.
2, antifogging self-cleaning glass according to claim 1 is characterized in that described TiO
2/ SiO
2The bottom TiO of two membranes
2Film thickness is 200nm--500nm, top layer Si O
2The thickness of film is about 10nm-40nm; Described SiO
2/ TiO
2/ SiO
2The bottom SiO of trilamellar membrane
2The thickness of film is 10nm-40nm, middle TiO
2Film thickness is between the 100nm-500nm, top layer Si O
2The thickness of film is generally about 20nm-40nm.
3, the preparation method of antifogging self-cleaning glass according to claim 1 and 2 is characterized in that step is as follows:
A, glass substrate to be coated is cleaned up, on the specimen holder of the coating chamber of then glass substrate being packed into;
B, adjusting coating chamber working parameter, coating chamber forvacuum to 1.0 * 10
-3-1.0 * 10
-4Pa, to the mixed gas of sputtering chamber feeding argon gas and oxygen, the content of oxygen is 10%-100% then, control the flow of argon gas and oxygen respectively with mass flowmeter, regulate the vacuum chamber main valve, make to reach the required total pressure of sputter in the coating chamber, its scope is between 0.1Pa-10Pa;
C, employing direct current reaction magnetron sputtering technology are coated with TiO
2Layer plated film, sputtering target material is 99.5% titanium plate, target-substrate distance 3-15cm, the Surface field intensity of titanium target plate is 200-500 Gauss, regulating sputtering voltage is-500V--800V, sputtering current is 100mA-600mA, and substrate temperature is set in 25 ℃ to 500 ℃ scopes, and depositing of thin film speed is controlled at 1nm/min to 30nm/min with the size of regulating sputtering current.Control TiO by the control sputtering time
2The thickness of layer;
D, employing radiofrequency magnetron sputtering technology are coated with SiO
2Film.Sputtering target material is 99.5% SiO
2Silica glass, target-substrate distance 3-15cm, radio frequency power are adjusted between the 20W-200W, depositing of thin film speed with regulate the radio-frequency sputtering watt level with rate-controlling at 1nm/min between the 10nm/min.
4, the preparation method of antifogging self-cleaning glass according to claim 3, when the substrate of glass temperature is lower than 200 ℃, need carry out anneal after thin film deposition finishes when it is characterized in that plated film, annealing temperature is generally about 500 ℃, heat treatment time 30 to 60 minutes, the TiO that obtains
2Film generally is the anatase octahedrite phase.
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|---|---|---|---|
| CNA2006100193387A CN1872758A (en) | 2006-06-13 | 2006-06-13 | Antifogging self-cleaning glass, and preparation method |
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|---|---|---|---|
| CNA2006100193387A CN1872758A (en) | 2006-06-13 | 2006-06-13 | Antifogging self-cleaning glass, and preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432195A (en) * | 2011-09-06 | 2012-05-02 | 华中科技大学 | Rain-fog proof self-cleaning glass |
| CN102677054A (en) * | 2012-05-28 | 2012-09-19 | 广州市番禺双石钛金厂 | Decorative composite coating with dewatering self-cleaning function and preparation method of decorative composite coating |
| CN102108010B (en) * | 2009-12-29 | 2012-12-19 | 比亚迪股份有限公司 | glass composite material, preparation method thereof and anti-reflection self-cleaning glass product |
| CN103443043A (en) * | 2010-11-10 | 2013-12-11 | 肖特公开股份有限公司 | Glass or glass-eramic product with high temperature-stable, low-energy layer |
| CN113636760A (en) * | 2021-09-02 | 2021-11-12 | 青岛理工大学 | Antifogging self-cleaning glass and preparation method thereof |
| CN116103619A (en) * | 2022-10-27 | 2023-05-12 | 重庆文理学院 | Preparation method of silicon oxide film |
-
2006
- 2006-06-13 CN CNA2006100193387A patent/CN1872758A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108010B (en) * | 2009-12-29 | 2012-12-19 | 比亚迪股份有限公司 | glass composite material, preparation method thereof and anti-reflection self-cleaning glass product |
| CN103443043A (en) * | 2010-11-10 | 2013-12-11 | 肖特公开股份有限公司 | Glass or glass-eramic product with high temperature-stable, low-energy layer |
| CN103443043B (en) * | 2010-11-10 | 2016-08-10 | 肖特公开股份有限公司 | There is glass or the glass ceramics product of the low ergosphere of high-temperature stable |
| CN102432195A (en) * | 2011-09-06 | 2012-05-02 | 华中科技大学 | Rain-fog proof self-cleaning glass |
| CN102432195B (en) * | 2011-09-06 | 2014-06-18 | 华中科技大学 | Rain-fog proof self-cleaning glass |
| CN102677054A (en) * | 2012-05-28 | 2012-09-19 | 广州市番禺双石钛金厂 | Decorative composite coating with dewatering self-cleaning function and preparation method of decorative composite coating |
| CN113636760A (en) * | 2021-09-02 | 2021-11-12 | 青岛理工大学 | Antifogging self-cleaning glass and preparation method thereof |
| CN113636760B (en) * | 2021-09-02 | 2023-05-30 | 青岛理工大学 | Antifog self-cleaning glass and preparation method thereof |
| CN116103619A (en) * | 2022-10-27 | 2023-05-12 | 重庆文理学院 | Preparation method of silicon oxide film |
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