CN1298883C - Ag/TiO2 composite film with adjustable contact angle and preparation method thereof - Google Patents
Ag/TiO2 composite film with adjustable contact angle and preparation method thereof Download PDFInfo
- Publication number
- CN1298883C CN1298883C CNB2004100007276A CN200410000727A CN1298883C CN 1298883 C CN1298883 C CN 1298883C CN B2004100007276 A CNB2004100007276 A CN B2004100007276A CN 200410000727 A CN200410000727 A CN 200410000727A CN 1298883 C CN1298883 C CN 1298883C
- Authority
- CN
- China
- Prior art keywords
- film
- contact angle
- titanium deoxid
- tio2
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to an Ag/TiO2 composite film with an adjustable contact angle and a preparation method thereof, which belongs to the technical field of semiconductor photoproduction hydrophilicity. The present invention is characterized in that the Ag/TiO2 composite film with an adjustable contact angle is a composite film formed in such a manner that nano Ag particles are deposited on the surface of a TiO2 film. The preparation method comprises the following steps: a TiO2 film is prepared by a reactive magnetron sputtering method first, the reactive magnetron sputtering method can effectively control the crystal texture of the TiO2 film, and the hydrophilicity of the TiO2 film is increased; then, nano Ag particles are deposited on the prepared TiO2 film, and in this way, a composite film is prepared, which can be regulated between hydrophobicity and hydrophilicity. The Ag/TiO2 composite film with an adjustable contact angle is a film whose contact angle can be changed within a large range, and the film has strong hydrophobicity without ultraviolet radiation on present form and can be used for antifogging occasions. When cleared up, the Ag/TiO2 composite film with an adjustable contact angle is irradiated by ultraviolet to make the surface contact angle substantially descend, which is favorable for clearing up. When the ultraviolet radiation is stopped, the Ag/TiO2 composite film with an adjustable contact angle regains the hydrophobicity.
Description
Technical field
The Ag/TiO of contact angle adjustable
2Laminated film and preparation method thereof relates to semi-conductor photoproduction hydrophilicity technical field.
Technical background
Because many harm of knot mist phenomenon, the exotic materials with anti-caking mist has been subjected to people's attention.The material that is applied to anti-caking mist aspect at present mainly can be divided into two classes: water wetted material and hydrophobic material.The application principle of water wetted material mainly is because in general water spend less than 5 at the contact angle on water wetted material surface, and water forms the layer of even moisture film at material surface, thus the generation that prevents to tie the mist phenomenon.The anti-caking mist principle of hydrophobic material is: water is excessive at the contact angle of material surface, can't just as the globule on the lotus leaf, can slip away rapidly automatically attached to material surface, so also can not form knot mist phenomenon at all.Two kinds of material compared, the fog resistance of hydrophobic material can be more superior, but the easier cleaning of water wetted material.By retrieval, in present anti-caking mist material, promptly do not possess hydrophilicity, have the anti-caking mist material of hydrophobicity performance again.
In addition, existing water wetted material such as titanium deoxid film, most sol-gel process and the electrolysis processs of adopting of its preparation method, for example Chinese patent 1400185 discloses a kind of preparation high-activity titanium dioxide film self-cleaning glass preparation methods, comprises colloidal sol preparation, immersion plating, purification thermal treatment.Technology such as acid soak and surperficial aftertreatment.Chinese patent 1386916 provides a kind of preparation method who prepares optically catalytic TiO 2 film, adopts electrochemical oxidation and heating crystallization to handle the optically catalytic TiO 2 film that obtains to be grown in the nanocrystalline structure on the titanium base material.Chinese patent 1417147 discloses a kind of low temperature preparation method of nano titanium oxide self-cleaning glass, is basic components with the sol material, adopts crystal pulling method, room temperature or less than the dry down preparation titanium deoxid film of 300 degree.In these methods, sol-gel method is unfavorable for preparing large-area uniform thin film, and colloidal sol becomes loose easily in heat treatment process, so film is good inadequately with combining of matrix.Electrochemical oxidation process has limited the depositing of thin film matrix, is unfavorable for that film utilizes widely, especially needs to use under the higher occasion of the transmitance of matrix in windshield, eyes glass one class.
Summary of the invention
The objective of the invention is to propose a kind of surface has the Ag/TiO of contact angle adjustable of the silver-colored particle modification of nanoscale
2Laminated film.Because the nanoscale on surface silver particle modification makes Ag/TiO
2Laminated film becomes a kind of contact angle at variable in a big way thin-film material.This film presentation under the situation of no uv irradiation is stronger hydrophobicity performance, can be used for anti-caking mist occasion; Can its surface contact angle be declined to a great extent with uv irradiation when needing cleaning, be beneficial to cleaning; This material can recover its hydrophobicity performance after stopping uv irradiation.
