CN102898035A - Composite film, its preparation method and composite material - Google Patents
Composite film, its preparation method and composite material Download PDFInfo
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- CN102898035A CN102898035A CN2011102122758A CN201110212275A CN102898035A CN 102898035 A CN102898035 A CN 102898035A CN 2011102122758 A CN2011102122758 A CN 2011102122758A CN 201110212275 A CN201110212275 A CN 201110212275A CN 102898035 A CN102898035 A CN 102898035A
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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, the surface has the water-wet behavior of height, can with the organic pollutant deep oxidation, finally generate CO
2And H
2O etc.Have 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 being used in building glass, cladding glass, partition glass, decorating and drill the article surfaces such as glass, automobile windshield, automobile side window glass, speculum, skylight glass, light fixture lamp shade 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 relatively poor, can only just have under given conditions the automatically cleaning effect, and simultaneously, the self_cleaning effect time is short, substrate surface is exposed to cross in the contaminated air long-time after because the surface is covered the dirty inefficacy that is easy to by dust.
Chinese patent CN101372394A discloses a kind of method of utilizing surfactant modified titanium dioxide synthesizing ultra-hydrophilic film, its composition comprises: the preparation TiO 2 sol, pre-treatment, flood-lift, adhere to colloidal sol, dry, the standby titanium dioxide nano-particle of Sol-Hydrothermal legal system, the pre-treatment titanium dioxide nano-particle, spin coating, dry, roasting, it is characterized in that: at ambient temperature, the preparation TiO 2 sol, the method that employing is flooded-lifted is attached to layer of titanium dioxide colloidal sol on glass or the conductive glass ITO with the pull rate of 60 mm/min, lifting the dipping time of front glass substrate in TiO 2 sol is 2 minutes, 60 ℃ of dryings, obtain egative film, the standby surfactant modified paste titanium dioxide of the Sol-Hydrothermal legal system nanoparticle of admiring is carried out pre-treatment before the spin coating, the method that then adopts spin coating is at the fixing standby surfactant modified titanium dioxide nano-particle of one deck Sol-Hydrothermal legal system of above-mentioned egative film, dry, roasting finally obtains the nanometer titanium dioxide film of admiring.
The time that the wetting ability of the film that aforesaid method prepares continues is short, thereby makes its automatically cleaning ability low, and the transmittance rate of the film for preparing of the method is low, can not satisfy the demands.
Summary of the invention
The present invention is for solving the low technical problem of low, the glossy rate of automatically cleaning ability of titanium deoxid film of the prior art, thereby a kind of matrix material that can have for a long time high titanium deoxid film of automatically cleaning ability and transmittance and preparation method thereof and contain this film is provided.
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, take the total mole number of film as 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.
The present invention also provides the preparation method of above-mentioned laminated film, and the method may further comprise the steps:
The method may further comprise the steps:
S1, preparation SiO
2Colloidal sol
SS1 mixes tetraethoxy, hydration dehydrated alcohol and the formation mixing solutions that stirs; Wherein, the mol ratio of each material is: tetraethoxy: water: dehydrated alcohol=1:3-5:35-45, then with acid the pH value is adjusted to 2-4, and stir ageing;
SS2 with alkali with the pH regulator of the mixing solutions among the step SS1 to 8-10, and ageing forms colloidal sol;
SS3 is adjusted to 2-4 with acid with the pH value with the colloidal sol among the step S2, obtains acid SiO
2Colloidal sol;
S2, preparation TiO
2Colloidal sol
Tetrabutyl titanate, water, methyl ethyl diketone and dehydrated alcohol are mixed and stir TiO
2The molar ratio of each material is tetrabutyl titanate in the colloidal sol: then water: methyl ethyl diketone: dehydrated alcohol=1:2-3:0.5-1.5:16-20 is 3-5 with acid for adjusting pH value, stirs ageing;
S3, preparation SiO
2-TiO
2Complex sol
Stirring above-mentioned acid SiO
2In the time of colloidal sol, with above-mentioned TiO
2Colloidal sol slowly joins above-mentioned SiO
