CN107601917A - A kind of preparation method of titania-based self-cleaning glass - Google Patents
A kind of preparation method of titania-based self-cleaning glass Download PDFInfo
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- CN107601917A CN107601917A CN201711060957.5A CN201711060957A CN107601917A CN 107601917 A CN107601917 A CN 107601917A CN 201711060957 A CN201711060957 A CN 201711060957A CN 107601917 A CN107601917 A CN 107601917A
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- cleaning glass
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- titania
- based self
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000005348 self-cleaning glass Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 24
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 238000003618 dip coating Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 229910010251 TiO2(B) Inorganic materials 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000007747 plating Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 38
- 230000015556 catabolic process Effects 0.000 description 19
- 238000006731 degradation reaction Methods 0.000 description 19
- 239000004408 titanium dioxide Substances 0.000 description 14
- -1 octadecyl trichlorosilane alkane Chemical class 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000001237 Raman spectrum Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 150000007522 mineralic acids Chemical class 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The present invention relates to a kind of preparation method of titania-based self-cleaning glass, solve the problems, such as that tradition prepares complex process during self-cleaning glass, manpower and materials etc. required with high and plating membrane efficiency is low to be difficult to be widely applied.The preparation method is that being prepared with simple sol-gal process, size uniform, particle are less to contain TiO2(B) nanoparticle sol of crystalline phase, by glass-impregnated into colloidal sol, with 0.5cm/s 1.0cm/s speed by glass from TiO2Lifting is come out in colloidal sol, and 300 600 DEG C of annealings are carried out to sample, can obtain large area, the TiO of uniform film2Base self-cleaning glass.The TiO of the present invention2Base self-cleaning glass has preferable catalytic organism degrading activity, is highly suitable for the fields such as building outer glass wall, windshield and is promoted.The method of the present invention is not high to equipment requirement, greatly reduces production cost, while the production efficiency of this method is high, and film thickness can be controlled flexibly.With higher transmitance, it is properly applied in daily production and living.
Description
Technical field
The present invention relates to a kind of preparation method, and in particular to a kind of preparation method of titania-based self-cleaning glass.
Background technology
With to environmental degradation the understanding of harm and the raising to environmental protection requirement, people couple are brought to human lives
Reach automated cleaning effect using with environmental-protection function and using natural conditions, the green construction material that and can is beautified the environment is wanted
Ask more and more urgent, and the appearance of self-cleaning glass, exactly meet this wonderful dream of people.Self-cleaning glass is that one kind will
Titanium dioxide optical catalyst is carried on glass surface, so as to the novel environment friendly material with performances such as photocatalytic degradation automatically cleaning decontaminations
Material, has broad application prospects in building trade.
Preparation for common titanium deoxid film, chemical vapour deposition technique be carry out earliest research and on a production line
Self-cleaning glass preparation method [Sanderson K D, Mills A, Hurst S, the et al.The use of used
titanium dioxide coatings deposited by APCVD on glass substrates to provide a
dual action self cleaning[C]//46th Annual Society of Vacuum Coaters Technical
Conference.2003.].The advantages of chemical vapour deposition technique, there is at following 2 points：First, the film purity prepared is high, compactness is good,
Easily form good crystalline material.During deposition reaction, the composition of chemical reaction is participated in by being altered or modified, with regard to energy
Easily control the composition and feature of deposit.The film and material of a variety of functions is made.Once second, technology controlling and process
Parameter determines, can be easily controllable in technique with scale continuous production, and product quality is stable.But chemical vapour deposition technique also has
Individual shortcoming, equipment requirement is high, and cost is high, causes production cost height.At the same time, magnetron sputtering method is thin film physical vapor deposition
(PVD) another method.Under the conditions of glow discharge under being controlled in ring-type magnetic field, using cation caused by gas discharge,
High energy particle is accelerated as under electric field action, hits the surface of solid film material.After carrying out energy and momentum-exchange, film layer
The atom or molecule of material leave surface under bombardment and sputtered along certain direction to substrate, thin on substrate so as to realize
Deposition [Okada M, Yamada Y, Jin P, the et al.Fabrication of multifunctional coating of film
which combines low-e property and visible-light-responsive photocatalytic
activity[J].Thin Solid Films,2003,442(1):217-221.].But this method is unsuitable for largely producing, together
When method plating membrane efficiency it is low, and thickness does not reach the photocatalysis effect of requirement.And sol-gel high-temperature sintering process be at present
Industrialization and automatically cleaning effect it is maximally efficient self-cleaning glass production method.This method is from solution, by solution
After solation, gelation, nano thin-film is prepared under cryogenic, and then carry out plated film to glass obtains automatically cleaning with tempering
Glass.The nano-TiO that common sol-gel method obtains2All it is anatase titanium dioxide, so its photocatalysis efficiency highest.And pass through drying
Or the glass-film that tempering is handled, because the gasification volatilization of wherein organic matter makes film surface be in porous state, photocatalysis efficiency is more preferable
[Paz Y,Luo Z,Rabenberg L,et al.Photooxidative self-cleaning transparent
titanium dioxide films on glass[J].Journal of Materials Research,1995,10(11):
2842-2848.]。
Based on above-mentioned a variety of factors, a kind of new, efficient, cheap and easy to get titanium dioxide self-cleaning glass how is found
Already become the important topic studied now.
