CN101712536B - Method for preparing super-hydrophilic film with funnel-shaped or step-shaped structure - Google Patents

Method for preparing super-hydrophilic film with funnel-shaped or step-shaped structure Download PDF

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CN101712536B
CN101712536B CN2009101855896A CN200910185589A CN101712536B CN 101712536 B CN101712536 B CN 101712536B CN 2009101855896 A CN2009101855896 A CN 2009101855896A CN 200910185589 A CN200910185589 A CN 200910185589A CN 101712536 B CN101712536 B CN 101712536B
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tio
sol
colloidal sol
water soluble
funnel
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CN101712536A (en
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王琪
林承朴
崔鹏
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Hefei University of Technology
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Hefei University of Technology
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Abstract

The invention discloses a method for preparing a super-hydrophilic film with a funnel-shaped or step-shaped structure, which is characterized by comprising the following steps: dissolving 0.1 to 50.0 g/L of each of two or more different water-soluble polymers or same water-soluble polymers with different molecular weights into TiO2 sol respectively, and stirring the mixture uniformly and standing the mixture till obtaining individual water-soluble polymer-TiO2 sol or obtaining blended water-soluble polymer-TiO2 sol; and coating the obtained sol on the surface of a base material, heating the base material to between 200 and 800 DEG C at 0.5 to 5 DEG C per minute and roasting the base material for 1 to 24 hours, and cooling the base material to room temperature so as to obtain the TiO2 film with the funnel-shaped or step-shaped structure. The film has super-hydrophilic property, over 90 percent of photo-catalytic decoloring rate, higher light transmittance and antibacterial property and high adhesive force with the base material, and can be widely applied to building glass, ceramic, cast iron and stainless steel surface.

Description

A kind of preparation method with super-hydrophilic film of funnel-form or step structure
Technical field
The invention belongs to the super-hydrophilic film technical field, have funnel-form or a step structure nano-TiO on the solid material of roastings such as simple glass, building glass, vehicle glass, glasses, pottery, iron and steel but be specifically related to be applied in 2The preparation method of super-hydrophilic film.
Background technology
A kind of inorganic hydrophilic hard coating antifogging product that one Chinese patent application publication number CN1395131A proposes with a plurality of nano-scale sunk parts, its sunk part is filled by tensio-active agent and can be flowed out continuously, but because TiO 2The photocatalysis meeting decompose antifog required tensio-active agent, so the antifog cycle of this product is very short.
The low temperature preparation method of a kind of nano titanium oxide self-cleaning glass that one Chinese patent application publication number CN1417147A proposes because this coated glass just can reach anti-fog function after will under uv lamp, shine 40min, so greatly limitations its range of application.
In general, when the contact angle of water droplet and solid surface during less than 10 °, this solid is considered to have wetting ability.The so-called ultra hydrophilic contact angle of working as water droplet and solid surface that is meant is less than 5 °.The method of utilizing the synthetic super-hydrophilic film of surfactant modified titanium oxide that one Chinese patent application publication number CN101372394A proposes; Because the X 2073 modifier that is utilized has just suppressed the growth of titanium oxide crystallite; And the polar end of X 2073 is connected through static with titanium dioxide surface; In the drying process of non-polar end C-C chain and polyoxyethylene glycol effect; Along with the volatilization of solvent, macromolecular chain is assembled the surface tissue that causes intergranular reunion generation protuberance, therefore can not control the pore structure of film well; And the pore structure of Superhydrophilic and film is closely related.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with funnel-form or step structure super-hydrophilic film; To overcome the above-mentioned defective of prior art, make film can reach that ultra hydrophilic, hydrophilic hold facility is strong, transmittance is high, photocatalytic activity is high, with base material sticking power high-technology effect.
The present invention has the preparation method of funnel-form or step structure super-hydrophilic film, comprises base material is carried out pre-treatment, and preparation TiO 2Colloidal sol; Then with TiO 2Colloidal sol prepares water soluble polymer-TiO 2 sol; Water soluble polymer-the TiO 2 sol that makes is coated in substrate surface, again with 0.5-5 ℃ of min -1Temperature rise rate be warmed up to 200-800 ℃, at 200-800 ℃ of following roasting 1-24 hour, be cooled to room temperature naturally at last, promptly obtain the super-hydrophilic film with funnel-form or step structure of the present invention; It is characterized in that: said preparation water soluble polymer-TiO 2 sol is: (1) with two or more different water soluble polymers or same a kind of water soluble polymer of different molecular weight, each presses 0.1-50.0gL with it respectively -1, wherein preferred range is 1.0-10.0gL -1, be dissolved in TiO 2In the colloidal sol, left standstill after stirring 24 hours, make each independent water soluble polymer-TiO respectively 2Colloidal sol; Or same a kind of water soluble polymer of different water soluble polymers or different molecular weight that two or more is got in (2) is by 0.1-50.0gL -1, wherein preferred range is 1.0-10.0gL -1, blend is dissolved in TiO 2In the colloidal sol, left standstill after stirring 24 hours, make a kind of water soluble polymer-TiO 2 sol of blend;
When adopting each independent water soluble polymer-TiO 2 sol; Dried base material is immersed in this independent arbitrary water soluble polymer-TiO 2 sol; Adopt dipping-pulling method or spin-coating method, film at substrate surface, behind this dried coating film; On this basis by being immersed in one or more colloidal sols in addition, film again with above-mentioned same mode; When the water soluble polymer that adopts blend-TiO 2 sol, the exsiccant film base material is immersed in the water soluble polymer-TiO 2 sol of this blend, adopt dipping-pulling method or spin-coating method, film on the film base material surface, dry then.
Saidly base material carried out pre-treatment be: with film base material successively at 0.01-2.0molL -1NaOH solution, 0.01-2.0molL -1HNO 3The difference ultrasonic cleaning is 30-120 minute in solution, absolute ethyl alcohol and the zero(ppm) water, drying.
Said preparation TiO 2Colloidal sol can be selected sol-gel method or low temperature liquid polymerization process for use.
Said sol-gel method is: press tetra-n-butyl titanate: absolute ethyl alcohol: HNO 3: H 2O=(5-10): (1-8): (4-8): volume ratio (75-90), tetra-n-butyl titanate is joined in the absolute ethyl alcohol, add zero(ppm) water again, stir; Then with HNO 3Be added drop-wise in the above-mentioned mixing solutions, be warming up to 90 ℃, constant temperature stirring and refluxing 12 hours promptly makes TiO 2Colloidal sol.
