CN102898035B - Composite film, its preparation method and composite material - Google Patents
Composite film, its preparation method and composite material Download PDFInfo
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- CN102898035B CN102898035B CN201110212275.8A CN201110212275A CN102898035B CN 102898035 B CN102898035 B CN 102898035B CN 201110212275 A CN201110212275 A CN 201110212275A CN 102898035 B CN102898035 B CN 102898035B
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Abstract
The invention provides a composite film containing titanium dioxide and silicon dioxide, wherein the titanium dioxide is nitrogen doped titanium dioxide. In terms of the total mole number of the film, the titanium dioxide accounts for 9.8-49.8 mole percent, the silicon dioxide accounts for 44.8-88.2 mole percent, and the nitrogen element accounts for 0.4-2 mole percent. Being spherical, the silicon dioxide has an average particle size of 80-100nm. The invention also provides a preparation method of the thin film and a composite material containing the film. The film provided in the invention has high light transmittance and a strong self-cleaning ability.
Description
Technical field
The present invention relates to a kind of laminated film and preparation method thereof and matrix material.
Background technology
TiO
2film is a kind of important functional materials, and under UV-irradiation, surface has the water-wet behavior of height, by organic pollutant deep oxidation, finally can generate CO
2and H
2o etc.There is the functions such as sterilization, self-cleaning, photocatalytic degradation dirt.Be commonly used in the substrate surfaces such as glass, preparation has self-cleaning product.As can be used in building glass, cladding glass, partition glass, decoration dress drill the article surfaces such as glass, automobile windshield, automobile side window glass, speculum, skylight glass, lamp lampshade glass, cover-plate glass, hospital surgical equipment, kitchen glass, glass for lenses, household appliance glass, instrument glass, wall tile and sanitary ware.But, at present from TiO
2the automatically cleaning effect of film is poor, can only just have automatically cleaning effect under given conditions, and meanwhile, the self_cleaning effect time is short, substrate surface is exposed in contaminated air and crosses for a long time, be easy to lose efficacy because surface is covered dirty by dust.
Chinese patent CN101372394A discloses a kind of method utilizing surfactant modified titanium dioxide synthesizing ultra-hydrophilic film, its composition comprises: prepare TiO 2 sol, pre-treatment, dipping-lift, attachment colloidal sol, dry, sol-gel self-combustion synthesis prepares titanium dioxide nano-particle, pre-treatment titanium dioxide nano-particle, spin coating, dry, roasting, it is characterized in that: at ambient temperature, prepare TiO 2 sol, the method of dipping-lift is adopted to be attached on glass or conductive glass ITO with the pull rate of 60 mm/min by layer of titanium dioxide colloidal sol, the dipping time of lift front glass substrate in TiO 2 sol is 2 minutes, 60 DEG C of dryings, obtain egative film, the surfactant modified paste titanium dioxide prepared sol-gel self-combustion synthesis before spin coating nanoparticle of admiring carries out pre-treatment, then the surfactant modified titanium dioxide nano-particle adopting the method for spin coating to fix one deck sol-gel self-combustion synthesis on above-mentioned egative film to prepare, dry, roasting, finally obtain nanometer titanium dioxide to admire film.
The time that the wetting ability of the film that aforesaid method prepares continues is short, thus makes its automatically cleaning ability low, and the transmittance rate of film that the method prepares is low, can not satisfy the demands.
Summary of the invention
The present invention solves the low technical problem of low, the glossy rate of automatically cleaning ability of titanium deoxid film of the prior art, thus provides a kind of and can have automatically cleaning ability and the high titanium deoxid film of transmittance and preparation method thereof and the matrix material containing this film for a long time.
The invention provides a kind of laminated film, this film contains titanium dioxide and silicon-dioxide; Described titanium dioxide is nitrogen-doped titanium dioxide, wherein, with the total mole number of film for benchmark, the molar percentage of described titanium dioxide is 9.8-49.8%, the molar percentage of described silicon-dioxide is 44.8-88.2%, the molar percentage of described nitrogen element is 0.4-2%, and described silicon-dioxide is spherical, and the median size of silicon-dioxide is 80-100nm.