The method for preparing this film is a magnetically controlled sputter method, magnetically controlled sputter method is widely used in the preparation of thin-film material, and because the uniformity of film that this method makes is good, film quality is high and good with matrix bond, be easy to control the film crystal phase structure, therefore especially be fit to large-scale industrial production.
The Ag/TiO of contact angle adjustable proposed by the invention
2Laminated film, it is characterized in that, it be a kind of the titanium deoxid film surface deposition have the silver-colored particulate laminated film of nanoscale, described titanium deoxid film be the titanium deoxid film of anatase octahedrite phase or anatase octahedrite mutually and the titanium deoxid film of the mixed phase of amorphous phase.
The Ag/TiO of contact angle adjustable
2The preparation method of laminated film, it is characterized in that, it at first adopts intermediate frequency reaction magnetocontrol sputtering method to obtain titanium deoxid film in the carrier surface deposition, adopts the medium frequency magnetron sputtering method to deposit the silver-colored particle with nanoscale then on above-mentioned titanium deoxid film, and it contains following steps:
1) adopt intermediate frequency reaction magnetocontrol sputtering method at carrier surface deposition of titanium oxide film:
1.1) carrier that will be used to prepare film carries out clean;
1.2) carrier that above-mentioned cleaning is good sends in the vacuum apparatus that is provided with the pure metallic titanium target;
1.3) utilizing the pure titanium target of intermediate frequency reaction magnetocontrol sputtering method sputter, reactant gases is a high purity oxygen gas, dividing potential drop is 0.05Pa～5Pa; Working gas is an argon gas, and pressure is 0.5～3Pa; Operating voltage is 200V～600V, and supply frequency is 15kHz～60kHz, and current density is 1mA/cm
2～10.0mA/cm
2, substrate temperature is 80 ℃～500 ℃; Sputtering time is more than 30 minutes;
1.4) reaction obtains titanium deoxid film after finishing;
2) the silver-colored particle of employing medium frequency magnetron sputtering method depositing nano yardstick on the above-mentioned titanium deoxid film for preparing:
2.1) the above-mentioned carrier that deposits titanium deoxid film is sent in the vacuum apparatus that is equipped with the fine silver target;
2.2) utilize medium frequency magnetron sputtering method sputter fine silver target, wherein
Operating voltage is 200～300V, and supply frequency is 15kHz～60kHz, and current density is 0.05mA/cm
2～0.5mA/cm
2
Working gas is an argon gas, and pressure-controlling is 1.0Pa～3.0Pa; Substrate temperature is 100 ℃～250 ℃; Sputtering time is 0.5～5 minute;
2.3) reaction obtains the silver-colored particulate titanium deoxid film that there is nanoscale on the surface after finishing.
Experiment showed, Ag/TiO proposed by the invention
2Laminated film presentation under the situation of no uv irradiation is stronger hydrophobicity performance, makes it have very strong light wetting ability with uv irradiation; Stop to recover its hydrophobicity performance behind the uv irradiation; Present method can prepare Ag/TiO
2Laminated film has reached its intended purposes.
Description of drawings
Fig. 1 is TiO among the embodiment 1
2The film sample X-ray diffraction spectrum;
Fig. 2 is the TiO of water at superior hydrophilicity
2The photo on film sample surface;
Fig. 3 is Ag/TiO
2The contact angle photo of the different irradiation times of laminated film sample.
Embodiment:
Ag/TiO proposed by the invention
2Laminated film adopts magnetically controlled sputter method to prepare in two steps: at first adopt reaction magnetocontrol sputtering to prepare titanium deoxid film, this method can effectively be controlled the film crystal structure, has improved the hydrophilicity of film; Deposition has the silver-colored particle of nanoscale on the titanium deoxid film for preparing then, so just prepare can hydrophobic and hydrophilic between freely regulated laminated film.
Embodiment 1
1) is carrier with the sheet glass, after clean, puts into the vacuum coating film equipment that is provided with the pure metallic titanium target, base vacuum 3.0 * 10
-3Pa;
2) utilize intermediate frequency reaction magnetocontrol sputtering technology:
The frequency that the midfrequent AC arc suppresses power supply is 25Hz, and operating voltage is 300V, and current density is 2mA/cm
2, working gas is 99.99% high-purity argon gas, its pressure is 2.0Pa; Reactant gases is a high purity oxygen gas, is 0.2Pa with mass rate controller control dividing potential drop; Bed temperature is 400 ℃ during thin film deposition; Sputtering time is 60 minutes.Sputter finishes to obtain the hydrophilic titanium deoxid film of light.