2In the colloidal sol, continue to stir formation SiO
2-TiO
2Complex sol;
The N-SiO that S4, preparation nitrogen mix
2-TiO
2Complex sol
Tensio-active agent is joined above-mentioned SiO
2-TiO
2Stir in the complex sol; Then to wherein adding nitrogenous substances, stir and form the N-SiO that nitrogen mixes
2-TiO
2Complex sol;
S5, preparation laminated film
Substrate slowly is inserted into above-mentioned N-SiO
2-TiO
2Dipping formed one deck N-SiO by liquid level method at substrate surface after 1-2 minute in the complex sol
2-TiO
2Then film is placed on glass substrate in the air and naturally dries, and substrate is put into baking oven dry, and then roasting forms load and on-chip laminated film, divests substrate, namely obtains laminated film;
Wherein, nitrogenous substances is in N, the N-SiO that nitrogen mixes
2-TiO
2In the complex sol, take the integral molar quantity of titanium dioxide, silicon-dioxide and nitrogen element as 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%; N-SiO with the nitrogen 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 that invests on the 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 the pure silicon dioxide antireflective coating has higher reflection preventing ability, but because silicon-dioxide self does not have the automatically cleaning characteristic, therefore will make light transmission greatly descend owing to the pollution in the environment in a short time, pure titinium dioxide automatically cleaning film is then because himself specific refractory power too high (up to 2.45), thereby light transmission descended greatly affected the application in being similar to area of solar cell.This product is by rational ratio of regulating titanium dioxide and silicon-dioxide, and the film forming porosity of adjusting, thereby the effective refractive index of this kind laminated film is reduced, and has guaranteed high light transmittance.In addition, because the elements such as N that in the laminated film preparation process, titanium dioxide partly mixed, effectively regulate the band gap width of titanium dioxide, thereby even made the photocatalytic activity of titanium dioxide in the situation of the low light level (without uviolizing), also have photocatalytic activity.This performance can be removed environmental pollutant timely from film surface, thus the self-cleaning performance that makes film keep for a long time.In addition, silicon-dioxide is Lewis acid in general sense, at normal temperatures and pressures the water with nucleophilicity is had stronger adsorption, that is so-called " lock water " Performance Ratio is better.But silicon-dioxide does not have photocatalytic activity, polluting and the moisture film on surface is disappeared through causing after the placement of certain period, and the adding of titanium dioxide can remedy this, because its photocatalytic activity can make film keep clean, and have all the time a large amount of oh groups, thereby 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, take the total mole number of film as 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, for the wetting ability that makes film is 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, for the wetting ability that makes film is 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 because itself band gap higher (block rutile titanium dioxide band gap is at 3.3 electron-volts), thereby make its in the sun extremely a little less than; Anatase titanium dioxide then has than low band gaps (block anatase titanium dioxide band gap is at 3.1 electron-volts) with respect to rutile-type, has than the high light catalytic activity under solar radiation.Relevant report is not only relevant with the actual crystal band gap with the power that experimental results show that the optically catalytic TiO 2 activity, and is also closely related with the crystal interface attitude.When Detitanium-ore-type and rutile titanium dioxide exist simultaneously and mutually be close to, show the photocatalytic activity stronger than unicity crystal.It is generally acknowledged that this is because the existence of this interfacial state is strengthened the photoelectronic life-span of generation greatly, in case produce after the photoelectron since the existence at interface hindered again compound, thereby make 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, if will reduce the reflection at this interface, then surperficial institute coating film must meet λ/4.According to Theoretical Calculation, if will make visible light have the strongest projection, then film forming effective refractive index is about 1.3.