Present invention also offers the preparation method of above-mentioned laminated film, the method comprises the following steps:
The method comprises the following steps:
S1, preparation SiO
2colloidal sol
Tetraethoxy, hydration dehydrated alcohol mix and the formation mixing solutions that stirs by SS1; Wherein, the mol ratio of each material is: tetraethoxy: water: dehydrated alcohol=1:3-5:35-45, then with acid, pH value is adjusted to 2-4, stirs ageing;
SS2 alkali by the pH regulator of the mixing solutions in step SS1 to 8-10, and ageing formed colloidal sol;
PH value is adjusted to 2-4 by the colloidal sol acid in step SS2 by SS3, obtains acid SiO
2colloidal sol;
S2, preparation TiO
2colloidal sol
Tetrabutyl titanate, water, methyl ethyl diketone and dehydrated alcohol are mixed and stirs, TiO
2in colloidal sol, the molar ratio of each material is tetrabutyl titanate: water: methyl ethyl diketone: dehydrated alcohol=1:2-3:0.5-1.5:16-20, is then 3-5 with acid for adjusting pH value, stirs ageing;
S3, preparation SiO
2-TiO
2complex sol
At the above-mentioned acid SiO of stirring
2while colloidal sol, by above-mentioned TiO
2colloidal sol slowly joins above-mentioned SiO
2in colloidal sol, continue to stir formation SiO
2-TiO
2complex sol;
S4, prepare the N-SiO of N doping
2-TiO
2complex sol
Tensio-active agent is joined above-mentioned SiO
2-TiO
2stir in complex sol; Then add nitrogenous substances wherein, stir the N-SiO forming N doping
2-TiO
2complex sol;
S5, prepare laminated film
Substrate is slowly inserted into above-mentioned N-SiO
2-TiO
2after flooding 1-2 minute in complex sol, form one deck N-SiO by liquid level method at substrate surface
2-TiO
2film, then placed by glass substrate and naturally dry in atmosphere, substrate is put into baking oven and dries, then roasting is formed and is carried on on-chip laminated film, divests substrate, namely obtains laminated film;
Wherein, nitrogenous substances in N, the N-SiO of N doping
2-TiO
2in complex sol, with the integral molar quantity of titanium dioxide, silicon-dioxide and nitrogen element for benchmark, the molar percentage of described titanium dioxide is 3-45%, and the molar percentage of described silicon-dioxide is 15-81%, and the molar percentage of described nitrogen element is 10-70%; With the N-SiO of N doping
2-TiO
2the total mass of complex sol is benchmark, and the content of described tensio-active agent is 1-20%.
The present invention also provides a kind of matrix material, and this material comprises base material and the laminated film invested on base material, and wherein, described laminated film is laminated film of the present invention.
Film of the present invention, has the automatically cleaning ability more lasting than other products.Although pure silicon dioxide antireflective coating has higher reflection preventing ability, but because silicon-dioxide self does not have automatically cleaning characteristic, therefore light transmission will be made greatly to decline due to the pollution in environment in a short time, pure titinium dioxide automatically cleaning film, then due to himself specific refractory power too high (up to 2.45), makes light transmission greatly decline thus have impact on be similar to the application in area of solar cell.This product by reasonably regulating the ratio of titanium dioxide and silicon-dioxide, and regulates film forming porosity, thus is reduced by the effective refractive index of this kind of laminated film, ensure that high light transmittance.In addition, due in laminated film preparation process to the element such as N of titania part doping, effectively have adjusted the band gap width of titanium dioxide, even if thus make the photocatalytic activity of titanium dioxide also have photocatalytic activity when the low light level (without uviolizing).This performance enables environmental pollutant be removed by from film surface timely, thus makes the self-cleaning performance that film can keep for a long time.In addition, silicon-dioxide is Lewis acid in general sense, has stronger adsorption at normal temperatures and pressures to the water with nucleophilicity, that is so-called " lock water " Performance Ratio is better.But silicon-dioxide does not have photocatalytic activity, will cause polluting after the placement through the certain period and the moisture film on surface is disappeared, and adding of titanium dioxide can make up this, because its photocatalytic activity can make film keep clean, and there is a large amount of oh groups all the time, thus the maintenance that the Superhydrophilic on order surface can be permanent.