Said low temperature liquid polymerization process is: with 0.1-2.0molL -1Ammoniacal liquor adds in the flask, stirs, and slowly drips 0.25-0.5molL -1The tetra-n-butyl titanate ethanolic soln, dropwise continued and stir 30min, obtain TiO 2Deposition, centrifugal, washing is to neutral; With TiO 2Deposition is transferred in the flask, and the control butyl(tetra)titanate is 1 with the ratio of nitric acid amount of substance: 3-1: 4, add 0.05-0.15molL -1Salpeter solution places 70 ℃ of waters bath with thermostatic control with said mixture, and stirring and refluxing 2 hours promptly obtains TiO 2Colloidal sol.
Said raw material water soluble polymer is that polyalcohols ethers, polyamide-based, cellulose ethers, polyoxyalkylene class, polyene acids, polyurethanes, Z 150PH, XG 550 are or/and a kind of or two kinds and the two or more mixtures in the PVP K120 (PVP); Get is 200-5 as the molecular weight ranges of the water soluble polymer of raw material, 000,000.
Said polyalcohols ethers comprises that polyoxyethylene glycol (PEG), methoxy poly (ethylene glycol) (mPEG), polyglycerol (PGL) are or/and W 166 (PPG).
Said polyamide-based SEPIGEL 305 (PAM), the sulfonated methyl polyacrylamide (SPAM) of comprising is or/and amine methyl SEPIGEL 305 (APAM).
Said cellulose ethers comprises that methylcellulose gum (MC), Natvosol (HEC), hydroxypropylcellulose (HPC), CMC 99.5 (CMC), Vltra tears (HPMC), TKK 021 (EC) are or/and methyl hydroxyethylcellulose (HEMC).
Said polyoxyalkylene class comprises polyoxyethylene (PEO) or/and polyoxytrimethylene (PTO).
Said polyene acids comprises ROHM (PAA) or/and polymethyl acrylic acid (PMMA).
Said polyurethanes comprises cation polyurethane or/and anion polyurethane.
The impregnating speed of said dipping-pulling method is 10-500cmmin -1, time of immersion is 2-10 minute, pull rate is 10-100cmmin -1Said spin-coating method is spared glue with the 1500-8000rpm speed of rotation then for the 50-1000rpm speed of rotation colloidal sol is dripped to above the base material.
Said drying is that nature dries to water cut and is lower than 5wt% or in 60-100 ℃ of baking 30-120 minute or low fiery dry 2-30 minute in microwave oven.
But said film base material is the solid material of roasting, comprises glass, ophthalmic lens, pottery or steel substrate.
The present invention produces pore owing to utilized the water soluble polymer that adds in roasting process, to decompose the back; The different apertures that produce of molecular weight are also inequality; The volume of pore increased when the volume ratio that forms pore in funnel-form or the stair-stepping ad hoc structure was thus added single polymer, thereby had improved water-holding capacity.Because film surface has bigger surface energy, very easily absorbs moisture, thereby has improved the wetting ability of film.The specific surface area of film increases, and improves the roughness of film surface, forms better adsorption potential on the surface, produces more polarity hydroxyl radical free radical.The inventive method is filled with the available technology adopting tensio-active agent or the way of interpolation silicon-dioxide is compared, and has overcome it and need just can reach the shortcoming of super hydrophilicity at ultra violet lamp, has realized working as water droplet at TiO 2The effect that can spread out fully in the time of on the film.
The funnel-form or the ultra hydrophilic film of step structure that adopt the inventive method to make also have following fundamental property:
1, because coarse film surface can produce more polarity hydroxyl radical free radical; Hydroxyl groups stops the compound of electron-hole pair as the position of catching in hole, generates the activity hydroxy of strong oxidizing property; Can decompose adsorbed organic matter, thereby have higher photocatalytic activity.Because the activity hydroxy of strong oxidizing property can decompose cell walls and then destroy the 26S Proteasome Structure and Function of cytoplasmic membrane, adopts the 20W uv lamp to being added with TiO 2The lower concentration methylene blue solution irradiation of catalyzer is after 2 hours, and the solution degradation percent of decolourization reaches more than 90%.
2, owing to adopted thermal treatment, increased the bonding force between film and glass baseplate, its sticking power reaches more than 1 grade.
3, the funnel-form or the ultra hydrophilic film of step structure that adopt the inventive method to prepare, its chemical property is stable, nontoxic, harmless, is a kind of environment-friendly energy-saving material; Its raw material sources are abundant, cost is low and easy to use, and to the glass non-corrosiveness, the transmittance of visible light reaches more than 85%; Biggest advantage is to have Superhydrophilic; Particularly in rainy season; Its meliority is particularly outstanding; Only need to rely on the nature rainwater just can wash away dust at glass surface, organism etc., make the glass bright and clean, reached human dream of save time, water-saving, use manpower and material resources sparingly, safe wonderful dream.Adopt the funnel-form or the ultra hydrophilic film of step structure of the inventive method preparation, its big specific surface area can absorbed air in more obnoxious flavour, and when solar light irradiation is arranged, pollutent is decomposed.
4, because the activity hydroxy of strong oxidizing property can decompose the 26S Proteasome Structure and Function of cell walls and then destruction cytoplasmic membrane, thereby ultra hydrophilic film of the present invention has bacterinertness; Ultra hydrophilic film of the present invention can produce negative oxygen ion, and cytolemma that can decomposing bacteria reaches the purpose of fresh air, deodorization and sterilization.
Adopt this funnel-form or the step structure film of the inventive method preparation to have Superhydrophilic, the photochemical catalysis percent of decolourization reaches more than 90%, has higher transmittance and bacterinertness, and is high with base material sticking power; Can be widely used in building glass, pottery, cast iron, stainless steel surface.
Description of drawings
Fig. 1 is AFM (AFM) the 3 D stereo skeleton diagram with funnel-form or step structure super-hydrophilic film of preparation among the embodiment 1.
Fig. 2 is for choosing the one-dimensional profile figure that a regional area extracts from Fig. 1.
Fig. 3 is sem (SEM) sectional drawing with funnel-form or step structure super-hydrophilic film of preparation among the embodiment 1, and film thickness is 77.4nm.
Fig. 4 is AFM (AFM) the 3 D stereo skeleton diagram with funnel-form or step structure super-hydrophilic film of preparation among the embodiment 2.
Fig. 5 is for choosing the one-dimensional profile figure that a regional area extracts from Fig. 2.
Fig. 6 is sem (SEM) sectional drawing with funnel-form or step structure super-hydrophilic film of preparation among the embodiment 2, and film thickness is 144nm.
Fig. 7 is AFM (AFM) the 3 D stereo skeleton diagram with funnel-form or step structure super-hydrophilic film of preparation among the embodiment 3.
Fig. 8 is for choosing the one-dimensional profile figure that a regional area extracts from Fig. 3.
Fig. 9 is sem (SEM) sectional drawing with funnel-form or step structure super-hydrophilic film of preparation among the embodiment 3, and film thickness is 292nm.
Figure 10 is sem (SEM) plat with funnel-form or step structure super-hydrophilic film of preparation among the embodiment 1.