The invention provides a kind of preparation method of said film, the method may further comprise the steps:
The method may further comprise the steps:
S1, preparation SiO
2Colloidal sol
SS1 mixes tetraethoxy, hydration dehydrated alcohol and the formation mixing solutions that stirs; Wherein, the mol ratio of each material is: tetraethoxy: water: dehydrated alcohol=1:3-5:35-45, then with acid the pH value is adjusted to 2-4, and stir ageing;
SS2 with alkali with the pH regulator of the mixing solutions among the step SS1 to 8-10, and ageing forms colloidal sol;
SS3 is adjusted to 2-4 with acid with the pH value with the colloidal sol among the step S2, obtains acid SiO
2Colloidal sol;
S2, preparation TiO
2Colloidal sol
Tetrabutyl titanate, water, methyl ethyl diketone and dehydrated alcohol are mixed and stir TiO
2The molar ratio of each material is tetrabutyl titanate in the colloidal sol: then water: methyl ethyl diketone: dehydrated alcohol=1:2-3:0.5-1.5:16-20 is 3-5 with acid for adjusting pH value, stirs ageing;
S3, preparation SiO
2-TiO
2Complex sol
Stirring above-mentioned acid SiO
2In the time of colloidal sol, with above-mentioned TiO
2Colloidal sol slowly joins above-mentioned SiO
2In the colloidal sol, continue to stir formation SiO
2-TiO
2Complex sol;
The N-SiO that S4, preparation nitrogen mix
2-TiO
2Complex sol
Tensio-active agent is joined above-mentioned SiO
2-TiO
2Stir in the complex sol; Then to wherein adding nitrogenous substances, stir and form the N-SiO that nitrogen mixes
2-TiO
2Complex sol;
S5, preparation laminated film
Substrate slowly is inserted into above-mentioned N-SiO
2-TiO
2Dipping formed one deck N-SiO by liquid level method at substrate surface after 1-2 minute in the complex sol
2-TiO
2Then film is placed on glass substrate in the air and naturally dries, and substrate is put into baking oven dry, and then roasting forms load and on-chip laminated film, divests substrate, namely obtains laminated film;
Wherein, nitrogenous substances is in N, the N-SiO that nitrogen mixes
2-TiO
2In the complex sol, take the integral molar quantity of titanium dioxide, silicon-dioxide and nitrogen element as 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%; N-SiO with the nitrogen 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 among the described step SS1 is 0.5-1.5 hour, and the time of ageing is 24-96 hour; The time of ageing is 24-96 hour among the described step SS2; The time of stirring among the step S2 is 0.5-1.5 hour, and the time of ageing is 24-96 hour; The time of stirring among the step S3 is 30-60 minute; Churning time among the step S4 behind the adding tensio-active agent is 30-60 minute, and the churning time behind the adding nitrogenous substances is 30-60 minute.The temperature of described oven dry is 70-90 ℃, and the time is 40-80min; The temperature of described roasting is 500-600 ℃, and the time is 1-3 hour.
N-SiO
2-TiO
2The content of the nitrogen element in the 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, can slowly be hydrolyzed, and becomes a small amount of crystal seed, for the reaction among the SS2 is prepared.In SS2, hydrolysis generates silicon-dioxide, owing to be to be hydrolyzed under alkaline condition, makes silicon-dioxide globulate and the particle diameter of generation little, and such silicon-dioxide can improve the hydrophilic persistence of the film of later stage formation.
According to preparation method provided by the present invention, acid used among step SS1 of the present invention, SS3 and the S2 can be various acid well known in the art, but can remove easily for follow-up, and preferably, used acid is hydrochloric acid or nitric acid among step SS1, SS3 and the S2.Hydrochloric acid and nitric acid at high temperature can form respectively HCl and NO
2Gas leaves.
According to preparation method provided by the present invention, alkali used among the step SS2 can be this area various alkali commonly used, but in order not introduce other impurity, preferably, used alkali is ammoniacal liquor among the step SS2, ammoniacal liquor can at high temperature partly become gas, and another part forms the N element doping and enters in the titanium dioxide crystal.Because the consumption of ammoniacal liquor is less, and forms the N element doping and enter in the titanium dioxide crystal still less.
