CN102503163A - Preparation method for titanium dioxide films with super-hydrophilic property under visible light - Google Patents

Preparation method for titanium dioxide films with super-hydrophilic property under visible light Download PDF

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CN102503163A
CN102503163A CN2011102836211A CN201110283621A CN102503163A CN 102503163 A CN102503163 A CN 102503163A CN 2011102836211 A CN2011102836211 A CN 2011102836211A CN 201110283621 A CN201110283621 A CN 201110283621A CN 102503163 A CN102503163 A CN 102503163A
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titanium dioxide
preparation
sol
room temperature
visible light
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CN102503163B (en
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王多书
王成伟
熊玉卿
李晨
王济洲
王军军
王建
李燕
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510 Research Institute of 5th Academy of CASC
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Abstract

The invention provides a preparation method for titanium dioxide films with super-hydrophilic property under visible light. The preparation method includes steps of dissolving Ti(OC4H9) in anhydrous ethanol, adding a proper amount of diethanol amine into the anhydrous ethanol added with the Ti(OC4H9), stirring mixture of the diethanol amine, the anhydrous ethanol and the Ti(OC4H9) by the aid of constant-temperature magnetic force at room temperature, further adding liquid mixture of water and ethanol, continuing stirring, realizing ageing at the room temperature, and obtaining uniform and stable titanium dioxide sol; coating the titanium dioxide sol on a clean glass substrate in a spinning manner by the aid of a spin coater, and drying the glass substrate coated with the titanium dioxide sol in a drying tank for 20 minutes to 40 minutes at the temperature ranging from 480 DEG C to 550 DEG C; and naturally cooling the glass substrate coated with the titanium dioxide sol to the room temperature after annealing is completed, and obtaining a super-hydrophilic titanium dioxide film. Traditional sol-gel process is adopted, and the titanium dioxide film with the super-hydrophilic property under visible light can be obtained by means of controlling annealing temperature, has the advantages of high quality and density, and can be used for various anti-fog places such as glass of buildings, rearview windows of automobiles, windshields, glass of bathrooms and the like.