The content of the invention
The invention solves technical problem of the prior art, there is provided a kind of simple and environmentally-friendly, high-purity, high porosity
The preparation method of titania-based self-cleaning glass.
In order to solve the above-mentioned technical problem, technical scheme is specific as follows：
A kind of preparation method of titania-based self-cleaning glass, comprises the following steps：
Titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide and glycolic are added sequentially in ice cube, and constantly carries out magnetic force and stirs
Mix, finally give shallow yellow transparent solution；The titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide, the dosage of glycolic are by weight
Titanium tetrachloride：Concentrated ammonia liquor：Hydrogen peroxide：Glycolic=1~2：3~5：11~15：1；Resulting solution is placed in into constant temperature air blast to do
60-100 DEG C of reaction 5-8 hour in dry case；Distilled water is added after taking-up, after stirring to the solution for turning into stable homogeneous, adds nothing
It is 0-3 that machine strong acid, which adjusts its pH, is placed in autoclave and is heated to reaction temperature as 130-180 DEG C of reaction 1-3 hour；Treat anti-
White depositions washing, the centrifugation that liquid obtains after cooling down are answered, by resulting solid sample ultrasonic disperse in absolute ethyl alcohol, is obtained
To TiO2Colloidal sol；
Glass is immersed in above-mentioned TiO2In colloidal sol, dip-coating method is taken to obtain the TiO of different-thickness2Film, it is final right
It is made annealing treatment, that is, obtains TiO2Base self-cleaning glass.
In the above-mentioned technical solutions, the temperature that resulting solution is reacted in constant temperature blast drying oven is 60-80 DEG C.
In the above-mentioned technical solutions, the time that resulting solution is reacted in constant temperature blast drying oven is 5-6 hours.
In the above-mentioned technical solutions, the temperature that reaction solution reacts in autoclave is 140-160 DEG C.
In the above-mentioned technical solutions, the time that reaction solution reacts in autoclave is 1-1.5 hours.
In the above-mentioned technical solutions, the TiO2The concentration of colloidal sol is 0.01g/mL-0.025g/mL.
In the above-mentioned technical solutions, the speed of described Best-Effort request is 0.5cm/s-1.0cm/s.
In the above-mentioned technical solutions, temperature gained sample made annealing treatment is 300-600 DEG C.
In the above-mentioned technical solutions, temperature gained sample made annealing treatment is 450-550 DEG C.
The beneficial effects of the invention are as follows：
The preparation method of titania-based self-cleaning glass provided by the invention, is prepared into simple sol-gel process
To size uniform, particle is less contains TiO2(B) crystalline phase nanoparticle sol, by the colloidal sol of glass-impregnated to gained, with
0.5cm/s-1.0cm/s speed is by glass from TiO2Lifting comes out in colloidal sol, only need to carry out simple 300-600 DEG C to sample
Annealing, it becomes possible to obtain large area, the TiO of uniform film2Base self-cleaning glass.The preparation method avoids traditional preparation
The a series of problems such as complex process, low to the requirement such as manpower and materials height and plating membrane efficiency, suitable work during self-cleaning glass
Industryization mass produces.