3) medium frequency magnetron sputtering deposition techniques Ag particle
The frequency that the midfrequent AC arc suppresses power supply is 25Hz, and operating voltage is 300V, and current density is 0.5mA/cm
2Working gas argon pressure 3.0Pa; Substrate temperature is that 250 ℃ of sputtering times are 30 seconds.
The Ag/TiO of Huo Deing under these conditions
2In the laminated film, titanium deoxid film is the anatase octahedrite phase, and silver-colored particle diameter is about 10nm, and the wetting ability experiment shows Ag/TiO
2Laminated film presents very strong hydrophobic effect when irradiation not, its contact angle even greater than the contact angle of Ag film, up to about 128 degree.And behind ultraviolet light irradiation, its contact angle can drop in 30min below 30 degree, and its contact angle is near 0 degree behind the 2h.Stop 3 days its Ag/TiO behind the irradiation
2The contact angle of laminated film can return to 100 degree.
Part steps parameter list among table 1 embodiment 2～5
| The titanium deoxid film preparation parameter | Deposition Ag particle parameter | ||||||||||||
| Working parameter | Supply frequency (kHz) | Operating voltage (V) | Current density (mA/ cm 2) | Argon pressure (Pa) | Oxygen pressure (Pa) | Substrate temperature (℃) | Sputtering time (min) | Supply frequency (kHz) | Operating voltage (V) | Current density (mA/ cm 2) | Argon pressure (Pa) | Substrate temperature (℃) | Sputtering time (min) |
| | 20 | 400 | 5 | 2 | 0.2 | 300 | 120 | 20 | 250 | 0.3 | 1.5 | 100 | 1 |
| Embodiment 3 | 15 | 200 | 1 | 0.5 | 0.05 | 200 | 180 | 15 | 200 | 0.05 | 2 | 150 | 3 |
| Embodiment 4 | 40 | 500 | 8 | 1 | 4 | 80 | 45 | 40 | 270 | 0.2 | 2.5 | 200 | 5 |
| Embodiment 5 | 60 | 600 | 10 | 3 | 5 | 500 | 30 | 60 | 300 | 0.1 | 1 | 250 | 2 |
The first step is as shown in table 1 with the parameter in 1, the second step of embodiment, the 3rd step in embodiment 2～5 preparation process, and the film performance that specifically obtains is estimated as follows:
The Ag/TiO of Huo Deing under these conditions
2In the laminated film, titanium deoxid film is the anatase octahedrite phase, and silver-colored particle is about 5nm, and the wetting ability experiment shows Ag/TiO
2Laminated film presents stronger hydrophobic effect when irradiation not, about 110 degree of its contact angle.Behind the uv-radiation, its contact angle drops in 30min below 20 degree, and its contact angle promptly drops to below 5 degree behind the 2h.Stop irradiation after 72 hours, its contact angle returns to about 100.
Embodiment 3
The Ag/TiO of Huo Deing under these conditions
2In the laminated film, titanium deoxid film is that anatase octahedrite phase and amorphous phase are mixed composition, and silver-colored particle is about 8nm, and the wetting ability experiment shows Ag/TiO
2Laminated film presents stronger hydrophobic effect when irradiation not, about 100 degree of its contact angle.Behind the uv-radiation, its contact angle drops in 30min below 10 degree, and its contact angle promptly drops to below 3 degree behind the 2h.Stop irradiation after 72 hours, its contact angle returns to about 80.
Embodiment 4
The Ag/TiO of Huo Deing under these conditions
2In the laminated film, titanium deoxid film is an amorphous phase, and silver-colored particle is about 8nm, and the wetting ability experiment shows Ag/TiO
2Laminated film presents stronger hydrophobic effect when irradiation not, about 120 degree of its contact angle.Behind the uv-radiation, its contact angle drops in 30min below 30 degree, and its contact angle promptly drops to below 15 degree behind the 2h.Stop irradiation after 72 hours, its contact angle returns to about 130.