Embodiment
The invention provides a kind of laminated film, this film contains titanium dioxide and silicon-dioxide; Described titanium dioxide is nitrogen-doped titanium dioxide, wherein, with the total mole number of film for benchmark, the molar percentage of described titanium dioxide is 9.8-49.8%, the molar percentage of described silicon-dioxide is 44.8-88.2%, the molar percentage of described nitrogen element is 0.4-2%, and described silicon-dioxide is spherical, and the median size of silicon-dioxide is 80-100nm.
According to film provided by the invention, in order to make the wetting ability of film more lasting, preferably, the molar percentage of described titanium dioxide is 30-40%, and the molar percentage of described silicon-dioxide is 70-60%, and the molar percentage of described nitrogen element is 0.5-1.5%.
According to film provided by the invention, in order to make the wetting ability of film more lasting, preferably, described titanium dioxide is the mixture of anatase titanium dioxide and rutile titanium dioxide.Although rutile titanium dioxide also has certain photocatalytic activity, due to itself band gap higher (block rutile titanium dioxide band gap is at 3.3 electron-volts), thus make it extremely weak in the sun; Anatase titanium dioxide then has comparatively low band gaps (block anatase titanium dioxide band gap is at 3.1 electron-volts) relative to rutile-type, has comparatively high light catalytic activity under solar radiation.Relevant report and experiment prove that the power of photocatalytic activity is not only relevant to actual crystal band gap, also closely related with crystal interface state.When Detitanium-ore-type and rutile titanium dioxide exist and be mutually close to simultaneously, show the photocatalytic activity stronger than unicity crystal.It is generally acknowledged, this is because the existence of this interfacial state makes the photoelectronic life-span of generation greatly strengthen, once because the existence at interface hinders compound again after producing photoelectron, thus makes photocatalytic activity increase.
According to film provided by the invention, preferably, the specific refractory power of described film is 1.25-1.4.Because film of the present invention is commonly used in glass surface, and the specific refractory power of general glass is 1.5, and air refraction is 1, and to reduce the reflection at this interface, then surperficial institute coating film must meet λ/4.According to Theoretical Calculation, have to make visible ray and project the most by force, then film forming effective refractive index is about 1.3.
The invention provides a kind of preparation method of above-mentioned film, the method comprises the following steps:
The method comprises the following steps:
S1, preparation SiO
2colloidal sol
Tetraethoxy, hydration dehydrated alcohol mix and the formation mixing solutions that stirs by SS1; Wherein, the mol ratio of each material is: tetraethoxy: water: dehydrated alcohol=1:3-5:35-45, then with acid, pH value is adjusted to 2-4, stirs ageing;
SS2 alkali by the pH regulator of the mixing solutions in step SS1 to 8-10, and ageing formed colloidal sol;
PH value is adjusted to 2-4 by the colloidal sol acid in step SS2 by SS3, obtains acid SiO
2colloidal sol;
S2, preparation TiO
2colloidal sol
Tetrabutyl titanate, water, methyl ethyl diketone and dehydrated alcohol are mixed and stirs, TiO
2in colloidal sol, the molar ratio of each material is tetrabutyl titanate: water: methyl ethyl diketone: dehydrated alcohol=1:2-3:0.5-1.5:16-20, is then 3-5 with acid for adjusting pH value, stirs ageing;
S3, preparation SiO
2-TiO
2complex sol
At the above-mentioned acid SiO of stirring
2while colloidal sol, by above-mentioned TiO
2colloidal sol slowly joins above-mentioned SiO
2in colloidal sol, continue to stir formation SiO
2-TiO
2complex sol;
S4, prepare the N-SiO of N doping
2-TiO
2complex sol
Tensio-active agent is joined above-mentioned SiO
2-TiO
2stir in complex sol; Then add nitrogenous substances wherein, stir the N-SiO forming N doping
2-TiO
2complex sol;
S5, prepare laminated film
Substrate is slowly inserted into above-mentioned N-SiO
2-TiO
2after flooding 1-2 minute in complex sol, form one deck N-SiO by liquid level method at substrate surface
2-TiO
2film, then placed by glass substrate and naturally dry in atmosphere, substrate is put into baking oven and dries, then roasting is formed and is carried on on-chip laminated film, divests substrate, namely obtains laminated film;
Wherein, nitrogenous substances in N, the N-SiO of N doping
2-TiO
2in complex sol, with the integral molar quantity of titanium dioxide, silicon-dioxide and nitrogen element for benchmark, the molar percentage of described titanium dioxide is 3-45%, and the molar percentage of described silicon-dioxide is 15-81%, and the molar percentage of described nitrogen element is 10-70%; With the N-SiO of N doping
2-TiO
2the total mass of complex sol is benchmark, and the content of described tensio-active agent is 1-20%.