Description

A kind of preparation method who under visible light, has ultra water-wet behavior titanium dioxide film
Technical field
The invention belongs to technical field of nano material, relate to a kind of preparation method of titanium deoxid film, relate in particular to a kind of preparation method who under the visible light condition, has ultra water-wet behavior titanium deoxid film.
Technical background
TiO 2As a kind of mineral-type materials; Has good chemicalstability, abrasion resistance, low cost; Advantages such as catalytic activity is high, oxidation capacity is strong, good stability, its these unique characteristics are used in various fields such as solar cell, photochemical catalysis and susceptible device susceptor widely.The preparation of titanium deoxid film in recent years and under visible light ultra water-wet behavior receive much concern.
Titanium deoxid film has Superhydrophilic under UV-irradiation; With this thin film coated in glass, pottery, polymkeric substance and metallic surface, airborne moisture or steam coagulation, water of condensation will form moisture film and sprawl uniformly from the teeth outwards; Even rainwater drenches in the above; Rainwater in surface attachment also can diffuse into uniform moisture film rapidly, makes film surface keep the transparency of height, has well anti-fog effect.Research for the ultra water-wet behavior of titanium oxide at present concentrates on photoinduction and doping aspect, and shows the bright and report of research of ultra water-wet behavior down for visible light.
Summary of the invention
The objective of the invention is provides a kind of preparation method who has ultra water-wet behavior titanium dioxide film in the visible light condition to the problem that exists in the prior art.
Having the preparation method of ultra water-wet behavior titanium dioxide film in the visible light condition, is the Ti (OC of elder generation with 10.0～13.0 m1 4H 9) 4Be dissolved in the absolute ethyl alcohol of 350～450.0ml; The diethylolamine that adds 14.5～16.0 ml constant temperature magnetic agitation 2～3 hours, adds entry and alcoholic acid mixing solutions under the room temperature again; Continue to stir 10～15 minutes; Obtaining the titanium volumetric molar concentration is the transparent light yellow colloidal sol of 0.45～0.55mol/L, and ageing is 48～72 hours under the room temperature, obtains uniform and stable TiO 2 sol; TiO 2 sol is spin-coated on the substrate of glass of cleaning with the spin coating appearance, places loft drier, 80～120 ℃ following dry 20～40 minutes; Taking-up is placed in the retort furnace, is that 2～3 ℃/min is warming up to 480～550 ℃ of condition annealing 2～3 hours with temperature rise rate; Annealing is cooled to room temperature after accomplishing naturally, makes ultra hydrophilic titanium dioxide film.
Above-mentioned spin coating rate-controlling is at 3900～4200rmp.
Describe below by the structure and the performance of concrete experiment the titanium deoxid film of the present invention's preparation.
1, structural characterization: Fig. 1 is the SEM figure that obtains titanium deoxid film after 100 ℃ of dryings, and as can beappreciated from fig. 1 the titanium dioxide film surface is more smooth.Fig. 2 is the SEM figure that obtains titanium deoxid film after 500 ℃ of annealing.From Fig. 1,2 contrast, can find out that the titanium deoxid film that after 500 ℃ of anneal, obtains is 8～15nm by particle diameter, the nanometer small-particle that is evenly distributed is formed, and thickness is about 80nm.Fig. 3 is the XRD spectrum that obtains titanium deoxid film after the differing temps annealing.As can beappreciated from fig. 3, when annealing temperature reaches 450 ℃, begin to occur anatase phase in the titanium deoxid film, along with the nanocrystal proportion of anatase octahedrite phase in the further rising film of annealing temperature progressively increases, 480～550 ℃ is optimum annealing temperature; When annealing temperature surpasses 550 ℃, the rutile phase will appear in the sample, and at this moment the ultra water-wet behavior of film begins variation.
2, water-wet behavior test: Fig. 4 is that water droplet is rigidly connecting the contact angle optical photograph figure that contacts the titanium dioxide film surface.The contact angle size is 13 o~ 15 oFig. 5 is the contact angle optical photograph figure of water droplet behind the double-layer porous film of titania/silica surface 1.08s, contact angle<3 oIn the contact angle test volume of water droplet be 4～6
Figure 366467DEST_PATH_IMAGE002
l.This shows that the titanium deoxid film of the present invention's preparation reveals ultra water-wet behavior in visible condition following table.
In sum; The present invention utilizes traditional sol-gel method; Through the control annealing temperature, obtain the visible light condition and have ultra water-wet behavior titanium dioxide film, it has high quality; Highdensity characteristics can be used for various antifog occasions such as glass of building, automotive rear-view window, windshield glass, bathroom glass.
Description of drawings
Fig. 1 is the SEM figure that obtains titanium deoxid film after 100 ℃ of dryings.
Fig. 2 is the SEM figure that obtains titanium deoxid film after 500 ℃ of annealing.
Fig. 3 is the XRD spectrum that obtains titanium deoxid film after the differing temps annealing.
Fig. 4 is that water droplet is rigidly connecting the contact angle optical photograph figure that contacts the titanium deoxid film surface.
Fig. 5 is that water droplet is at the contact angle optical photograph figure of titanium deoxid film after surperficial 1.08 seconds.