TiO prepared by preparation method provided by the invention2There is base self-cleaning glass preferable catalytic organism degraded to live
Property, it is highly suitable for the fields such as building outer glass wall, windshield and is promoted.
Preparation method provided by the invention, it is not high to equipment requirement in preparation process, production cost is greatly reduced, together
When this method production efficiency it is high, film thickness can be controlled flexibly.
TiO prepared by preparation method provided by the invention2Base self-cleaning glass has higher transmitance, is properly applied to
In daily production and living.
Brief description of the drawings
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the TiO prepared by embodiment 12The pictorial diagram displaying of base self-cleaning glass.
Fig. 2 is the TiO prepared by embodiment 12The X ray diffracting spectrum of base self-cleaning glass.
Fig. 3 is the TiO prepared by embodiment 12The Raman spectrum of base self-cleaning glass.
Fig. 4 is the TiO prepared by embodiment 12The scanning electron microscopic picture of base self-cleaning glass.
Fig. 5 is the TiO prepared by embodiment 12Contact angle picture before and after the degradation of organic substances of base self-cleaning glass.
Fig. 6 is the TiO prepared by embodiment 12Contact angle angle contrast before and after the degradation of organic substances of base self-cleaning glass.
Fig. 7 is the TiO prepared by embodiment 22The pictorial diagram displaying of base self-cleaning glass.
Fig. 8 is the TiO prepared by embodiment 22The X ray diffracting spectrum of base self-cleaning glass.
Fig. 9 is the TiO prepared by embodiment 22The Raman spectrum of base self-cleaning glass.
Figure 10 is the TiO prepared by embodiment 22The scanning electron microscopic picture of base self-cleaning glass.
Figure 11 is the TiO prepared by embodiment 22Contact angle picture before and after the degradation of organic substances of base self-cleaning glass.
Figure 12 is the TiO prepared by embodiment 22Contact angle angle pair before and after the degradation of organic substances of base self-cleaning glass
Than.
Figure 13 is the TiO prepared by embodiment 32The pictorial diagram displaying of base self-cleaning glass.
Figure 14 is the TiO prepared by embodiment 32The X ray diffracting spectrum of base self-cleaning glass.
Figure 15 is the TiO prepared by embodiment 32The Raman spectrum of base self-cleaning glass.
Figure 16 is the TiO prepared by embodiment 32The scanning electron microscopic picture of base self-cleaning glass.
Figure 17 is the TiO prepared by embodiment 32Contact angle picture before and after the degradation of organic substances of base self-cleaning glass.
Figure 18 is the TiO prepared by embodiment 32Contact angle angle pair before and after the degradation of organic substances of base self-cleaning glass
Than.
Embodiment
The present invention is described in detail below in conjunction with the accompanying drawings.
The preparation method of titania-based self-cleaning glass provided by the invention, comprises the following steps：
Titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide and glycolic are added sequentially in ice cube, and constantly carries out magnetic force and stirs
Mix, finally give shallow yellow transparent solution；The titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide, the dosage of glycolic are by weight
Titanium tetrachloride：Concentrated ammonia liquor：Hydrogen peroxide：Glycolic=1~2：3~5：11~15：1；Resulting solution is placed in into constant temperature air blast to do
60-100 DEG C of reaction 5-8 hour in dry case, preferable temperature are 60-80 DEG C, and the time is 5-6 hours；Distilled water is added after taking-up, is stirred
Mix to the solution as stable homogeneous, it is 0-3 to add inorganic acid and adjust its pH, stirs 5min, is placed in autoclave
It is 140-160 DEG C that reaction temperature, which is heated to, as 130-180 DEG C of reaction 1-3 hour, preferable temperature, and the time is 1-1.5 hours；Treat anti-
White depositions washing, the centrifugation that liquid obtains after cooling down are answered, by resulting solid sample ultrasonic disperse in absolute ethyl alcohol, is obtained
To the TiO that concentration is 0.01g/mL-0.025g/mL2Colloidal sol；
Glass is immersed in above-mentioned TiO2In colloidal sol, dip-coating method is taken to obtain the TiO of different-thickness2Film, preferably soak
The speed of stain lifting is 0.5cm/s-1.0cm/s, and finally it is made annealing treatment, and it is 300-600 preferably to make annealing treatment temperature
DEG C, it is 450-550 DEG C further preferably to make annealing treatment temperature, that is, obtains TiO2Base self-cleaning glass.