According to preparation method provided by the present invention, preferably, the time of stirring in described step SS1 is 0.5-1.5 hour, and the time of ageing is 24-96 hour; The time of ageing in described step SS2 is 24-96 hour; The time of stirring in step S2 is 0.5-1.5 hour, and the time of ageing is 24-96 hour; The time of stirring in step S3 is 30-60 minute; Adding the churning time after tensio-active agent in step S4 is 30-60 minute, and adding the churning time after nitrogenous substances is 30-60 minute.The temperature of described oven dry is 70-90 DEG C, and the time is 40-80min; The temperature of described roasting is 500-600 DEG C, and the time is 1-3 hour.
N-SiO
2-TiO
2the content of the nitrogen element in colloidal sol is very high, but in roasting process, most nitrogen element all vapors away with the form of nitrogen and oxynitride, only has a small amount of nitrogen element to enter titanium dioxide crystal.
Preparation method of the present invention, mixes each material in SS1, at ageing process, slowly can be hydrolyzed, become a small amount of crystal seed, for the reaction in SS2 is prepared.In SS2, hydrolysis generates silicon-dioxide, owing to being be hydrolyzed in the basic conditions, makes the silicon-dioxide globulate of generation and particle diameter is little, and such silicon-dioxide can improve the hydrophilic persistence of the film that the later stage is formed.
According to preparation method provided by the present invention, acid used in step SS1 of the present invention, SS3 and S2 can be various acid well known in the art, but can easily remove in order to follow-up, and preferably, acid used in step SS1, SS3 and S2 is hydrochloric acid or nitric acid.Hydrochloric acid and nitric acid at high temperature can form HCl and NO respectively
2gas leaves.
According to preparation method provided by the present invention, the various alkali that alkali used in step SS2 can be commonly used for this area, but in order to not introduce other impurity, preferably, alkali used in step SS2 is ammoniacal liquor, ammoniacal liquor at high temperature partly can become gas, and another part forms N element and is doped in titanium dioxide crystal.Because the consumption of ammoniacal liquor is less, and form that N element is doped in titanium dioxide crystal less.
According to preparation method provided by the present invention, the various tensio-active agents that described surfactivity can be commonly used for this area, preferably, described tensio-active agent is at least one in Qu Latong X100, diethanolamine, trolamine, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, oleic acid, polyoxyethylene glycol and ethylene glycol amine.
According to preparation method provided by the present invention, preferably, described nitrogenous substances is at least one in bicarbonate of ammonia and urea.
According to preparation method provided by the present invention, preferably, described substrate is glass or pottery.
According to preparation method provided by the present invention, in order to make the film thickness that obtains even, there is no other impurity, preferably, before preparing laminated film, base material being carried out surface treatment, to obtain the smooth base material of smooth surface.
The invention provides a kind of matrix material, this material comprises base material and the laminated film invested on base material, and wherein, described laminated film is laminated film of the present invention.
According to matrix material provided by the present invention, preferably, described base material is glass or pottery.
According to matrix material provided by the present invention, base material is directly placed in complex sol to prepare according to the preparation method of film by the preparation method of described matrix material, as long as in the end not by film and substrate glass, the bonding force of the matrix material obtained like this is relatively good.Also can by glass obtained above with bonding together with substrate bonding.
By embodiment, the present invention is described in further detail below.