Embodiment
Be elaborated through the structure and the performance of specific embodiment below to the titanium deoxid film of the present invention's preparation.
Embodiment 1
(1) simple glass was used acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 15 minutes successively.
(2) with the Ti (OC of 12.0m1 4H 9) 4(content>=98%, density 0.999-1.003g/ml) is dissolved in the absolute ethyl alcohol of 400.0ml, then adds the diethylolamine (NH (C of 15.2 ml 2H 4OH) 2), under the room temperature on constant temperature blender with magnetic force vigorous stirring 2 hours, adding volume ratio again is H 2O:C 2H 5The mixing solutions of OH=1.08 ml:10.8 m1 continued stir about 10 minutes, obtained even, transparent light yellow colloidal sol; Ageing at room temperature 48 hours has obtained uniform and stable TiO 2 sol.
(3) TiO 2 sol is spun to (spin coating rotating speed 3900rmp) on the substrate of glass of cleaning with spin coating appearance (MIDSA Spin-1200D), places loft drier, drying is 30 minutes under 90 ℃; Taking-up is placed in the retort furnace, and temperature rise rate is that 2 ℃/min is warming up to 480 ℃ of annealing 2 hours.After annealing finished, the temperature natural cool to room temperature obtained titanium deoxid film.
The contact angle test: water droplet is 13 rigidly connecting the contact angle that contacts the titanium dioxide film surface o~ 15 o, the contact angle behind the 1.0s is 3 o, therefore, reveal ultra water-wet behavior in visible condition following table.
Embodiment 2
(1) simple glass was used acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 15 minutes successively.
(2) with the Ti (OC of 12.0 m1 4H 9) 4(content>=98%; Density 0.999-1.003g/ml) is dissolved in absolute ethyl alcohol (analytical pure>=99.7% of 400ml; Density is 0.789-0.791g/ml) in; The diethylolamine (analytical pure) that then adds 15.2 ml, under the room temperature on constant temperature blender with magnetic force vigorous stirring 2 hours, adding volume ratio again is H 2O:C 2H 50H=1.08ml:10.8 the mixing solutions of m1 continued stir about 20 minutes, obtained even, transparent light yellow colloidal sol, ageing at room temperature 50 hours has obtained uniform and stable TiO 2 sol.
(3) TiO 2 sol is spun to (spin coating rotating speed 4000rmp) on the substrate of glass of cleaning with spin coating appearance (MIDSA Spin-1200D), after the spin coating, places loft drier, drying is 20 minutes under 100 ℃; Inserting after the taking-up in the retort furnace, is that 2 ℃/PM is warming up to 500 ℃ of annealing 3 hours with temperature rise rate; After annealing finished, the temperature natural cool to room temperature obtained titanium deoxid film.
The contact angle test: water droplet is 13 rigidly connecting the contact angle that contacts the titanium dioxide film surface o~ 15 o, the contact angle behind the 1.0s<3 o, therefore, reveal ultra water-wet behavior in visible condition following table.
Embodiment 3
(1) simple glass was used acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 15 minutes successively.
(2) with the Ti (OC of 13.0m1 4H 9) 4Be dissolved in the absolute ethyl alcohol of 450.0ml, then add the diethylolamine (NH (C of 16 ml 2H 4OH) 2), under the room temperature on constant temperature blender with magnetic force vigorous stirring 2 hours, adding volume ratio again is H 2O:C 2H 5The mixing solutions of OH=1.05 ml:10.6 m1 continued stir about 10 minutes, obtained even, transparent light yellow colloidal sol, and ageing is 48 hours under the room temperature, has obtained uniform and stable TiO 2 sol.
(3) TiO 2 sol is spun to (spin coating rotating speed 3900rmp) on the substrate of glass of cleaning with spin coating appearance (MIDSA Spin-1200D), after the spin coating, places loft drier, drying is 20 minutes under 120 ℃; Inserting after the taking-up in the retort furnace, is that 2 ℃/PM is warming up to 530 ℃ of annealing 2 hours with temperature rise rate; After annealing finished, the temperature natural cool to room temperature obtained titanium deoxid film.
The contact angle test: water droplet is 13 rigidly connecting the contact angle that contacts the titanium dioxide film surface o~ 15 o, the contact angle behind the 1.0s<3 o, therefore, reveal ultra water-wet behavior in visible condition following table.
Embodiment 4
(1) simple glass was used acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 15 minutes successively.
(2) with the Ti (OC of 11m1 4H 9) 4Be dissolved in the absolute ethyl alcohol of 430.0ml, then add the diethylolamine (NH (C of 15.2 ml 2H 4OH) 2), under the room temperature on constant temperature blender with magnetic force vigorous stirring 2 hours, adding volume ratio again is H 2O:C 2H 5The mixing solutions of OH=1.08 ml:10.8 m1 continued stir about 10 minutes, obtained even, transparent light yellow colloidal sol, and ageing is 48 hours under the room temperature, has obtained uniform and stable TiO 2 sol.
(3) TiO 2 sol is spun to (spin coating rotating speed 4000rmp) on the substrate of glass of cleaning with spin coating appearance (MIDSA Spin-1200D), after the spin coating, places loft drier, drying is 20 minutes under 100 ℃; Inserting after the taking-up in the retort furnace, is that 3 ℃/PM is warming up to 550 ℃ of annealing 3 hours with temperature rise rate; After annealing finished, the temperature natural cool to room temperature obtained titanium deoxid film.
The contact angle test: water droplet is 13 rigidly connecting the contact angle that contacts the titanium dioxide film surface o~ 15 o, the contact angle behind the 1.0s is 3 o, therefore, under visible condition, also show the excess of export water-wet behavior.