Embodiment
Embodiment 1:
With glass baseplate successively at 0.01molL -1NaOH solution, 0.01molL -1HNO 3The difference ultrasonic cleaning is 30 minutes in solution, absolute ethyl alcohol and the zero(ppm) water, drying.Adopt sol-gel method, the 40mL tetra-n-butyl titanate is joined in the 500mL there-necked flask that the 32mL absolute ethyl alcohol is housed, add 300mL zero(ppm) water again, stir; Be 2molL with 28mL concentration then -1HNO 3Be added drop-wise in the above-mentioned mixing solutions, be warming up to 90 ℃, constant temperature stirring and refluxing 12 hours makes TiO 2Colloidal sol.
Get 150mL TiO 2Colloidal sol toward the PEG200 that wherein adds 0.03g (refer to the polyoxyethylene glycol to be water soluble polymer, molecular-weight average is 200, down together), left standstill after stirring 24 hours, made 0.2gL -1PEG200-TiO 2Colloidal sol; Other gets 150mL TiO 2Colloidal sol, the PEG1000 toward wherein adding 0.75g left standstill after stirring 24 hours, made 5.0gL -1PEG1000-TiO 2Colloidal sol.Adopt dipping-pulling method, with glass baseplate with 10cmmin -1Speed be impregnated into PEG200-TiO 2In the colloidal sol, flood after 10 minutes, again with 50cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, and after the completion of filming that coated glass is low fiery dry 2 minutes in microwave oven, the number of plies of filming is 1 layer.Dry back is with 10cmmin -1Speed, glass baseplate is impregnated into PEG1000-TiO 2In the colloidal sol, flood after 10 minutes, again with 50cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, and after the completion of filming that coated glass is low fiery dry 2 minutes in microwave oven, the number of plies of filming is 1 layer.Then in retort furnace with 0.5 ℃ of min -1Temperature rise rate, 400 ℃ of roastings 24 hours, be cooled to room temperature naturally.Resulting film is designated as T1.
To the coated glass sheet after the above-mentioned film intercepting 0.5cm * 0.5cm roasting for preparing, carry out AFM (AFM) test, the 3 D stereo profile that obtains this film is as shown in Figure 1.Can see that from Fig. 1 " mountain peak " and " mountain valley " appearred in film surface, the water soluble polymer that hence one can see that is selected for use has played control action kou to film surface appearance.
Fig. 2 is for choosing the one-dimensional profile figure that a regional area extracts from Fig. 1.From Fig. 2, can see the microstructure of film or, it classified as funnel-shaped structure, or, it classified as step structure for the broached-tooth design shown in the frame of broken lines 1 in scheming for the inverted triangle structure shown in the frame of broken lines 2 among the figure.Be to have prepared film in the present embodiment with funnel-form or step structure.
To the coated glass sheet after the above-mentioned film intercepting 0.5cm * 0.5cm roasting for preparing, carry out sem (SEM) test.The sem sectional drawing that obtains this film is as shown in Figure 3.The thickness that from Fig. 3, can see this film is 77.4nm.
The water soluble polymer that is adopted in the present embodiment can also select for use methoxy poly (ethylene glycol) (mPEG), polyglycerol (PGL) or/and W 166 (PPG) can both obtain similar effects except that can selecting polyoxyethylene glycol (PEG) for use.
Embodiment 2:
With glass baseplate successively at 0.01molL -1NaOH solution, 0.01molL -1HNO 3The difference ultrasonic cleaning is 30 minutes in solution, absolute ethyl alcohol and the zero(ppm) water, drying.Adopt sol-gel method, the 36mL tetra-n-butyl titanate is joined in the 500mL there-necked flask that the 12mL absolute ethyl alcohol is housed, add 320mL zero(ppm) water again, stir; Be 2molL with 32mL concentration then -1HNO 3Be added drop-wise in the above-mentioned mixing solutions, be warming up to 90 ℃, constant temperature stirring and refluxing 12 hours promptly makes TiO 2Colloidal sol.
Get the TiO of the above-mentioned preparation of 150mL 2Colloidal sol, the PEG4000 toward wherein adding 3.0g left standstill after stirring 24 hours, made 20.0gL -1PEG4000-TiO 2Colloidal sol; Other gets the TiO of the above-mentioned preparation of 150mL 2Colloidal sol, the PEG20000 toward wherein adding 7.5g left standstill after stirring 24 hours, made 50.0gL -1PEG20000-TiO 2Colloidal sol.Adopt dipping-pulling method, with glass baseplate with 200cmmin -1Speed be impregnated into PEG4000-TiO 2In the colloidal sol, flood after 6 minutes, again with 50cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, and after the completion of filming that coated glass is low fiery dry 15 minutes in microwave oven, the number of plies of filming is 2 layers.Dry back is with 200cmmin -1Speed, glass baseplate is impregnated into PEG20000-TiO 2In the colloidal sol, flood after 6 minutes, again with 50cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, and after the completion of filming that coated glass is low fiery dry 15 minutes in microwave oven, the number of plies of filming is 2 layers.Then in retort furnace with 1 ℃ of min -1Temperature rise rate, 500 ℃ of roastings 12 hours, be cooled to room temperature naturally.This film for preparing is designated as T2.
To the coated glass sheet after the above-mentioned film intercepting 0.5cm * 0.5cm roasting for preparing, carry out AFM (AFM) test, the AFM 3 D stereo profile of the film that obtains preparing in the present embodiment is as shown in Figure 4.Can see that from Fig. 4 " mountain peak " and " mountain valley " appearred in film surface, the water soluble polymer that hence one can see that is selected for use has played control action kou to film surface appearance.
Fig. 5 is for choosing the one-dimensional profile figure that a regional area extracts from Fig. 4.From Fig. 5, can see the microstructure of film or, it classified as funnel-shaped structure, or, it classified as step structure for the broached-tooth design shown in the frame of broken lines 3 in scheming for the inverted triangle structure shown in the frame of broken lines 4 among the figure.Be to have prepared film in the present embodiment with funnel-form or step structure.
To the coated glass sheet after the above-mentioned film intercepting 0.5cm * 0.5cm roasting for preparing, carry out sem (SEM) test, the sem sectional drawing that obtains this super-hydrophilic film is as shown in Figure 6.The thickness that from Fig. 6, can see this film is 144nm.
Embodiment 3:
With glass baseplate successively at 0.01molL -1NaOH solution, 0.01molL -1HNO 3The difference ultrasonic cleaning is 30 minutes in solution, absolute ethyl alcohol and the zero(ppm) water, drying.Adopt sol-gel method, the 20mL tetra-n-butyl titanate is joined in the 500mL there-necked flask that the 4mL absolute ethyl alcohol is housed, add 360mL zero(ppm) water again, stir; Be 2molL with 16mL concentration then -1HNO 3Be added drop-wise in the above-mentioned mixing solutions, be warming up to 90 ℃, constant temperature stirring and refluxing 12 hours promptly makes TiO 2Colloidal sol.