Embodiment 5
The Ag/TiO of Huo Deing under these conditions
2In the laminated film, titanium deoxid film is the anatase octahedrite phase, and silver-colored particle is about 15nm, and the wetting ability experiment shows Ag/TiO
2Laminated film presents stronger hydrophobic effect when irradiation not, about 90 degree of its contact angle.Behind the uv-radiation, its contact angle drops in 30min below 15 degree, and its contact angle is about 0 degree behind the 2h.Stop irradiation after 72 hours, its contact angle returns to about 80.
As shown in Figure 1, the TiO that embodiment 1 is at first prepared
2Film is the anatase octahedrite phase structure by the titanium dioxide of the visible midfrequent AC magnetron sputtering preparation of XRD diffraction spectra.As shown in Figure 2, can find out the TiO for preparing
2Film contact angle to water under uv irradiation becomes rapidly about 0 degree, illustrates that it has stronger photoproduction wetting ability; (3a is during for irradiation not, and 3b is an irradiation after 2 hours, and 3c is for stopping irradiation 72 hours) Ag/TiO as can be seen among Fig. 3
2Laminated film is under uv irradiation, and through 2 hours, contact angle changed to about 0 degree from about 120 degree, stops irradiation after 72 hours, and the water contact angle of film changes about 100 degree, and Ag/TiO is described
2Laminated film is under uv irradiation, and its light wetting ability can be regulated in a big way.
Claims (2)
1, the Ag/TiO of contact angle adjustable
2Laminated film, it is characterized in that, it be a kind of the titanium deoxid film surface deposition have the silver-colored particulate laminated film of nanoscale, described titanium deoxid film be the titanium deoxid film of anatase octahedrite phase or anatase octahedrite mutually and the titanium deoxid film of the mixed phase of amorphous phase.
2, the Ag/TiO of contact angle adjustable as claimed in claim 1
2The preparation method of laminated film, it is characterized in that, it at first adopts intermediate frequency reaction magnetocontrol sputtering method to obtain titanium deoxid film in the carrier surface deposition, adopts the medium frequency magnetron sputtering method to deposit the silver-colored particle with nanoscale then on above-mentioned titanium deoxid film, and it contains following steps:
1) adopt intermediate frequency reaction magnetocontrol sputtering method at carrier surface deposition of titanium oxide film:
1.1) carrier that will be used to prepare film carries out clean;
1.2) carrier that above-mentioned cleaning is good sends in the vacuum apparatus that is provided with the pure metallic titanium target;
1.3) utilizing the pure titanium target of intermediate frequency reaction magnetocontrol sputtering method sputter, reactant gases is a high purity oxygen gas, dividing potential drop is 0.05Pa～5Pa; Working gas is an argon gas, and pressure is 0.5～3Pa; Operating voltage is 200V～600V, and supply frequency is 15kHz～60kHz, and current density is 1mA/cm
2～10.0mA/cm
2, substrate temperature is 80 ℃～500 ℃; Sputtering time is more than 30 minutes;
1.4) reaction obtains titanium deoxid film after finishing;
2) the silver-colored particle of employing medium frequency magnetron sputtering method depositing nano yardstick on the above-mentioned titanium deoxid film for preparing:
2.1) the above-mentioned carrier that deposits titanium deoxid film is sent in the vacuum apparatus that is equipped with the fine silver target;
2.2) utilize medium frequency magnetron sputtering method sputter fine silver target, wherein
Operating voltage is 200～300V, and supply frequency is 15kHz～60kHz, and current density is 0.05mA/cm
2～0.5mA/cm
2
Working gas is an argon gas, and pressure-controlling is 1.0Pa～3.0Pa; Substrate temperature is 100 ℃～250 ℃; Sputtering time is 0.5～5 minute;
2.3) reaction obtains the silver-colored particulate titanium deoxid film that there is nanoscale on the surface after finishing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100007276A CN1298883C (en) | 2004-01-16 | 2004-01-16 | Ag/TiO2 composite film with adjustable contact angle and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100007276A CN1298883C (en) | 2004-01-16 | 2004-01-16 | Ag/TiO2 composite film with adjustable contact angle and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1557990A CN1557990A (en) | 2004-12-29 |
| CN1298883C true CN1298883C (en) | 2007-02-07 |
Family
ID=34350483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100007276A Expired - Fee Related CN1298883C (en) | 2004-01-16 | 2004-01-16 | Ag/TiO2 composite film with adjustable contact angle and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1298883C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101903557B (en) * | 2007-12-18 | 2014-04-30 | Jx日矿日石金属株式会社 | Thin film mainly composed of titanium oxide, sintered sputtering target suitable for the production of thin film mainly composed of titanium oxide, and method for production of thin film mainly composed of titanium oxide |