Embodiment 1
Using titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide, glycolic as raw material, join it into appropriate ice cube, and constantly
Magnetic agitation is carried out, finally gives shallow yellow transparent solution, it is small that resulting solution is placed in into 80 DEG C of reactions 6 in constant temperature blast drying oven
When；Appropriate distilled water is added after taking-up, after stirring to the solution for turning into stable homogeneous, it is 1 to add inorganic acid and adjust its pH, is stirred
Mix 5min, be placed in autoclave be heated to reaction temperature for 160 DEG C react 1.5 hours；The titanium tetrachloride, concentrated ammonia liquor,
Hydrogen peroxide, the dosage of glycolic are by weight titanium tetrachloride：Concentrated ammonia liquor：Hydrogen peroxide：Glycolic=2：3：13：1, treat anti-
White depositions washing, the centrifugation obtained after should cooling down, by resulting solid sample ultrasonic disperse in absolute ethyl alcohol, is obtained
Concentration is 0.01g/mL TiO2Colloidal sol, to the Best-Effort request of the available glass piece collection difference number of plies, the speed of Best-Effort request is
0.5cm/s, and 550 DEG C of annealings are carried out to gained sample.By obtained film sample with certain density octadecyl three
The n-heptane solution of chlorosilane is modified, so that one layer of hydrophobic layer of sample surfaces uniform fold, to sample with certain light intensity
Ultraviolet light is irradiated to sample, has reached photocatalytic degradation effect of the titanium dioxide to organic substance, by different irradiation times
Sample carry out contact angle test.
The present embodiment is most preferred embodiment.Fig. 1 is film sample prepared in embodiment 1, and it is by 550 DEG C of annealing
Larger change does not occur in terms of translucency afterwards, still keeps the original higher translucency of glass.Fig. 2 is in embodiment 1
The X ray diffracting spectrum of prepared film sample, this it appears that the sample is the preferable anatase of crystallinity from figure
Phase titanic oxide.Fig. 3 is the Raman spectrum data of film sample prepared in embodiment 1, this it appears that institute from figure
It is purer anatase phase titanium dioxide to prepare titanium dioxide in film.Fig. 4 is film sample prepared in embodiment 1
Scanning electron microscopic picture, by its scanning electron microscope image can be seen that prepared sample its microstructure be rendered as it is more uniform
Planar structure.Film samples of the Fig. 5 prepared by embodiment 1 is before after modifying octadecyl trichlorosilane alkane by treatment with ultraviolet light
Contact angle pictorial diagram afterwards is shown, it is evident that the sample has obvious catalytic degradation to octadecyl trichlorosilane alkane in figure
Activity.Fig. 6 is the catalytic degradation curve of the octadecyl trichlorosilane alkane of prepared film sample in embodiment 1, can from the figure
Will become apparent from the sample has obvious catalytic degradation activity to octadecyl trichlorosilane alkane.
Embodiment 2
Using titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide, glycolic as raw material, join it into appropriate ice cube, and constantly
Magnetic agitation is carried out, finally gives shallow yellow transparent solution, it is small that resulting solution is placed in into 60 DEG C of reactions 5 in constant temperature blast drying oven
When；Appropriate distilled water is added after taking-up, after stirring to the solution for turning into stable homogeneous, it is 0 to add inorganic acid and adjust its pH, is stirred
Mix 5min, be placed in autoclave be heated to reaction temperature for 130 DEG C react 1 hour；The titanium tetrachloride, concentrated ammonia liquor, mistake
Hydrogen oxide, the dosage of glycolic are by weight titanium tetrachloride：Concentrated ammonia liquor：Hydrogen peroxide：Glycolic=1：5：11：1, question response
White depositions washing, the centrifugation obtained after cooling, by resulting solid sample ultrasonic disperse in absolute ethyl alcohol, is obtained dense
Spend the TiO for 0.025g/mL2Colloidal sol, to the Best-Effort request of the available glass piece collection difference number of plies, the speed of Best-Effort request is
1.0cm/s and 450 DEG C of annealings are carried out to gained sample.Hydrophobic layer is equally carried out to sample with octadecyl trichlorosilane alkane
Modification, ultraviolet light is carried out to it, and the test of contact angle is carried out in the different time.