Get in the 150mL present embodiment and prepare TiO 2Colloidal sol, the PEG4000 toward wherein adding 3.75g left standstill after stirring 24 hours, made 25.0gL -1PEG4000-TiO 2Colloidal sol; Other gets in the 150mL present embodiment and prepares TiO 2Colloidal sol, the PEG20000 toward wherein adding 6.0g left standstill after stirring 24 hours, made 40.0gL -1PEG20000-TiO 2Colloidal sol.Adopt dipping-pulling method, with glass baseplate with 200cmmin -1Speed be impregnated into PEG4000-TiO 2In the colloidal sol, flood after 5 minutes, again with 10cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, and after the completion of filming that coated glass is low fiery dry 30 minutes in microwave oven, the number of plies of filming is 5 layers.Dry back is with 200cmmin -1Speed, glass baseplate is impregnated into PEG20000-TiO 2In the colloidal sol, flood after 5 minutes, again with 10cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, and after the completion of filming that coated glass is low fiery dry 15 minutes in microwave oven, the number of plies of filming is 2 layers.Then in retort furnace with 2 ℃ of min -1Temperature rise rate, 500 ℃ of roastings 12 hours, be cooled to room temperature naturally.With this film for preparing, be designated as T3.
To the coated glass sheet after the above-mentioned film intercepting 0.5cm * 0.5cm roasting for preparing, carry out AFM (AFM) test, the AFM 3 D stereo profile of the film that obtains preparing in the present embodiment is as shown in Figure 7.Can see that from Fig. 7 " mountain peak " and " mountain valley " appearred in film surface, the water soluble polymer that hence one can see that is selected for use has played control action kou to film surface appearance.
Fig. 8 is for choosing the one-dimensional profile figure that a regional area extracts from Fig. 7.From Fig. 8, can see the microstructure of this film or, it classified as funnel-shaped structure, or, it classified as step structure for the broached-tooth design shown in the frame of broken lines 5 in scheming for the inverted triangle structure shown in the frame of broken lines 6 among the figure.Be to have prepared film in the present embodiment with funnel-form or step structure.
To the coated glass sheet after the above-mentioned film intercepting 0.5cm * 0.5cm roasting for preparing, carry out sem (SEM) test, the sem sectional drawing that obtains this film is as shown in Figure 9.The thickness that from Fig. 9, can see this film is 292nm.
Embodiment 4:
Cast iron surface plate is distinguished ultrasonic cleaning 120 minutes, drying successively in absolute ethyl alcohol and zero(ppm) water.Adopting low temperature liquid polymerization process, in 70 ℃ of thermostat water baths, is 1.5molL with 20mL concentration -1Ammoniacal liquor add in the 250mL there-necked flask, stir, slowly dripping 30mL concentration is 0.25molL -1The tetra-n-butyl titanate ethanolic soln.Dropwise continued and stir 30min, obtain TiO 2Deposition, centrifugal, washing is to neutral.With TiO 2Deposition is transferred in the 500mL there-necked flask, and the control butyl(tetra)titanate is 1: 3 with the ratio of nitric acid amount of substance, and adding 450mL concentration is 0.05molL -1Salpeter solution, said mixture is placed 70 ℃ of waters bath with thermostatic control, stirring and refluxing 2 hours obtains TiO 2Colloidal sol.
Get in the 150mL present embodiment and prepare TiO 2Colloidal sol, the PEG2000 toward wherein adding 2.25g left standstill after stirring 24 hours, made 15.0gL -1PEG2000-TiO 2Colloidal sol; Other gets in the 150mL present embodiment and prepares TiO 2Colloidal sol, the PEG6000 toward wherein adding 4.5g left standstill after stirring 24 hours, made 30.0gL -1PEG6000-TiO 2Colloidal sol.Adopt spin-coating method, with the 50rpm speed of rotation with PEG6000-TiO 2Colloidal sol drips to above the base material, spares glue with the 1500rpm speed of rotation then, the cast iron 60 ℃ of dryings 120 minutes in baking oven of will filming after accomplishing of filming, and the number of plies of filming is 4 layers.Dry back with the 50rpm speed of rotation with PEG2000-TiO 2Colloidal sol drips to above the base material, spares glue with the 1500rpm speed of rotation, the cast iron 60 ℃ of dryings 120 minutes in baking oven of will filming after accomplishing of filming, and the number of plies of filming is 4 layers.Then in retort furnace with 3 ℃ of min -1Temperature rise rate, 800 ℃ of roastings 1 hour, be cooled to room temperature naturally, the film for preparing is designated as T4.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 3 are similar.
Embodiment 5:
Adopt the base material pretreatment process of embodiment 1.Adopting low temperature liquid polymerization process, in 70 ℃ of thermostat water baths, is 2.0molL with 25mL concentration -1Ammoniacal liquor add in the 250mL there-necked flask, stir, slowly dripping 25mL concentration is 0.5molL -1The tetra-n-butyl titanate ethanolic soln.Dropwise continued and stir 30min, obtain TiO 2Deposition, centrifugal, washing is to neutral.With TiO 2Deposition is transferred in the 500mL there-necked flask, and the control butyl(tetra)titanate is 1: 3.5 with the ratio of nitric acid amount of substance, and adding 437.5mL concentration is 0.10molL -1Salpeter solution, said mixture is placed 70 ℃ of waters bath with thermostatic control, stirring and refluxing 2 hours obtains TiO 2Colloidal sol.
Get 150mL TiO 2Colloidal sol, toward the PEG400 that wherein adds 0.03g, the PEG2000 of 0.75g left standstill after stirring 24 hours, made 0.2gL -1PEG400 and 5.0gL -1PEG2000 blend-TiO 2Colloidal sol.Adopt spin-coating method, with the 500rpm speed of rotation with PEG400 and PEG2000 blend-TiO 2Colloidal sol drips to above the base material, spares glue with the 5000rpm speed of rotation then, film accomplish after with coated glass 80 ℃ of dryings 60 minutes in baking oven, the number of plies of filming is 8 layers.Then in retort furnace with 4 ℃ of min -1Temperature rise rate, 400 ℃ of roastings 8 hours, be cooled to room temperature naturally, the film for preparing is designated as T5.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 2 are similar.