| US8685593B2 (en) | 2009-09-22 | 2014-04-01 | GM Global Technology Operations LLC | Carbon based bipolar plate coatings for effective water management |
| US9520600B2 (en) | 2009-09-22 | 2016-12-13 | GM Global Technology Operations LLC | Conductive and hydrophilic bipolar plate coatings and method of making the same |
| CN101734615B (en) * | 2009-11-24 | 2013-03-27 | 哈尔滨工业大学 | Method for preparing metal/titanium dioxide composite nano material at low temperature by gamma-irradiation |
| CN102140621A (en) * | 2011-03-10 | 2011-08-03 | 苏州大学 | Preparation method of dense composite titanium dioxide film |
| CN106981295B (en) * | 2017-05-12 | 2019-02-19 | 东北师范大学 | It is a kind of can uvioresistant erasing holographic storage material and preparation method thereof |
| CN111069624B (en) * | 2019-12-30 | 2023-02-03 | 东北师范大学 | Preparation method and application of polarization-sensitive and ultraviolet-erasure-resistant silver nanostructure |
| CN113654951A (en) * | 2021-06-17 | 2021-11-16 | 河北工业大学 | Rapid and reversible regulation and control method for metal surface wettability |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6436442A (en) * | 1987-08-03 | 1989-02-07 | Teijin Ltd | Laminated glass |
| CN1354042A (en) * | 2001-10-31 | 2002-06-19 | 清华大学 | Titanium dioxide photocatalysis air-cleaning film and its preparation method |
-
2004
- 2004-01-16 CN CNB2004100007276A patent/CN1298883C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6436442A (en) * | 1987-08-03 | 1989-02-07 | Teijin Ltd | Laminated glass |
| CN1354042A (en) * | 2001-10-31 | 2002-06-19 | 清华大学 | Titanium dioxide photocatalysis air-cleaning film and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1557990A (en) | 2004-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9371250B2 (en) | Method for structuring a surface by means of ion-beam etching, structured surface and uses | |
| CN101429644B (en) | Production method of metal or metal oxide nano particle | |
| Tettey et al. | Progress in superhydrophilic surface development | |
| Chi et al. | Control of hydrophobic surface and wetting states in ultra-flat ZnO films by GLAD method | |
| CN1298883C (en) | Ag/TiO2 composite film with adjustable contact angle and preparation method thereof | |
| WO2009051271A1 (en) | Photocatalytic film, method for production of photocatalytic film, article, and hydrophilization method | |
| CN100465332C (en) | Process of preparing anatase crystal phase titanium dioxide film at low temp. | |
| WO2010005019A1 (en) | Inorganic thin film and process for production thereof, and glass | |
| JP2000096212A (en) | Photocatalyst film coated member and its production | |
| CN1417147A (en) | Low-temperature prepn process of self-cleaning nano Tio2 glass | |
| Srivatsa et al. | Synthesis of anatase titania nanostructures at room temperature by PECVD technique | |
| CN1304064C (en) | Titanium alloy biomedical composite material having titanium oxide coating layer on surface and its preparation method | |
| CN104818464B (en) | The method that large-specific surface area nano Argent grain film composite material is prepared without template | |
| CN102437209B (en) | A kind of photoelectrocatalysithin thin film and preparation method thereof | |
| CN105031950B (en) | A kind of method based on composite porous controlled evaporation surface temperature | |
| CN106167892B (en) | A kind of bimetallic/ceramic composite film and preparation method thereof | |
| CN1594646A (en) | Hydrophobic and ultraviolet radiation proof transparent film and preparation thereof | |
| Chi et al. | Photoirradiation caused controllable wettability switching of sputtered highly aligned c-axis-oriented zinc oxide columnar films | |
| WO2006090631A1 (en) | Multifunctional material | |
| Kim et al. | Enhanced hydrophilic property of TiO 2 thin film deposited on glass etched with O 2 plasma | |
| Kawakami et al. | Effects of nonequilibrium atmospheric-pressure O2 plasma-assisted annealing on anatase TiO2 nanoparticles | |
| KR20020045856A (en) | Photocatalyst coating sol capable of hardening at low temperature and preparation method thereof | |
| WO2011027872A1 (en) | Inorganic structure, method for producing same, and method for producing inorganic thin film | |
| Inoue et al. | TiO2 nanotube, nanowire, and rhomboid-shaped particle thin films fixed on a titanium metal plate | |
| CN1207095C (en) | TiO2 nano photocatalytic stainless steel and titanium fibre thread-line and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070207 Termination date: 20130116 |