Fig. 7 is film sample prepared in embodiment 2, and it does not send out after 450 DEG C of annealing in terms of translucency
Raw larger change, still keeps the original higher translucency of glass.Fig. 8 is the X ray of prepared film sample in embodiment 2
Diffracting spectrum, this it appears that the sample is crystallinity in general anatase phase titanium dioxide and B phase titanic oxides from figure
Mixed phase structure.Fig. 9 is the Raman spectrum data of film sample prepared in embodiment 2, as can be seen from the figure prepared
Titanium dioxide is the mixed phase structure of anatase phase titanium dioxide and B phase titanic oxides in film.Figure 10 is prepared in embodiment 2
Film sample scanning electron microscopic picture, can be seen that prepared sample its microstructure by its scanning electron microscope image is in
It is now more uniform planar structure.Figure 11 is that the film sample prepared by embodiment 2 passes through after octadecyl trichlorosilane alkane is modified
The contact angle pictorial diagram displaying crossed before and after treatment with ultraviolet light, it is evident that the sample has to octadecyl trichlorosilane alkane in figure
Preferable catalytic degradation activity.Figure 12 is the catalytic degradation of the octadecyl trichlorosilane alkane of prepared film sample in embodiment 2
Curve, it is evident that the sample has preferable catalytic degradation activity to octadecyl trichlorosilane alkane from the figure.
Embodiment 3
Using titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide, glycolic as raw material, join it into appropriate ice cube, and constantly
Magnetic agitation is carried out, finally gives shallow yellow transparent solution, resulting solution is placed in 100 DEG C of reactions 8 in constant temperature blast drying oven
Hour；Appropriate distilled water is added after taking-up, after stirring to the solution for turning into stable homogeneous, it is 3 to add inorganic acid and adjust its pH,
Stir 5min, be placed in autoclave be heated to reaction temperature for 180 DEG C react 3 hours；The titanium tetrachloride, concentrated ammonia liquor,
Hydrogen peroxide, the dosage of glycolic are by weight titanium tetrachloride：Concentrated ammonia liquor：Hydrogen peroxide：Glycolic=2：5：15：1, treat anti-
White depositions washing, the centrifugation obtained after should cooling down, by resulting solid sample ultrasonic disperse in absolute ethyl alcohol, is obtained
Concentration is 0.02g/mL TiO2Colloidal sol, carried out to the Best-Effort request of the available glass piece collection difference number of plies, and to gained sample
370 DEG C of annealings.Sample surfaces modify the octadecyl trichlorosilane alkane of one layer of normal heptane dilution, have reached hydrophobic effect, together
When with the ultraviolet lighting of some strength, it is right respectively at regular intervals to excite titanium dioxide to carry out catalytic degradation to organic matter
Sample carries out the test of contact angle.
Figure 13 is film sample prepared in embodiment 3, and it does not send out after 370 DEG C of annealing in terms of translucency
Raw larger change, still keeps the original higher translucency of glass.Figure 14 is the X of film sample prepared in embodiment 3
X ray diffraction collection of illustrative plates, it can be seen that the sample is the poor B phase titanic oxides of crystallinity from image.Figure 15 is in embodiment 3
The Raman spectrum data of prepared film sample, from image it can be seen that in prepared film titanium dioxide be crystallinity compared with
The B phase titanic oxides of difference.Figure 16 is the scanning electron microscopic picture of sample thin film prepared in embodiment 3, passes through its ESEM
Image can be seen that prepared sample its microstructure and be rendered as more uniform planar structure.Figure 17 is film in embodiment 3
Sample shows after octadecyl trichlorosilane alkane is modified by the contact angle pictorial diagram before and after treatment with ultraviolet light, can be obvious in image
Find out that the sample has certain catalytic degradation activity to octadecyl trichlorosilane alkane.Figure 18 is prepared film in embodiment 3
The catalytic degradation curve of the octadecyl trichlorosilane alkane of sample, it is evident that the sample is to octadecyl trichlorosilane from the figure
Alkane has certain catalytic degradation activity.