According to preparation method provided by the present invention, described surfactivity can be this area various tensio-active agents commonly used, preferably, described tensio-active agent is at least a in Qu Latong X100, diethanolamine, trolamine, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, oleic acid, polyoxyethylene glycol and the ethylene glycol amine.
According to preparation method provided by the present invention, preferably, described nitrogenous substances is at least a in bicarbonate of ammonia and the 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 not other impurity, preferably, before the preparation laminated film, base material is 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 that invests on the 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, described composite manufacture method can be base material directly to be placed in the complex sol prepare according to the thin film technology method, as long as in the end not with film and substrate glass, the bonding force of the matrix material that obtains like this is relatively good.Also can be with glass obtained above with bonding and substrate bonding together.
The below further describes in detail the present invention with embodiment.
Embodiment 1
S1, preparation SiO2 colloidal sol
SS1 mixes tetraethoxy, hydration dehydrated alcohol and the formation mixing solutions that stirs; Wherein, the mol ratio of each material is: tetraethoxy: water: dehydrated alcohol=1:4:40, then with hydrochloric acid the pH value is adjusted to 3, and stirred ageing 24 hours 4 hours;
SS2 is with the pH regulator to 9 of sodium hydroxide with the mixing solutions among the step SS1, and ageing 24 hours, forms colloidal sol;
SS3 is adjusted to 3 with hydrochloric acid with the pH value with the colloidal sol among the step S2, obtains acid SiO2 colloidal sol;
S2, preparation TiO2 colloidal sol
Tetrabutyl titanate, water, methyl ethyl diketone and dehydrated alcohol are mixed and stir, the molar ratio of each material is tetrabutyl titanate in the TiO2 colloidal sol: water: methyl ethyl diketone: dehydrated alcohol=1:2.5:1:18, then be 4 with the salt acid for adjusting pH value, stirred ageing 24 hours 2 hours;
S3, preparation SiO2-TiO2 complex sol
When stirring above-mentioned acid SiO2 colloidal sol, above-mentioned TiO2 colloidal sol is slowly joined in the above-mentioned SiO2 colloidal sol, continue to stir 30 minutes, form the SiO2-TiO2 complex sol;
The N-SiO2-TiO2 complex sol that S4, preparation nitrogen mix
Triton X-100 is joined in the above-mentioned SiO2-TiO2 complex sol, and stirred 30 minutes; Then contain urea to wherein adding, stir and form the N-SiO2-TiO2 complex sol that nitrogen mixes after 60 minutes;
S5, preparation laminated film
Glass substrate slowly was inserted in the above-mentioned N-SiO2-TiO2 complex sol dipping after 5 minutes, form one deck N-SiO2-TiO2 film by liquid level method at substrate surface, then glass substrate is placed in the air and naturally dries, after substrate being put into 80 ℃ baking oven oven dry 30min, 540 ℃ of lower roastings 2 hours, form and be carried on on-chip laminated film A1.
In the N-SiO2-TiO2 complex sol that nitrogen mixes, the content of titanium dioxide is 9mol, and the content of silicon-dioxide is 81mol, and the content of urea is 5mol; The total mass of the N-SiO2-TiO2 complex sol that mixes take nitrogen is as benchmark, and the content of described tensio-active agent is 10%.
Embodiment 2
Method preparation according to embodiment 1 is carried on on-chip laminated film A2, and difference exists: in the N-SiO2-TiO2 complex sol that nitrogen mixes, the content of titanium dioxide is 16mol, and the content of silicon-dioxide is 64mol, and the content of urea is 10mol; The total mass of the N-SiO2-TiO2 complex sol that mixes take nitrogen is as benchmark, and the content of described tensio-active agent is 5%.