Embodiment 1
S1, preparation SiO2 colloidal sol
Tetraethoxy, hydration dehydrated alcohol mix and the formation mixing solutions that stirs by SS1; Wherein, the mol ratio of each material is: tetraethoxy: water: dehydrated alcohol=1:4:40, then with hydrochloric acid, pH value is adjusted to 3, stirs 4 hours, ageing 24 hours;
SS2 sodium hydroxide is by the pH regulator of the mixing solutions in step SS1 to 9, and ageing 24 hours, forms colloidal sol;
PH value is adjusted to 3 by the colloidal sol hydrochloric acid in step SS2 by SS3, obtains acid SiO2 colloidal sol;
S2, preparation TiO2 colloidal sol
Tetrabutyl titanate, water, methyl ethyl diketone and dehydrated alcohol are mixed and stirs, in TiO2 colloidal sol, the molar ratio of each material is tetrabutyl titanate: water: methyl ethyl diketone: dehydrated alcohol=1:2.5:1:18, then be 4 with salt acid for adjusting pH value, stir 2 hours, ageing 24 hours;
S3, preparation SiO2-TiO2 complex sol
While the above-mentioned acid SiO2 colloidal sol of stirring, above-mentioned TiO2 colloidal sol is slowly joined in above-mentioned SiO2 colloidal sol, continue stirring 30 minutes, form SiO2-TiO2 complex sol;
S4, prepare the N-SiO2-TiO2 complex sol of N doping
Triton X-100 is joined in above-mentioned SiO2-TiO2 complex sol, and stir 30 minutes; Then add wherein containing urea, stir the N-SiO2-TiO2 complex sol forming N doping after 60 minutes;
S5, prepare laminated film
Glass substrate is slowly inserted in above-mentioned N-SiO2-TiO2 complex sol and floods after 5 minutes, one deck N-SiO2-TiO2 film is formed at substrate surface by liquid level method, then glass substrate is placed and naturally dry in atmosphere, after baking oven substrate being put into 80 DEG C dries 30min, roasting 2 hours at 540 DEG C, is formed and is carried on on-chip laminated film A1.
In the N-SiO2-TiO2 complex sol of N doping, the content of titanium dioxide is 9mol, and the content of silicon-dioxide is 81mol, and the content of urea is 5mol; With the total mass of the N-SiO2-TiO2 complex sol of N doping for benchmark, the content of described tensio-active agent is 10%.
Embodiment 2
Be carried on on-chip laminated film A2 according to the method preparation of embodiment 1, distinguish: in the N-SiO2-TiO2 complex sol of N doping, the content of titanium dioxide is 16mol, and the content of silicon-dioxide is 64mol, and the content of urea is 10mol; With the total mass of the N-SiO2-TiO2 complex sol of N doping for benchmark, the content of described tensio-active agent is 5%.
Embodiment 3
Be carried on on-chip laminated film A3 according to the method preparation of embodiment 1, distinguish: in the N-SiO2-TiO2 complex sol of N doping, the content of titanium dioxide is 21mol, and the content of silicon-dioxide is 49mol, and the content of urea is 15mol; With the total mass of the N-SiO2-TiO2 complex sol of N doping for benchmark, the content of described tensio-active agent is 7%.
Embodiment 4
Be carried on on-chip laminated film A4 according to the method preparation of embodiment 1, distinguish: in the N-SiO2-TiO2 complex sol of N doping, the content of titanium dioxide is 24mol, and the content of silicon-dioxide is 36mol, and the content of urea is 20mol; With the total mass of the N-SiO2-TiO2 complex sol of N doping for benchmark, the content of described tensio-active agent is 1%.
Embodiment 5
Be carried on on-chip laminated film A5 according to the method preparation of embodiment 1, distinguish: in the N-SiO2-TiO2 complex sol of N doping, the content of titanium dioxide is 10mol, and the content of silicon-dioxide is 40mol, and the content of urea is 25mol; With the total mass of the N-SiO2-TiO2 complex sol of N doping for benchmark, the content of described tensio-active agent is 15%.
Embodiment 6
Be carried on on-chip laminated film A6 according to the method preparation of embodiment 1, distinguish: in the N-SiO2-TiO2 complex sol of N doping, the content of titanium dioxide is 10mol, and the content of silicon-dioxide is 30mol, and the content of urea is 30mol; With the total mass of the N-SiO2-TiO2 complex sol of N doping for benchmark, the content of described tensio-active agent is 20%.
Embodiment 7
Be carried on on-chip laminated film A7 according to the method preparation of embodiment 1, distinguish: in the N-SiO2-TiO2 complex sol of N doping, the content of titanium dioxide is 3mol, and the content of silicon-dioxide is 27mol, and the content of urea is 35mol; With the total mass of the N-SiO2-TiO2 complex sol of N doping for benchmark, the content of described tensio-active agent is 10%.