Embodiment 6:
Adopt the base material pretreatment process of embodiment 1.Adopting low temperature liquid polymerization process, in 70 ℃ of thermostat water baths, is 1.0molL with 56mL concentration -1Ammoniacal liquor add in the 250mL there-necked flask, stir, slowly dripping 40mL concentration is 0.35molL -1The tetra-n-butyl titanate ethanolic soln.Dropwise continued and stir 30min, obtain TiO 2Deposition, centrifugal, washing is to neutral.With TiO 2Deposition is transferred in the 500mL there-necked flask, and the control butyl(tetra)titanate is 1: 4 with the ratio of nitric acid amount of substance, and adding 374mL concentration is 0.15molL -1Salpeter solution places 70 ℃ of waters bath with thermostatic control with said mixture, and stirring and refluxing 2 hours obtains TiO 2Colloidal sol.
Get 150mL TiO 2Colloidal sol, toward the PEG1000 that wherein adds 0.45g, the methoxy poly (ethylene glycol) mPEG of 0.75g left standstill after stirring 24 hours, made 3.0gL -1PEG1000 and 5.0gL -1MPEG blend-TiO 2Colloidal sol.Adopt spin-coating method, with the 1000rpm speed of rotation with PEG1000 and mPEG blend-TiO 2Colloidal sol drips to above the base material, spares glue with the 8000rpm speed of rotation then, the pottery 100 ℃ of dryings 30 minutes in baking oven of will filming after accomplishing of filming, and the number of plies of filming is 10 layers.Then in retort furnace with 5 ℃ of min -1Temperature rise rate, 600 ℃ of roastings 10 hours, be cooled to room temperature naturally, the film for preparing is designated as T6.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 3 are similar.
Embodiment 7:
Adopt base material pretreatment process and the sol-gel method of embodiment 1 to prepare TiO 2Colloidal sol.Get 150mL TiO 2Colloidal sol, the PEG2000 toward wherein adding 2.25g left standstill after stirring 24 hours, made 15.0gL -1PEG2000-TiO 2Colloidal sol.At TiO 2Add the PVA1750 of 0.75g in the colloidal sol, left standstill after stirring 24 hours, make 5.0gL -1PVA1750-TiO 2Colloidal sol.Adopt dipping-pulling method, with stainless steel substrate with 10cmmin -1Speed be impregnated into PEG2000-TiO 2In the colloidal sol, flood after 10 minutes, again with 10cmmin -1Pull rate lifts out colloidal sol with stainless steel substrate and films at stainless steel surface, and the stainless steel of will filming after the completion of filming dries naturally, and the number of plies of filming is 1 layer.Dry back with the stainless steel of will filming with 10cmmin -1Speed be impregnated into PVA1750-TiO 2In the colloidal sol, flood after 10 minutes, again with 10cmmin -1Pull rate lifts out colloidal sol with stainless steel substrate and films at stainless steel surface, and the stainless steel of will filming after accomplishing of filming dries naturally, and the number of plies of filming is 1 layer, then in retort furnace with 0.5 ℃ of min -1Temperature rise rate, 800 ℃ of roastings 1 hour, be cooled to room temperature naturally, the film for preparing is designated as T7.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 1 are similar.
Embodiment 8:
Adopt base material pretreatment process and the sol-gel method of embodiment 2 to prepare TiO 2Colloidal sol.Get 150mLTiO 2Colloidal sol, the PVA124 toward wherein adding 1.2g left standstill after stirring 24 hours, made 8.0gL -1PVA124-TiO 2Colloidal sol.Other gets 150mL TiO 2Colloidal sol, the PPG toward wherein adding 1.5g left standstill after stirring 24 hours, made 10.0gL -1PPG-TiO 2Colloidal sol.With the glass plate is base material, adopts dipping-pulling method, with glass baseplate with 500cmmin -1Speed be impregnated into PPG-TiO 2In the colloidal sol, flood after 2 minutes, again with 100cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, after the completion of filming coated glass is dried naturally, and the number of plies of filming is 2 layers.Dry back is with 500cmmin -1Speed, will smear glass-impregnated to PVA124-TiO 2In the colloidal sol, flood after 2 minutes, again with 100cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, after the completion of filming coated glass is dried naturally, and the number of plies of filming is 2 layers.Then in retort furnace with 1 ℃ of min -1Temperature rise rate, 450 ℃ of roastings 15 hours, be cooled to room temperature naturally, the film for preparing is designated as T8.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 1 are similar.
Embodiment 9:
Adopt base material pretreatment process and the low temperature liquid polymerization process of embodiment 6 to prepare TiO 2Colloidal sol.Get 150mL TiO 2Colloidal sol, the PEG4000 toward wherein adding 3.75g left standstill after stirring 24 hours, made 25.0gL -1PEG4000-TiO 2Colloidal sol.Other gets 150mL TiO 2Colloidal sol, toward the PAM5 that wherein adds 0.75g, 000,000, left standstill after stirring 24 hours, make 5.0gL -1PAM5,000,000-TiO 2Colloidal sol.With the earthenware slab is base material, adopts dipping-pulling method, with ceramic base material with 10cmmin -1Speed be impregnated into PEG4000-TiO 2In the colloidal sol, flood after 10 minutes, again with 10cmmin -1Pull rate lifts out colloidal sol with ceramic base material and films at ceramic surface, and the pottery of will filming after the completion of filming dries naturally, and the number of plies of filming is 3 layers.Dry back 10cmmin -1Speed, will smear glass-impregnated to PVA124-TiO 2In the colloidal sol, flood after 10 minutes, again with 10cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, after the completion of filming coated glass is dried naturally, and the number of plies of filming is 3 layers.Then in retort furnace with 2 ℃ of min -1Temperature rise rate, 550 ℃ of following roastings 10 hours, be cooled to room temperature naturally, the film for preparing is designated as T9.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 2 are similar.
Said water soluble polymer can also be selected sulfonated methyl polyacrylamide (SPAM) for use or/and amine methyl SEPIGEL 305 (APAM) can both obtain similar effects except that can selecting SEPIGEL 305 (PAM) for use.
Embodiment 10:
Cast iron surface plate is distinguished ultrasonic cleaning 120 minutes, drying successively in absolute ethyl alcohol and zero(ppm) water.Adopt the low temperature liquid polymerization process of embodiment 4 to prepare TiO 2Colloidal sol.Get 150mL TiO 2Colloidal sol, toward the PVA1750 that wherein adds 1.5g, the non-ionic type PAM1 of 0.9g, 000,000, left standstill after stirring 24 hours, make 10.0gL -1PVA1750 and 6.0gL -1PAM1,000,000 blend-TiO 2Colloidal sol.With the cast iron surface plate is base material, adopts spin-coating method, with the 800rpm speed of rotation with PVA1750 and PAM1,000,000 blend-TiO 2Colloidal sol drips to above the base material, spares glue with the 6000rpm speed of rotation then, and the cast iron of will filming after the completion of filming is low fiery dry 20 minutes in microwave oven, and the number of plies of filming is 6 layers.Then in retort furnace with 3 ℃ of min -1Temperature rise rate, 700 ℃ of roastings 5 hours, be cooled to room temperature naturally, the film for preparing is designated as T10.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 1 are similar.