Embodiment 3
Method preparation according to embodiment 1 is carried on on-chip laminated film A3, and difference exists: in the N-SiO2-TiO2 complex sol that nitrogen mixes, the content of titanium dioxide is 21mol, and the content of silicon-dioxide is 49mol, and the content of urea is 15mol; The total mass of the N-SiO2-TiO2 complex sol that mixes take nitrogen is as benchmark, and the content of described tensio-active agent is 7%.
Embodiment 4
Method preparation according to embodiment 1 is carried on on-chip laminated film A4, and difference exists: in the N-SiO2-TiO2 complex sol that nitrogen mixes, the content of titanium dioxide is 24mol, and the content of silicon-dioxide is 36mol, and the content of urea is 20mol; The total mass of the N-SiO2-TiO2 complex sol that mixes take nitrogen is as benchmark, and the content of described tensio-active agent is 1%.
Embodiment 5
Method preparation according to embodiment 1 is carried on on-chip laminated film A5, and difference exists: in the N-SiO2-TiO2 complex sol that nitrogen mixes, the content of titanium dioxide is 10mol, and the content of silicon-dioxide is 40mol, and the content of urea is 25mol; The total mass of the N-SiO2-TiO2 complex sol that mixes take nitrogen is as benchmark, and the content of described tensio-active agent is 15%.
Embodiment 6
Method preparation according to embodiment 1 is carried on on-chip laminated film A6, and difference exists: in the N-SiO2-TiO2 complex sol that nitrogen mixes, the content of titanium dioxide is 10mol, and the content of silicon-dioxide is 30mol, and the content of urea is 30mol; The total mass of the N-SiO2-TiO2 complex sol that mixes take nitrogen is as benchmark, and the content of described tensio-active agent is 20%.
Embodiment 7
Method preparation according to embodiment 1 is carried on on-chip laminated film A7, and difference exists: in the N-SiO2-TiO2 complex sol that nitrogen mixes, the content of titanium dioxide is 3mol, and the content of silicon-dioxide is 27mol, and the content of urea is 35mol; The total mass of the N-SiO2-TiO2 complex sol that mixes take nitrogen is as benchmark, and the content of described tensio-active agent is 10%.
Embodiment 8
Method preparation according to embodiment 1 is carried on on-chip laminated film A8, and difference exists: in the N-SiO2-TiO2 complex sol that nitrogen mixes, the content of titanium dioxide is 45mol, and the content of silicon-dioxide is 45mol, and the content of urea is 5mol; The total mass of the N-SiO2-TiO2 complex sol that mixes take nitrogen is as benchmark, and the content of described tensio-active agent is 10%.
Comparative Examples 1
Utilize the method for surfactant modified titanium dioxide synthesizing ultra-hydrophilic film, its composition comprises:
The preparation TiO 2 sol, pre-treatment, flood-lift, adhere to colloidal sol, dry, the standby titanium dioxide nano-particle of Sol-Hydrothermal legal system, the pre-treatment titanium dioxide nano-particle, spin coating, dry, roasting, at ambient temperature, the preparation TiO 2 sol, the method that employing is flooded-lifted is attached to layer of titanium dioxide colloidal sol on glass or the conductive glass ITO with the pull rate of 60 mm/min, lifting the dipping time of front glass substrate in titanium dioxide glue is 2 minutes, 60 ℃ of dryings, obtain egative film, before the spin coating the standby surfactant modified paste titanium dioxide nano-particle of Sol-Hydrothermal legal system is carried out pre-treatment, the method that then adopts spin coating is at the fixing standby surfactant modified titanium dioxide nano-particle of one deck Sol-Hydrothermal legal system of above-mentioned egative film, dry, roasting finally obtains nano-titanium dioxide film CA1.
Testing method
1, transmittance test
Adopt ultraviolet-visible pectrophotometer that A1-A8 and CA1 are carried out the transmittance detection, the results are shown in Table 1.