Embodiment 8
Be carried on on-chip laminated film A8 according to the method preparation of embodiment 1, distinguish: in the N-SiO2-TiO2 complex sol of N doping, the content of titanium dioxide is 45mol, and the content of silicon-dioxide is 45mol, and the content of urea is 5mol; With the total mass of the N-SiO2-TiO2 complex sol of N doping for benchmark, the content of described tensio-active agent is 10%.
Comparative example 1
Utilize the method for surfactant modified titanium dioxide synthesizing ultra-hydrophilic film, its composition comprises:
Prepare TiO 2 sol, pre-treatment, dipping-lift, attachment colloidal sol, dry, sol-gel self-combustion synthesis prepares titanium dioxide nano-particle, pre-treatment titanium dioxide nano-particle, spin coating, dry, roasting, at ambient temperature, prepare TiO 2 sol, the method of dipping-lift is adopted to be attached on glass or conductive glass ITO with the pull rate of 60 mm/min by layer of titanium dioxide colloidal sol, the dipping time of lift front glass substrate in titanium dioxide glue is 2 minutes, 60 DEG C of dryings, obtain egative film, before spin coating, pre-treatment is carried out to surfactant modified paste titanium dioxide nano-particle prepared by sol-gel self-combustion synthesis, then the surfactant modified titanium dioxide nano-particle adopting the method for spin coating to fix one deck sol-gel self-combustion synthesis on above-mentioned egative film to prepare, dry, roasting, finally obtain nano-titanium dioxide film CA1.
Testing method
1, transmittance test
Adopt ultraviolet-visible pectrophotometer to carry out transmittance detection to A1-A8 and CA1, the results are shown in Table 1.
2, contact angle test
Adopt static contact angle instrument to carry out contact angle detection to A1-A8 and CA1, the results are shown in Table 1.
Table 1
。
As can be seen from Table 1, the transmittance of film of the present invention reaches more than 93%, and contact angle is less than 5 °.And the transmittance of the film prepared by the method for comparative example 1 only has 88.73%.Contact angle is 34 °.So the transmittance of film of the present invention is large, automatically cleaning is very capable.
Claims (14)
1. a laminated film, is characterized in that, this film contains titanium dioxide and silicon-dioxide; Described titanium dioxide is nitrogen-doped titanium dioxide, wherein, with the total mole number of film for benchmark, the molar percentage of described titanium dioxide is 9.8-49.8%, the molar percentage of described silicon-dioxide is 44.8-88.2%, the molar percentage of described nitrogen element is 0.4-2%, and described silicon-dioxide is spherical, and the median size of silicon-dioxide is 80-100nm.
2. laminated film according to claim 1, is characterized in that: the molar percentage of described titanium dioxide is 30-40%, and the molar percentage of described silicon-dioxide is 60-70%, and the molar percentage of described nitrogen element is 0.5-1.5%.
3.
laminated film according to claim 1 and 2, is characterized in that, described titanium dioxide is the mixture of anatase titanium dioxide and rutile titanium dioxide.
4. laminated film according to claim 1 and 2, is characterized in that, the specific refractory power of described film is 1.25-1.4.