Embodiment 11:
Adopt base material pretreatment process and the sol-gel method of embodiment 3 to prepare TiO 2Colloidal sol.Get 150mL TiO 2Colloidal sol, toward the sulfonated methyl polyacrylamide SPAM that wherein adds 1.5g, the MC of 3.0g left standstill after stirring 24 hours, made 10.0gL -1SPAM and 20.0gL -1MC blend-TiO 2Colloidal sol.With the glass plate is base material, adopts spin-coating method, with the 600rpm speed of rotation with SPAM and MC blend-TiO 2Colloidal sol drips to above the base material, spares glue with the 4000rpm speed of rotation then, and after the completion of filming that coated glass is low fiery dry 10 minutes in microwave oven, the number of plies of filming is 10 layers.Then in retort furnace with 4 ℃ of min -1Temperature rise rate, 350 ℃ of roastings 20 hours, be cooled to room temperature naturally, the film for preparing is designated as T11.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 3 are similar.
Said water soluble polymer is except that can selecting methylcellulose gum (MC) for use; Can also select for use Natvosol (HEC), hydroxypropylcellulose (HPC), CMC 99.5 (CMC), Vltra tears (HPMC), TKK 021 (EC) or/and methyl hydroxyethylcellulose (HEMC) can both obtain similar effects.
Embodiment 12:
Adopt base material pretreatment process and the low temperature liquid polymerization process of embodiment 6 to prepare TiO 2Colloidal sol.Get 150mL TiO 2Colloidal sol, toward the PEG6000 that wherein adds 4.5g, the Natvosol HEC of 0.75g left standstill after stirring 24 hours, made 30.0gL -1PEG6000 and 5.0gL -1HEC blend-TiO 2Colloidal sol.With the earthenware slab is base material, adopts spin-coating method, with the 400rpm speed of rotation with PEG6000 and HEC blend-TiO 2Colloidal sol drips to above the base material, spares glue with the 2000rpm speed of rotation then, and the pottery of will filming after the completion of filming is low fiery dry 10 minutes in microwave oven, and the number of plies of filming is 4 layers.Then in retort furnace with 5 ℃ of min -1Temperature rise rate, 500 ℃ of roastings 12 hours, be cooled to room temperature naturally, the film for preparing is designated as T12.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 1 are similar.
Embodiment 13:
Adopt base material pretreatment process and the sol-gel method of embodiment 1 to prepare TiO 2Colloidal sol.Get 150mL TiO 2Colloidal sol, the MC toward wherein adding 6.0g left standstill after stirring 24 hours, made 40.0gL -1MC-TiO 2Colloidal sol.Other gets a certain amount of TiO 2Colloidal sol, the polyoxyethylene PEO toward wherein adding 2.25g makes 15.0gL -1PEO-TiO 2Colloidal sol.With the stainless steel flat plate is base material, adopts dipping-pulling method, with stainless steel substrate to be impregnated into PEO-TiO 2In the colloidal sol, flood after 4 minutes, again with 40cmmin -1Pull rate lifts out colloidal sol with stainless steel substrate and films at stainless steel surface, and the stainless steel of will filming after the completion of filming dries naturally, and the number of plies of filming is 3 layers.Dry back is with 150cmmin -1Speed, coated glass is impregnated into MC-TiO 2In the colloidal sol, flood after 4 minutes, again with 40cmmin -1Pull rate lifts out colloidal sol with stainless steel substrate and films at stainless steel surface, and the stainless steel of will filming after the completion of filming dries naturally, and the number of plies of filming is 3 layers.Then in retort furnace with 0.5 ℃ of min -1Temperature rise rate, 550 ℃ of roastings 10 hours, be cooled to room temperature naturally, the film for preparing is designated as T13.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 1 are similar.
Embodiment 14:
Adopt base material pretreatment process and the low temperature liquid polymerization process of embodiment 5 to prepare TiO 2Colloidal sol.Get 150mL TiO 2Colloidal sol, the polyoxytrimethylene PTO toward wherein adding 3.75g left standstill after stirring 24 hours, made 25.0gL -1PTO-TiO 2Colloidal sol.Other gets 150mL TiO 2Colloidal sol, the ROHM PAA toward wherein adding 2.25g makes 15.0gL -1PAA-TiO 2Colloidal sol.With the glass plate is base material, adopts dipping-pulling method, with glass baseplate with 250cmmin -1Speed be impregnated into PTO-TiO 2In the colloidal sol, flood after 8 minutes, again with 60cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, after the completion of filming coated glass is dried naturally, and the number of plies of filming is 4 layers.Dry back is with 250cmmin -1Speed, coated glass is impregnated into PAA-TiO 2In the colloidal sol, flood after 8 minutes, again with 60cmmin -1Pull rate lifts out colloidal sol with glass baseplate and films at glass surface, after the completion of filming coated glass is dried naturally, and the number of plies of filming is 4 layers.Then in retort furnace with 1 ℃ of min -1Temperature rise rate, 600 ℃ of roastings 8 hours, be cooled to room temperature naturally, the film for preparing is designated as T14.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 2 are similar.
Embodiment 15:
Adopt base material pretreatment process and the low temperature liquid polymerization process of embodiment 6 to prepare TiO 2Colloidal sol.Get 150mL TiO 2Colloidal sol, the polymethyl acrylic acid PMMA toward wherein adding 0.75g left standstill after stirring 24 hours, made 5.0gL -1PMMA-TiO 2Colloidal sol.Other gets 150mL TiO 2Colloidal sol, the cation polyurethane toward wherein adding 2.25g makes 15.0gL -1Cation polyurethane-TiO 2 sol.With the earthenware slab is base material, adopts dipping-pulling method, with ceramic base material with 50cmmin -1Speed be impregnated in cation polyurethane-TiO 2 sol, flood after 20 minutes, again with 20cmmin -1Pull rate lifts out colloidal sol with ceramic base material and films at ceramic surface, and the pottery of will filming after the completion of filming dries naturally, and the number of plies of filming is 5 layers.Dry back is with 50cmmin -1Speed, the cerdip of will filming is to PMMA-TiO 2Film in the colloidal sol, flood after 20 minutes, again with 20cmmin -1Pull rate lifts out colloidal sol with ceramic base material and films at ceramic surface, and the pottery of will filming after the completion of filming dries naturally, and the number of plies of filming is 5 layers.Then in retort furnace with 2 ℃ of min -1Temperature rise rate, 700 ℃ of roastings 3 hours, be cooled to room temperature naturally, the film for preparing is designated as T15.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 3 are similar.