2, contact angle test
Adopt the static contact angle instrument that A1-A8 and CA1 are carried out contact angle detection, 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 only have 88.73% with the transmittance of the film of the method for Comparative Examples 1 preparation.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, take the total mole number of film as 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, it 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 claimed in claim 1 is characterized in that, the method may further comprise the steps:
S1, preparation SiO
2Colloidal sol
SS1 mixes tetraethoxy, hydration dehydrated alcohol and the formation mixing solutions that stirs; Wherein, the mol ratio of each material is: tetraethoxy: water: dehydrated alcohol=1:3-5:35-45, then with acid the pH value is adjusted to 2-4, and stir ageing;
SS2 with alkali with the pH regulator of the mixing solutions among the step SS1 to 8-10, and ageing forms colloidal sol;
SS3 is adjusted to 2-4 with acid with the pH value with the colloidal sol among the step S2, obtains acid SiO
2Colloidal sol;
S2, preparation TiO
2Colloidal sol
Tetrabutyl titanate, water, methyl ethyl diketone and dehydrated alcohol are mixed and stir TiO
2The molar ratio of each material is tetrabutyl titanate in the colloidal sol: then water: methyl ethyl diketone: dehydrated alcohol=1:2-3:0.5-1.5:16-20 is 3-5 with acid for adjusting pH value, stirs ageing;
S3, preparation SiO
2-TiO
2Complex sol
Stirring above-mentioned acid SiO
2In the time of colloidal sol, with above-mentioned TiO
2Colloidal sol slowly joins above-mentioned SiO
2In the colloidal sol, continue to stir formation SiO
2-TiO
2Complex sol;
The N-SiO that S4, preparation nitrogen mix
2-TiO
2Complex sol
Tensio-active agent is joined above-mentioned SiO
2-TiO
2Stir in the complex sol; Then to wherein adding nitrogenous substances, stir and form the N-SiO that nitrogen mixes
2-TiO
2Complex sol;
S5, preparation laminated film
Substrate slowly is inserted into above-mentioned N-SiO
2-TiO
2Dipping formed one deck N-SiO by liquid level method at substrate surface after 1-2 minute in the complex sol
2-TiO
2Then film is placed on glass substrate in the air and naturally dries, and substrate is put into baking oven dry, and then roasting forms load and on-chip laminated film, divests substrate, namely obtains laminated film;
Wherein, nitrogenous substances is in N, the N-SiO that nitrogen mixes
2-TiO
2In the complex sol, take the integral molar quantity of titanium dioxide, silicon-dioxide and nitrogen element as 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%; N-SiO with the nitrogen 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 among the described step SS1 is 0.5-1.5 hour, and the time of ageing is 24-96 hour; The time of ageing is 24-96 hour among the described step SS2; The time of stirring among the step S2 is 0.5-1.5 hour, and the time of ageing is 24-96 hour; The time of stirring among the step S3 is 30-60 minute; Churning time among the step S4 behind the adding tensio-active agent is 30-60 minute, and the churning time behind the adding 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 ℃, and the time is 40-80min; The temperature of described roasting is 500-600 ℃, and the time is 1-3 hour.
8. preparation method according to claim 5 is characterized in that, used acid is hydrochloric acid or nitric acid among step SS1, SS3 and the S2.
9. preparation method according to claim 5 is characterized in that, used alkali is ammoniacal liquor among the step SS2.
10. preparation method according to claim 5, it is characterized in that described tensio-active agent is at least a in Qu Latong X100, diethanolamine, trolamine, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, oleic acid, polyoxyethylene glycol and the ethylene glycol amine.
11. preparation method according to claim 5 is characterized in that, described nitrogenous substances is at least a in bicarbonate of ammonia and the urea.
12. preparation method according to claim 5 is characterized in that, described substrate is glass or pottery.
13. a matrix material, this material comprise base material and the laminated film that invests on the base material, it is characterized in that described laminated film is laminated film claimed in claim 1.