5. the preparation method of laminated film according to claim 1, is characterized in that, the method comprises the following steps:
S1, preparation SiO
2colloidal sol
Tetraethoxy, hydration dehydrated alcohol mix and the formation mixing solutions that stirs by SS1; Wherein, the mol ratio of each material is: tetraethoxy: water: dehydrated alcohol=1:3-5:35-45, then with acid, pH value is adjusted to 2-4, stirs ageing;
SS2 alkali by the pH regulator of the mixing solutions in step SS1 to 8-10, and ageing formed colloidal sol;
PH value is adjusted to 2-4 by the colloidal sol acid in step SS2 by SS3, obtains acid SiO
2colloidal sol;
S2, preparation TiO
2colloidal sol
Tetrabutyl titanate, water, methyl ethyl diketone and dehydrated alcohol are mixed and stirs, TiO
2in colloidal sol, the molar ratio of each material is tetrabutyl titanate: water: methyl ethyl diketone: dehydrated alcohol=1:2-3:0.5-1.5:16-20, is then 3-5 with acid for adjusting pH value, stirs ageing;
S3, preparation SiO
2-TiO
2complex sol
At the above-mentioned acid SiO of stirring
2while colloidal sol, by above-mentioned TiO
2colloidal sol slowly joins above-mentioned SiO
2in colloidal sol, continue to stir formation SiO
2-TiO
2complex sol;
S4, prepare the N-SiO of N doping
2-TiO
2complex sol
Tensio-active agent is joined above-mentioned SiO
2-TiO
2stir in complex sol; Then add nitrogenous substances wherein, stir the N-SiO forming N doping
2-TiO
2complex sol;
S5, prepare laminated film
Substrate is slowly inserted into above-mentioned N-SiO
2-TiO
2after flooding 1-2 minute in complex sol, form one deck N-SiO by liquid level method at substrate surface
2-TiO
2film, then placed by glass substrate and naturally dry in atmosphere, substrate is put into baking oven and dries, then roasting is formed and is carried on on-chip laminated film, divests substrate, namely obtains laminated film;
Wherein, nitrogenous substances in N, the N-SiO of N doping
2-TiO
2in complex sol, with the integral molar quantity of titanium dioxide, silicon-dioxide and nitrogen element for benchmark, the molar percentage of described titanium dioxide is 3-45%, and the molar percentage of described silicon-dioxide is 15-81%, and the molar percentage of described nitrogen element is 10-70%; With the N-SiO of N doping
2-TiO
2the total mass of complex sol is benchmark, and the content of described tensio-active agent is 1-20%.
6. preparation method according to claim 5, is characterized in that, the time of stirring in described step SS1 is 0.5-1.5 hour, and the time of ageing is 24-96 hour; The time of ageing in described step SS2 is 24-96 hour; The time of stirring in step S2 is 0.5-1.5 hour, and the time of ageing is 24-96 hour; The time of stirring in step S3 is 30-60 minute; Adding the churning time after tensio-active agent in step S4 is 30-60 minute, and adding the churning time after nitrogenous substances is 30-60 minute.
7. preparation method according to claim 5, is characterized in that, the temperature of described oven dry is 70-90 DEG C, and the time is 40-80min; The temperature of described roasting is 500-600 DEG C, and the time is 1-3 hour.
8. preparation method according to claim 5, is characterized in that, acid used in step SS1, SS3 and S2 is hydrochloric acid or nitric acid.
9. preparation method according to claim 5, is characterized in that, alkali used in step SS2 is ammoniacal liquor.
10. preparation method according to claim 5, it is characterized in that, described tensio-active agent is at least one in Qu Latong X100, diethanolamine, trolamine, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, oleic acid, polyoxyethylene glycol and ethylene glycol amine.
11. preparation method according to claim 5, is characterized in that, described nitrogenous substances is at least one in bicarbonate of ammonia and urea.
12. preparation method according to claim 5, is characterized in that, described substrate is glass or pottery.
13. 1 kinds of matrix materials, this material comprises base material and the laminated film invested on base material, and it is characterized in that, described laminated film is laminated film according to claim 1.
14. matrix material according to claim 13, is characterized in that, described base material is glass or pottery.
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| CN103468086B (en) * | 2013-08-12 | 2015-07-29 | 广东南亮玻璃科技有限公司 | SiO 2base self-cleaning coating and self-cleaning glass and preparation method thereof |
| CN103757618A (en) * | 2014-01-08 | 2014-04-30 | 同济大学 | Preparation method of antireflection film applicable to different bases |
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| CN111718129B (en) * | 2020-06-23 | 2022-07-15 | 上海西源新能源技术有限公司 | PEG-modified SiO2-TiO2Composite self-cleaning antireflection film and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546226A (en) * | 2003-12-17 | 2004-11-17 | 同济大学 | TiO2/SiO2 aerogel and method for making same |
-
2011
- 2011-07-28 CN CN201110212275.8A patent/CN102898035B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546226A (en) * | 2003-12-17 | 2004-11-17 | 同济大学 | TiO2/SiO2 aerogel and method for making same |
Non-Patent Citations (1)
| Title |
|---|
| 氮掺杂TiO2-ZrO2复合光催化薄膜的研究;梅乐夫等;《稀有金属材料与工程》;20080531;第37卷(第5期);第758-761页 * |
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