Embodiment 16:
Adopt base material pretreatment process and the low temperature liquid polymerization process of embodiment 4 to prepare TiO 2Colloidal sol.Get 150mL TiO 2Colloidal sol toward wherein adding the anion polyurethane of 1.5g and the XG 550 of 0.45g, left standstill after stirring 24 hours, made 10.0gL -1Urethane and 3.0gL -1XG 550 blend-TiO 2 sol.With the cast iron surface plate is base material; Adopt spin-coating method; With the 100rpm speed of rotation urethane and XG 550 blend-TiO 2 sol are dripped to above the base material; Spare glue with the 1500rpm speed of rotation then, the cast iron 60 ℃ of dryings 100 minutes in baking oven of will filming after accomplishing of filming, the number of plies of filming is 5 layers.Then in retort furnace with 3 ℃ of min -1Temperature rise rate, 800 ℃ of roastings 2 hours, be cooled to room temperature naturally, the film for preparing is designated as T16.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 1 are similar.
Embodiment 17:
Adopt base material pretreatment process and the sol-gel method of embodiment 2 to prepare TiO 2Colloidal sol.Get 150mL TiO 2Colloidal sol, toward the PEG20000 that wherein adds 6.75g, the MC of 1.5g, the PVP of 0.45g left standstill after stirring 24 hours, made 45.0gL -1PEG20000 and 10.0gL -1MC and 3.0gL -1PVP blend-TiO 2Colloidal sol.With the stainless steel flat plate is base material, adopts spin-coating method, with the 200rpm speed of rotation with PEG20000 and MC and PVP blend-TiO 2Colloidal sol drips to above the base material, spares glue with the 3000rpm speed of rotation then, the stainless steel 80 ℃ of dryings 60 minutes in baking oven of will filming after accomplishing of filming, and the number of plies of filming is 7 layers.Then in retort furnace with 4 ℃ of min -1Temperature rise rate, 500 ℃ of roastings 10 hours, be cooled to room temperature naturally, the film for preparing is designated as T17.
The above-mentioned film for preparing is carried out AFM (AFM) and sem (SEM) test, and gained result and embodiment 2 are similar.
The performance of the above T1-T17 film for preparing is listed in table 1 so that relatively together with estimating:
The performance evaluation of table 1 T1-T17 laminated film
Numbering Contact angle/° Photochemical catalysis percent of decolourization/% Transmittance/% Bactericidal properties/% Sticking power/level
T1 4.3 92.0 89.8 80.6 ?1
T2 1.5 91.3 87.8 75.9 ?0
T3 1.4 93.3 88.6 91.0 ?0
T4 3.3 90.3 -- 78.6 ?0
T5 4.8 91.8 88.1 85.1 ?1
T6 1.7 90.6 -- 83.7 ?0
T7 3.0 90.2 -- 88.5 ?0
T8 2.1 90.8 90.0 87.3 ?1
T9 1.4 95.4 -- 71.2 0
T10 2.8 92.9 -- 88.7 0
T11 4.5 92.3 88.8 89.8 1
T12 1.5 90.1 -- 76.7 0
T13 1.8 92.8 -- 70.8 0
T14 2.5 90.8 89.0 83.2 0
T15 3.9 91.2 -- 80.6 0
T16 4.3 90.9 -- 83.5 0
T17 2.1 90.3 -- 84.4 0
Employed explanation of nouns is following in the his-and-hers watches 1:
Contact angle: a contact angle of water droplet and film, employing direct measurement or photo method calculate after measuring;
The photochemical catalysis percent of decolourization: the photocatalytic oxidation degradation starting point concentration is the 10ppm methylene blue solution, the 20W uv lamp, and the 1000mL flat-plate reactor, reaction times 100min representes with the variation of methylene blue solution absorbancy;
Transmittance: under the visible wavelength 600nm,, measure the transmittance of coated glass with respect to coated glass not;
Bactericidal properties: the employing intestinal bacteria are bacterial classification, adopt the bacterium method to measure;
Sticking power: adopt GB9286-1998 cross cut test method.
Visible from table 1: the TiO of preparation 2A contact angle of film reaches below 5 °, promptly has Superhydrophilic; The photochemical catalysis percent of decolourization reaches more than 90%; Have good transmittance and bactericidal properties; Has good sticking power with base material.
Compare, conclude and sum up by top analysis, can draw: adopt same a kind of water soluble polymer of two or more water soluble polymer or different molecular weight can prepare TiO with funnel-form and stepped microstructure to embodiment result 2Film.Film has Superhydrophilic, and good photocatalysis performance and bactericidal properties are filmed on glass baseplate, still have higher transmittance, and be good with the sticking power of base material.
The present invention produces pore owing to utilized the water soluble polymer that adds in roasting process, to decompose the back, and the different apertures that produce of molecular weight are also inequality.Figure 10 is sem (SEM) plat with funnel-form or step structure super-hydrophilic film of preparation among the embodiment 1.Shown in figure 10: as can be seen from Figure 10 film surface has produced equally distributed micropore.The volume of pore increased when the volume ratio that forms pore in funnel-form or the stair-stepping ad hoc structure was thus added single polymer, thereby had improved water-holding capacity.Because film surface has bigger surface energy, very easily absorbs moisture, thereby has improved the wetting ability of film.The specific surface area of film increases, and improves the roughness of film surface, forms better adsorption potential on the surface, produces more polarity hydroxyl radical free radical.The inventive method is filled with the available technology adopting tensio-active agent or the way of interpolation silicon-dioxide is compared, and has overcome it and need just can reach the shortcoming of super hydrophilicity at ultra violet lamp, has realized working as water droplet at TiO 2The effect that can spread out fully in the time of on the film.
The ultra hydrophilic film of funnel-form that the inventive method makes or step structure also has following fundamental property:
1, because coarse film surface can produce more polarity hydroxyl radical free radical; Hydroxyl groups stops the compound of electron-hole pair as the position of catching in hole, generates the activity hydroxy of strong oxidizing property; Can decompose adsorbed organic matter, thereby have higher photocatalytic activity.Because the activity hydroxy of strong oxidizing property can decompose cell walls and then destroy the 26S Proteasome Structure and Function of cytoplasmic membrane, after employing 20W uv lamp shone 2 hours to the lower concentration methylene blue solution that is added with the TiO2 catalyzer, the solution degradation percent of decolourization reached more than 90%.
2, owing to adopted thermal treatment, increased the bonding force between film and glass baseplate, its sticking power reaches more than 1 grade.
3, the funnel-form or the ultra hydrophilic film of step structure that adopt the inventive method to prepare, its chemical property is stable, nontoxic, harmless, is a kind of environment-friendly energy-saving material; Its raw material sources are abundant, cost is low and easy to use, and to the glass non-corrosiveness, the transmittance of visible light reaches more than 85%; Biggest advantage is to have Superhydrophilic; Particularly in rainy season; Its meliority is particularly outstanding; Only need to rely on the nature rainwater just can wash away dust at glass surface, organism etc., make the glass bright and clean, reached human dream of save time, water-saving, use manpower and material resources sparingly, safe wonderful dream.Adopt the funnel-form or the ultra hydrophilic film of step structure of the inventive method preparation, its big specific surface area can absorbed air in more obnoxious flavour, and when solar light irradiation is arranged, pollutent is decomposed.