14. matrix material according to claim 13 is characterized in that, described base material is glass or pottery.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103468086A (en) * | 2013-08-12 | 2013-12-25 | 广东南亮玻璃科技有限公司 | SiO2 based self-cleaning paint, 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 |
| CN103922610A (en) * | 2014-04-21 | 2014-07-16 | 镇江市晶利玻璃有限公司 | High-transparency solar photovoltaic glass |
| CN105271811A (en) * | 2015-10-29 | 2016-01-27 | 苏州市灵通玻璃制品有限公司 | Super-hydrophilic self-cleaning glass preparation method |
| CN105785590A (en) * | 2016-05-20 | 2016-07-20 | 四川梅塞尔科技有限公司 | Preparation method and products for color-changing wearable self-cleaning concave lens |
| CN107604311A (en) * | 2017-08-10 | 2018-01-19 | 酒泉职业技术学院 | A kind of preparation method of automatically cleaning solar thermal collector antireflective coating |
| CN110117167A (en) * | 2019-04-30 | 2019-08-13 | 马鞍山钢铁股份有限公司 | A kind of aludip and its manufacturing method with photocatalytic activity and excellent high temperature resistance performance |
| CN110407480A (en) * | 2019-06-21 | 2019-11-05 | 刘其云 | A kind of preparation method of high light transmission high tenacity antireflective film |
| CN110729363A (en) * | 2018-06-28 | 2020-01-24 | 蓝海新技术开发(潍坊)有限公司 | Solar panel and preparation method of surface coating for solar panel |
| CN111718129A (en) * | 2020-06-23 | 2020-09-29 | 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 |
| CN115745419A (en) * | 2022-11-25 | 2023-03-07 | 常州君合科技股份有限公司 | Method for synthesizing high-performance photovoltaic glass antireflection film by segmented hydrolysis of tetraethoxysilane |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103468086A (en) * | 2013-08-12 | 2013-12-25 | 广东南亮玻璃科技有限公司 | SiO2 based self-cleaning paint, 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 |
| CN103922610A (en) * | 2014-04-21 | 2014-07-16 | 镇江市晶利玻璃有限公司 | High-transparency solar photovoltaic glass |
| CN105271811A (en) * | 2015-10-29 | 2016-01-27 | 苏州市灵通玻璃制品有限公司 | Super-hydrophilic self-cleaning glass preparation method |
| CN105785590B (en) * | 2016-05-20 | 2018-10-26 | 四川梅塞尔科技有限公司 | A kind of preparation method and product of the wear-resisting automatically cleaning concave lens of discoloration |
| CN105785590A (en) * | 2016-05-20 | 2016-07-20 | 四川梅塞尔科技有限公司 | Preparation method and products for color-changing wearable self-cleaning concave lens |
| CN107604311A (en) * | 2017-08-10 | 2018-01-19 | 酒泉职业技术学院 | A kind of preparation method of automatically cleaning solar thermal collector antireflective coating |
| CN110729363A (en) * | 2018-06-28 | 2020-01-24 | 蓝海新技术开发(潍坊)有限公司 | Solar panel and preparation method of surface coating for solar panel |
| CN110117167A (en) * | 2019-04-30 | 2019-08-13 | 马鞍山钢铁股份有限公司 | A kind of aludip and its manufacturing method with photocatalytic activity and excellent high temperature resistance performance |
| CN110407480A (en) * | 2019-06-21 | 2019-11-05 | 刘其云 | A kind of preparation method of high light transmission high tenacity antireflective film |
| CN111718129A (en) * | 2020-06-23 | 2020-09-29 | 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 |
| 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 |
| CN115745419A (en) * | 2022-11-25 | 2023-03-07 | 常州君合科技股份有限公司 | Method for synthesizing high-performance photovoltaic glass antireflection film by segmented hydrolysis of tetraethoxysilane |
| CN115745419B (en) * | 2022-11-25 | 2024-04-12 | 常州君合科技股份有限公司 | Method for synthesizing high-performance photovoltaic glass antireflection film by sectionally hydrolyzing tetraethoxysilane |
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