CN102503163B - 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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CN102503163B
CN102503163B CN 201110283621 CN201110283621A CN102503163B CN 102503163 B CN102503163 B CN 102503163B CN 201110283621 CN201110283621 CN 201110283621 CN 201110283621 A CN201110283621 A CN 201110283621A CN 102503163 B CN102503163 B CN 102503163B
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titanium dioxide
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room temperature
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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 super 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 super water-wet behavior titanium deoxid film.
Technical background
TiO 2As a kind of mineral-type materials, has good chemical stability, abrasion resistance, low cost, the advantages such as catalytic activity is high, oxidation capacity is strong, good stability, these characteristics of its uniqueness are widely used in various fields such as solar cell, photochemical catalysis and susceptible device susceptores.The in recent years preparation of titanium deoxid film and under visible light super 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 rapidly uniform moisture film, makes film surface keep the transparency of height, has well anti-fog effect.The at present research for the super water-wet behavior of titanium dioxide concentrates on photoinduction and doping aspect, and for the research aquatic foods and report that show super water-wet behavior under the visible light.
Summary of the invention
The objective of the invention is for problems of the prior art, a kind of preparation method who has super water-wet behavior titanium dioxide film in the visible light condition is provided.
The preparation method who has super water-wet behavior titanium dioxide film in the visible light condition is first with the Ti (OC of 10.0～13.0 mL 4H 9) 4Be dissolved in the dehydrated alcohol of 350～450.0mL, the diethanolamine that adds 14.5～16.0 mL, under the room temperature temperature constant magnetic stirring 2～3 hours, the mixing solutions that adds again entry and ethanol, 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 instrument, places loft drier, 80～120 ℃ lower dry 20～40 minutes; Taking-up is placed in the retort furnace, is warming up to 480～550 ℃ of condition annealing 2～3 hours take temperature rise rate as 2～3 ℃/min; After annealing is finished, naturally be cooled to room temperature, make super hydrophilic titanium dioxide film.
Above-mentioned spin coating rate-controlling is at 3900～4200rpm.
Describe below by structure and the performance of concrete experiment to 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 the titanium dioxide film surface is more smooth as can be seen from Figure 1.Fig. 2 is the SEM figure that obtains titanium deoxid film after 500 ℃ of annealing.Can find out from Fig. 1,2 contrast, the titanium deoxid film that obtains after 500 ℃ of anneal is 8～15nm by particle diameter, and the nanometer small-particle that is evenly distributed forms, and thickness is about 80nm.Fig. 3 is the XRD spectrum that obtains titanium deoxid film after the differing temps annealing.As can be seen from Figure 3, begin to occur anatase phase in the titanium deoxid film when annealing temperature reaches 450 ℃, along with the nanocrystal proportion of Anatase in the further rising film of annealing temperature progressively increases, 480～550 ℃ is optimum annealing temperature; When annealing temperature surpasses 550 ℃, Rutile Type will appear in the sample, and at this moment the super 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 that water droplet is in the contact angle optical photograph figure of titanium deoxid film surface after 1.08 seconds, contact angle＜3 oThe volume of water droplet is 4～6 in the contact angle test
Figure DEST_PATH_IMAGE001
L.This shows, the titanium deoxid film of the present invention's preparation reveals super water-wet behavior in visible condition following table.
In sum, the present invention utilizes traditional sol-gel method, by the control annealing temperature, obtain the visible light condition and have super water-wet behavior titanium dioxide film, it has high quality, highdensity characteristics can be used for the various antifog occasions such as glass of building, automobile rearview 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 surface after 1.08 seconds.
Embodiment
Be elaborated below by structure and the performance of specific embodiment to the titanium deoxid film of the present invention's preparation.
Embodiment 1
(1) simple glass was used successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning 15 minutes.
(2) with the Ti (OC of 12.0mL 4H 9) 4(content 〉=98%, density 0.999-1.003g/mL) is dissolved in the dehydrated alcohol of 400.0mL, then adds the diethanolamine (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 is H again 2O:C 2H 5The mixing solutions of OH=1.08 mL:10.8 mL continued stir about 10 minutes, obtained even, transparent light yellow colloidal sol; At room temperature ageing 48 hours has obtained uniform and stable TiO 2 sol.