4, because the activity hydroxy of strong oxidizing property can decompose the 26S Proteasome Structure and Function of cell walls and then destruction cytoplasmic membrane, thereby ultra hydrophilic film of the present invention has bacterinertness; Ultra hydrophilic film of the present invention can produce negative oxygen ion, and cytolemma that can decomposing bacteria reaches the purpose of fresh air, deodorization and sterilization.
Adopt this funnel-form or the step structure film of the inventive method preparation to have Superhydrophilic, the photochemical catalysis percent of decolourization reaches more than 90%, has higher transmittance and bacterinertness, and is high with base material sticking power; Can be widely used in building glass, pottery, cast iron, stainless steel surface.

Claims (9)

1. the preparation method with funnel-form or step structure super-hydrophilic film comprises base material is carried out pre-treatment, and preparation TiO 2Colloidal sol; Then with TiO 2Colloidal sol prepares water soluble polymer-TiO 2 sol; Water soluble polymer-the TiO 2 sol that makes is coated in substrate surface, again with 0.5-5 ℃ of min -1Temperature rise rate be warmed up to 200-800 ℃, at 200-800 ℃ of following roasting 1-24 hour, be cooled to room temperature naturally at last, promptly obtain the super-hydrophilic film with funnel-form or step structure of the present invention; It is characterized in that: said preparation water soluble polymer-TiO 2 sol is: (1) with two or more different water soluble polymers or same a kind of water soluble polymer of different molecular weight, each presses 0.1-50.0gL with it respectively -1Be dissolved in TiO 2In the colloidal sol, left standstill after stirring 24 hours, make each independent water soluble polymer-TiO respectively 2Colloidal sol; Or same a kind of water soluble polymer of different water soluble polymers or different molecular weight that two or more is got in (2) is by 0.1-50.0gL -1, blend is dissolved in TiO 2In the colloidal sol, left standstill after stirring 24 hours, make a kind of water soluble polymer-TiO 2 sol of blend;
When adopting each independent water soluble polymer-TiO 2 sol; Dried base material is immersed in this independent arbitrary water soluble polymer-TiO 2 sol; Adopt dipping-pulling method or spin-coating method, film at substrate surface, behind this dried coating film; On this basis by being immersed in one or more colloidal sols in addition, film again with above-mentioned same mode; When the water soluble polymer that adopts blend-TiO 2 sol, the exsiccant film base material is immersed in the water soluble polymer-TiO 2 sol of this blend, adopt dipping-pulling method or spin-coating method, film on the film base material surface, dry then;
Said raw material water soluble polymer is a kind of in polyalcohols ethers, polyamide-based, cellulose ethers, polyoxyalkylene class, polyene acids, polyurethanes, Z 150PH, XG 550 or the PVP K120 or two or more mixture; The molecular weight ranges of this raw material water soluble polymer is 200-5,000,000.
2. the preparation method who has funnel-form or step structure super-hydrophilic film according to claim 1 is characterised in that said polyalcohols ethers is selected from polyoxyethylene glycol, methoxy poly (ethylene glycol), polyglycerol or/and W 166.
3. the preparation method who has funnel-form or step structure super-hydrophilic film according to claim 1 is characterised in that said polyamide-based SEPIGEL 305, the sulfonated methyl polyacrylamide of comprising is or/and amine methyl SEPIGEL 305.
4. the preparation method who has funnel-form or step structure super-hydrophilic film according to claim 1 is characterised in that said cellulose ethers is selected from methylcellulose gum, Natvosol, hydroxypropylcellulose, CMC 99.5, Vltra tears, TKK 021 or/and methyl hydroxyethylcellulose.
5. the preparation method who has funnel-form or step structure super-hydrophilic film according to claim 1 is characterised in that said polyoxyalkylene class is selected from polyoxyethylene or/and polyoxytrimethylene.
6. the preparation method who has funnel-form or step structure super-hydrophilic film according to claim 1 is characterised in that said polyene acids is selected from ROHM or/and polymethyl acrylic acid.
7. the preparation method who has funnel-form or step structure super-hydrophilic film according to claim 1 is characterised in that said polyurethanes is selected from cation polyurethane or/and anion polyurethane.
8. the preparation method who has funnel-form or step structure super-hydrophilic film according to claim 1, the impregnating speed that is characterised in that said dipping-pulling method is 10-500cmmin -1, time of immersion is 2-10 minute, pull rate is 10-100cmmin -1
9. the preparation method who has funnel-form or step structure super-hydrophilic film according to claim 1 is characterised in that said spin-coating method for the 50-1000rpm speed of rotation colloidal sol is dripped to above the base material, spares glue with the 1500-8000rpm speed of rotation then.
CN2009101855896A 2009-11-23 2009-11-23 Method for preparing super-hydrophilic film with funnel-shaped or step-shaped structure Expired - Fee Related CN101712536B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1342517A (en) * 2001-08-31 2002-04-03 清华大学 Process for preparing mesoporous TiOw powder and film photocatalyst by sol-gel method
EP1275624A1 (en) * 2001-06-29 2003-01-15 Crystal Systems Inc. Antifogging product, inorganic hydrophilic hard layer forming material and process for producing antifogging lens
CN1696063A (en) * 2004-05-14 2005-11-16 泉耀科技股份有限公司 Method for synthesizing sol of Nano powder of titanium dioxide in visible light type
CN101372394A (en) * 2007-08-21 2009-02-25 黑龙江大学 Method for synthesizing ultra-hydrophilic film using surfactant modified titania

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1275624A1 (en) * 2001-06-29 2003-01-15 Crystal Systems Inc. Antifogging product, inorganic hydrophilic hard layer forming material and process for producing antifogging lens
CN1342517A (en) * 2001-08-31 2002-04-03 清华大学 Process for preparing mesoporous TiOw powder and film photocatalyst by sol-gel method
CN1696063A (en) * 2004-05-14 2005-11-16 泉耀科技股份有限公司 Method for synthesizing sol of Nano powder of titanium dioxide in visible light type
CN101372394A (en) * 2007-08-21 2009-02-25 黑龙江大学 Method for synthesizing ultra-hydrophilic film using surfactant modified titania

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
田清华.PEG对二氧化钛薄膜的微观结构和染色吸附性能的影响.《功能材料》.2004,第35卷(第2期),195-199页. *
陈文梅.溶胶凝胶法制备TiO2多孔纳米薄膜.《武汉工业大学学报》.2000,第22卷(第1期),6-9页. *

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