Embodiment 4
Using titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide, glycolic as raw material, join it into appropriate ice cube, and constantly
Magnetic agitation is carried out, finally gives shallow yellow transparent solution, it is small that resulting solution is placed in into 80 DEG C of reactions 6 in constant temperature blast drying oven
When；Appropriate distilled water is added after taking-up, after stirring to the solution for turning into stable homogeneous, it is 1 to add inorganic acid and adjust its pH, is stirred
Mix 5min, be placed in autoclave be heated to reaction temperature for 140 DEG C react 1.5 hours；The titanium tetrachloride, concentrated ammonia liquor,
Hydrogen peroxide, the dosage of glycolic are by weight titanium tetrachloride：Concentrated ammonia liquor：Hydrogen peroxide：Glycolic=2：3：13：1, treat anti-
White depositions washing, the centrifugation obtained after should cooling down, by resulting solid sample ultrasonic disperse in absolute ethyl alcohol, is obtained
Concentration is 0.01g/mL TiO2Colloidal sol, to the Best-Effort request of the available glass piece collection difference number of plies, the speed of Best-Effort request is
0.5cm/s, and 300 DEG C of annealings are carried out to gained sample.By obtained film sample with certain density octadecyl three
The n-heptane solution of chlorosilane is modified, so that one layer of hydrophobic layer of sample surfaces uniform fold, to sample with certain light intensity
Ultraviolet light is irradiated to sample, has reached photocatalytic degradation effect of the titanium dioxide to organic substance, by different irradiation times
Sample carry out contact angle test.
As a result show：Film sample obtained by the present embodiment is a small amount of anatase and TiO2(B) film of mixed phase, it is formed
For TiO2(B) main component is accounted for, anatase accounts for least a portion of mixed phase structure, while has the catalytic degradation of certain organic matter
Effect.
Embodiment 5
Using titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide, glycolic as raw material, join it into appropriate ice cube, and constantly
Magnetic agitation is carried out, finally gives shallow yellow transparent solution, it is small that resulting solution is placed in into 80 DEG C of reactions 6 in constant temperature blast drying oven
When；Appropriate distilled water is added after taking-up, after stirring to the solution for turning into stable homogeneous, a certain amount of inorganic acid is added and adjusts its pH
For 1,5min is stirred, is placed in autoclave and is heated to reaction temperature and is reacted 1.5 hours for 140 DEG C；It is the titanium tetrachloride, dense
Ammoniacal liquor, hydrogen peroxide, the dosage of glycolic are by weight titanium tetrachloride：Concentrated ammonia liquor：Hydrogen peroxide：Glycolic=2：3：13：
1, white depositions washing, the centrifugation obtained after question response cooling, by resulting solid sample ultrasonic disperse in absolute ethyl alcohol
In, obtain the TiO that concentration is 0.01g/mL2Colloidal sol, to the Best-Effort request of the available glass piece collection difference number of plies, Best-Effort request
Speed is 0.5cm/s, and 600 DEG C of annealings are carried out to gained sample.By obtained film sample with certain density 18
The n-heptane solution of alkyltrichlorosilanes is modified, so that one layer of hydrophobic layer of sample surfaces uniform fold, to sample with certain
The ultraviolet light of light intensity is irradiated to sample, has reached photocatalytic degradation effect of the titanium dioxide to organic substance, by different photographs
The sample for penetrating the time carries out contact angle test.