(3) TiO 2 sol is spun to (spin coating rotating speed 3900rpm) on the substrate of glass of cleaning with spin coating instrument (MIDSA Spin-1200D), places loft drier, lower dry 30 minutes at 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, temperature naturally cooled to room temperature, obtains 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 super water-wet behavior in visible condition following table.
Embodiment 2
(1) simple glass was used successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning 15 minutes.
(2) with the Ti (OC of 12.0 mL 4H 9) 4(content 〉=98%, density 0.999-1.003g/mL) is dissolved in dehydrated alcohol (analytical pure 〉=99.7% of 400ml, density is 0.789-0.791g/mL) in, the diethanolamine (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 is H again 2O:C 2H 50H=1.08mL:10.8 the mixing solutions of mL continued stir about 20 minutes, obtained even, transparent light yellow colloidal sol, at room temperature ageing 50 hours has obtained uniform and stable TiO 2 sol.
(3) TiO 2 sol is spun to (spin coating rotating speed 4000rpm) on the substrate of glass of cleaning with spin coating instrument (MIDSA Spin-1200D), after the spin coating, places loft drier, lower dry 20 minutes at 100 ℃; Insert after the taking-up in the retort furnace, be warming up to 500 ℃ of annealing 3 hours take temperature rise rate as 2 ℃/per minute; After annealing finished, temperature naturally cooled to room temperature, obtains 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 super water-wet behavior in visible condition following table.
Embodiment 3
(1) simple glass was used successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning 15 minutes.
(2) with the Ti (OC of 13.0mL 4H 9) 4Be dissolved in the dehydrated alcohol of 450.0mL, then add the diethanolamine (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 is H again 2O:C 2H 5The mixing solutions of OH=1.05 mL:10.6 mL 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 3900rpm) on the substrate of glass of cleaning with spin coating instrument (MIDSA Spin-1200D), after the spin coating, places loft drier, lower dry 20 minutes at 120 ℃; Insert after the taking-up in the retort furnace, be warming up to 530 ℃ of annealing 2 hours take temperature rise rate as 2 ℃/per minute; After annealing finished, temperature naturally cooled to room temperature, obtains 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 super water-wet behavior in visible condition following table.
Embodiment 4
(1) simple glass was used successively acetone, dehydrated alcohol, deionized water ultrasonic cleaning 15 minutes.
(2) with the Ti (OC of 11mL 4H 9) 4Be dissolved in the dehydrated alcohol of 430.0mL, then add the diethanolamine (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 is H again 2O:C 2H 5The mixing solutions of OH=1.08 mL:10.8 mL 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 4000rpm) on the substrate of glass of cleaning with spin coating instrument (MIDSA Spin-1200D), after the spin coating, places loft drier, lower dry 20 minutes at 100 ℃; Insert after the taking-up in the retort furnace, be warming up to 550 ℃ of annealing 3 hours take temperature rise rate as 3 ℃/per minute; After annealing finished, temperature naturally cooled to room temperature, obtains 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 (1)

1. the preparation method who has super water-wet behavior titanium dioxide film in the visible light condition is first with the Ti (OC of 10.0～13.0 m1 4H 9) 4Be dissolved in the dehydrated alcohol of 350～450.0ml, the diethanolamine that adds 14.5～16.0 ml, under the room temperature temperature constant magnetic stirring 2～3 hours, the mixing solutions that adds again entry and ethanol, 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 instrument, places loft drier, 80～120 ℃ lower dry 20～40 minutes; Taking-up is placed in the retort furnace, is warming up under 480～550 ℃ of conditions take temperature rise rate as 2～3 ℃/min and anneals 2～3 hours; After annealing is finished, naturally be cooled to room temperature, make super hydrophilic titanium dioxide film;
In the mixing solutions of described water and ethanol, the volume ratio of water and ethanol is: 1.0～1.1ml:10.0～11.0 m1; Described spin coating rate-controlling is at 3900～4200rpm.
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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
EP3090990A1 (en) * 2015-05-04 2016-11-09 Rioglass Solar, S.A. Coated glass for solar reflectors
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
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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