Claims (3)

1. the preparation method who has ultra water-wet behavior titanium dioxide film in the visible light condition is the Ti (OC of elder generation with 10.0～13.0 m1 4H 9) 4Be dissolved in the absolute ethyl alcohol of 350～450.0ml; The diethylolamine that adds 14.5～16.0 ml constant temperature magnetic agitation 2～3 hours, adds entry and alcoholic acid mixing solutions under the room temperature again; Continue to stir 10～15 minutes; Obtaining the titanium volumetric molar concentration is the transparent light yellow colloidal sol of 0.45～0.55mol/L, and ageing is 48～72 hours under the room temperature, obtains uniform and stable TiO 2 sol; TiO 2 sol is spin-coated on the substrate of glass of cleaning with the spin coating appearance, places loft drier, 80～120 ℃ following dry 20～40 minutes; Taking-up is placed in the retort furnace, is that 2～3 ℃/min is warming up under 480～550 ℃ of conditions and annealed 2～3 hours with temperature rise rate; Annealing is cooled to room temperature after accomplishing naturally, makes ultra hydrophilic titanium dioxide film.
2. have the preparation method of ultra water-wet behavior titanium dioxide film according to claim 1 in the visible light condition, it is characterized in that: in said water and the alcoholic acid mixing solutions, water and alcoholic acid volume ratio are: 1.0～1.1ml:10.0～11.0 m1.
3. have the preparation method of ultra water-wet behavior titanium dioxide film according to claim 1 in the visible light condition, it is characterized in that: said spin coating rate-controlling is at 3900～4200rmp.
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CN104629612A (en) * 2013-11-14 2015-05-20 江南大学 Preparation method of high-refractive anti-fog film coating
CN105322094A (en) * 2015-06-08 2016-02-10 南开大学 Preparation method of titanium dioxide thin film for perovskite solar cell
CN107567430A (en) * 2015-05-04 2018-01-09 里奥玻璃太阳能有限公司 Coated glass for solar reflector
CN109485267A (en) * 2017-09-12 2019-03-19 中国科学院大连化学物理研究所 A kind of preparation method of the ultra-hydrophilic transparent anti-fog coating based on glass surface
CN111077600A (en) * 2020-01-07 2020-04-28 重庆金山医疗技术研究院有限公司 Lens glass, endoscope, and lens glass processing method
CN114105677A (en) * 2021-12-28 2022-03-01 中国科学院长春光学精密机械与物理研究所 Method for realizing lasting super-hydrophilicity of sapphire surface

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104629612A (en) * 2013-11-14 2015-05-20 江南大学 Preparation method of high-refractive anti-fog film coating
CN104629612B (en) * 2013-11-14 2017-06-27 江南大学 A kind of preparation method of refractive power anti-fog thin film coating high
CN107567430A (en) * 2015-05-04 2018-01-09 里奥玻璃太阳能有限公司 Coated glass for solar reflector
CN105322094A (en) * 2015-06-08 2016-02-10 南开大学 Preparation method of titanium dioxide thin film for perovskite solar cell
CN109485267A (en) * 2017-09-12 2019-03-19 中国科学院大连化学物理研究所 A kind of preparation method of the ultra-hydrophilic transparent anti-fog coating based on glass surface
CN111077600A (en) * 2020-01-07 2020-04-28 重庆金山医疗技术研究院有限公司 Lens glass, endoscope, and lens glass processing method
CN114105677A (en) * 2021-12-28 2022-03-01 中国科学院长春光学精密机械与物理研究所 Method for realizing lasting super-hydrophilicity of sapphire surface
CN114105677B (en) * 2021-12-28 2022-12-06 中国科学院长春光学精密机械与物理研究所 Method for realizing lasting super-hydrophilicity of sapphire surface

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