As a result show：Film sample obtained by the present embodiment is anatase and TiO2(B) film of mixed phase, while have
The catalytic degradation effect of certain organic matter.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (9)
1. a kind of preparation method of titania-based self-cleaning glass, it is characterised in that comprise the following steps：
Titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide and glycolic are added sequentially in ice cube, and constantly carry out magnetic agitation, most
Shallow yellow transparent solution is obtained eventually；The titanium tetrachloride, concentrated ammonia liquor, hydrogen peroxide, the dosage of glycolic are by weight tetrachloro
Change titanium：Concentrated ammonia liquor：Hydrogen peroxide：Glycolic=1~2：3~5：11~15：1；Resulting solution is placed in constant temperature blast drying oven
Middle 60-100 DEG C of reaction 5-8 hour；Distilled water is added after taking-up, after stirring to the solution for turning into stable homogeneous, is added inorganic strong
It is 0-3 that acid, which adjusts its pH, is placed in autoclave and is heated to reaction temperature as 130-180 DEG C of reaction 1-3 hour；Question response liquid
White depositions washing, the centrifugation obtained after cooling, by resulting solid sample ultrasonic disperse in absolute ethyl alcohol, is obtained
TiO2Colloidal sol；
Glass is immersed in above-mentioned TiO2In colloidal sol, dip-coating method is taken to obtain the TiO of different-thickness2Film, finally it is entered
Row annealing, that is, obtain TiO2Base self-cleaning glass.
2. the preparation method of titania-based self-cleaning glass according to claim 1, it is characterised in that resulting solution in
The temperature reacted in constant temperature blast drying oven is 60-80 DEG C.
3. the preparation method of titania-based self-cleaning glass according to claim 1, it is characterised in that resulting solution in
The time reacted in constant temperature blast drying oven is 5-6 hours.
4. the preparation method of titania-based self-cleaning glass according to claim 1, it is characterised in that reaction solution is in height
The temperature reacted in pressure reactor is 140-160 DEG C.
5. the preparation method of titania-based self-cleaning glass according to claim 1, it is characterised in that reaction solution is in height
The time reacted in pressure reactor is 1-1.5 hours.
6. the preparation method of titania-based self-cleaning glass according to claim 1, it is characterised in that the TiO2It is molten
The concentration of glue is 0.01g/mL-0.025g/mL.
7. the preparation method of titania-based self-cleaning glass according to claim 1, it is characterised in that described dipping
The speed of lifting is 0.5cm/s-1.0cm/s.
8. the preparation method of the titania-based self-cleaning glass according to claim 1-7 any one, it is characterised in that
The temperature that gained sample is made annealing treatment is 300-600 DEG C.
9. the preparation method of titania-based self-cleaning glass according to claim 8, it is characterised in that by gained sample
The temperature made annealing treatment is 450-550 DEG C.
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| CN112939482A (en) * | 2021-01-15 | 2021-06-11 | 邵阳学院 | TiO 22Nano needle film and preparation method thereof |
| CN116116399A (en) * | 2023-03-10 | 2023-05-16 | 东北师范大学 | Bimetallic oxide-supported titanium dioxide (B) photocatalytic material and preparation method and application thereof |
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| CN101293787A (en) * | 2008-05-28 | 2008-10-29 | 上海金博石材建设有限公司 | Modification method for nano-titanium dioxide on natural stone surface |
| CN102897833A (en) * | 2012-09-13 | 2013-01-30 | 北京科技大学 | Preparation method for titanium dioxide sol used for self-cleaning glass |
| CN104226287A (en) * | 2014-08-18 | 2014-12-24 | 江苏恒智纳米科技有限公司 | Preparation method of nano titanium dioxide photocatalyst thin film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101293787A (en) * | 2008-05-28 | 2008-10-29 | 上海金博石材建设有限公司 | Modification method for nano-titanium dioxide on natural stone surface |
| CN102897833A (en) * | 2012-09-13 | 2013-01-30 | 北京科技大学 | Preparation method for titanium dioxide sol used for self-cleaning glass |
| CN104226287A (en) * | 2014-08-18 | 2014-12-24 | 江苏恒智纳米科技有限公司 | Preparation method of nano titanium dioxide photocatalyst thin film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939482A (en) * | 2021-01-15 | 2021-06-11 | 邵阳学院 | TiO 22Nano needle film and preparation method thereof |
| CN112939482B (en) * | 2021-01-15 | 2022-12-02 | 邵阳学院 | TiO (titanium dioxide) 2 Nano needle film and preparation method thereof |
| CN116116399A (en) * | 2023-03-10 | 2023-05-16 | 东北师范大学 | Bimetallic oxide-supported titanium dioxide (B) photocatalytic material and preparation method and application thereof |
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