CN104192901A - Preparation method of titanium oxide film and titanium oxide film - Google Patents
Preparation method of titanium oxide film and titanium oxide film Download PDFInfo
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- CN104192901A CN104192901A CN201410425891.5A CN201410425891A CN104192901A CN 104192901 A CN104192901 A CN 104192901A CN 201410425891 A CN201410425891 A CN 201410425891A CN 104192901 A CN104192901 A CN 104192901A
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Abstract
The invention provides a preparation method of a titanium oxide film and a titanium oxide film. The preparation method comprises the following steps: 1) preparation of titanium oxide precursor; and 2) film coating and after-treatment. The preparation method is simple in preparation technique and can implement large-scale production.
Description
Technical field
The invention belongs to chemical materials synthesis technical field, relate to a kind of preparation method and thin film of titanium oxide of thin film of titanium oxide, the super hydrophilic porous thin film of titanium oxide that relates in particular to a kind of preparation method of super hydrophilic porous thin film of titanium oxide and obtain based on this preparation method.
Background technology
In recent years, there is the semiconductor material of photocatalytic activity because it has broad application prospects and become the focus of research in the field such as photochemical catalysis, opto-electronic conversion, comprise titanium oxide, zinc oxide, zinc sulphide, Cadmium Sulfide and ferric oxide etc.Wherein titanium oxide not only stable chemical nature (acidproof, alkaline-resisting, fast light chemical corrosion) cost low, nontoxic, be easy to film forming and there is good adhesion property with glass surface, and there is unique energy gap (3.2eV), excellent photocatalytic activity, can be carbonic acid gas and water by the mineralization of organic material of difficult degradation, thereby make titanium oxide become the photocatalytic activity inorganic semiconductor material that application prospect is the widest, research is the hottest.Titanium oxide has 3 kinds of crystal formations: rutile, anatase octahedrite and brookite, and wherein Rutile Type is the most stable, and Anatase has the highest photocatalytic activity.
The light-catalyzed reaction that titanium oxide semiconductor material surface causes, all has profound significance for control, automatically cleaning field and the improvement environment of photochemical reaction process.Powdery titania meterial, due to its easy inactivation, the easy fatal shortcoming such as cohesion and difficult recovery, has seriously limited the application development of titania meterial in every field.For overcoming this shortcoming, be carried on suitable baseplate material, preparing film-type titania meterial becomes new study hotspot gradually.
The preparation method of thin film of titanium oxide mainly contains the methods such as sol-gel method, physical vaporous deposition, chemical Vapor deposition process and spraying thermolysis, structure, outward appearance and the performance of different preparation methods on film has different impacts, and every kind of technology of preparing has the relative merits of self, wherein magnetron sputtering method plated film is the technique of comparative maturity, produce thin film of titanium oxide film forming even, hardness is high, the transparency is good, photocatalytic activity is high, but it is high that this method vacuum tightness requires, equipment complexity, investment are larger.Chemical Vapor deposition process can be on production line direct plated film, plated film is even, film material consumption is few, but comparison in equipment complexity, initial cost are high.Sol-gel method masking has advantages of and is much better than other processing methodes, comprising: 1) processing unit simple, without expensive device such as vacuum conditions; 2) can big area prepare film in the substrate of different shapes, differing materials; 3) be easy to quantitative doping, and can effectively control thin film composition and microtexture; 4) low, the applicable big area suitability for industrialized production of coating cost.Therefore select sol-gel method to prepare high-quality thin film of titanium oxide, and the problem that solves the existence such as its product is easy to crack, the transparency is poor have important industrial application value.
For improving the property of some aspect of thin film of titanium oxide material, as reducing film reflection, raising transmitance, raising film anti-fog performance (Superhydrophilic or super-hydrophobicity), increase light utilization efficiency, specific surface area etc., the design of membrane structure (as vesicular structure) and preparation have become the up-to-date focus of research thin film of titanium oxide.Conventionally adopt template (first designing and prepare the template of various patterns), etching method, electrochemical process etc. effectively to transform the surface tissue of film, to reach the requirement that improves film performance.But these methods on the one hand more complicated, length consuming time, repeatability and homogeneity are poor; On the other hand, these methods are only applicable to prepare the thin film of titanium oxide of smaller area, are not suitable for the production of big area thin film of titanium oxide in enormous quantities.Therefore, how simple and effectively prepare and there is thin film of titanium oxide special appearance and that can big area produce, become main starting point of the present invention.
Summary of the invention
In order to solve the above-mentioned technical problem existing in background technology, the invention provides preparation method and the thin film of titanium oxide of simple and the thin film of titanium oxide that can large-scale production of a kind of preparation technology.
Technical solution of the present invention is: a kind of preparation method of thin film of titanium oxide is provided, and its special character is: said method comprising the steps of:
1) preparation of titania precursor thing:
1.1) diethanolamine is dropwise joined in the ethanol in stirring, 40 DEG C of lower seals stir 10-20 minute to evenly mixing, and obtain solution A;
1.2) butyl (tetra) titanate is dropwise joined to step 1.1) in the solution A that obtains, continue to stir 100-150 minute at 40 DEG C of lower seals, obtain solution B;
1.3) to step 1.2) slowly drip deionized water in the solution B that obtains, 30-40 minute is stirred in sealing, obtains light yellow transparent precursor solution C;
1.4) to step 1.3) in to add weight percent in the light yellow transparent precursor solution C that obtains be the polyvinylpyrrolidone of 0-6.0%, sealing is stirred to dissolves completely, static ageing 5 to 20 hours, obtains solution D; Described solution D is titania precursor thing; The molecular weight Mw of described polyvinylpyrrolidone is 55000 dalton;
2) film and aftertreatment:
2.1) substrate is cleaned 5 minutes respectively with acetone, ethanol and deionized water successively under ultrasonication;
2.2) by step 1) preparation-obtained titania precursor thing adopts rotation, printing or method of pulling up in step 2.1) in the substrate obtaining of processing carry out surface coatings, obtain being coated with membrane sample;
2.3) by step 2.2) the painting membrane sample that obtains dries at 100 DEG C, 15-30 minute;
2.4) by step 2.3) in sample after drying take out heat-treat two hours in 550 DEG C of pipe type stoves or retort furnace after, cool to room temperature, obtains thin film of titanium oxide.
Above-mentioned steps 1.1) in, the mol ratio of diethanolamine and ethanol is 1:31.2.
Above-mentioned steps 1.2) in, the mol ratio of butyl (tetra) titanate and diethanolamine is 1:1.62.
Above-mentioned steps 1.3) in, the mol ratio of butyl (tetra) titanate and deionized water is 1:1.26.
The thin film of titanium oxide that a kind of preparation method based on thin film of titanium oxide as above prepares.
Main innovate point of the present invention and advantage comprise:
The present invention has used polyvinylpyrrolidone to prepare ordered porous thin film of titanium oxide as pore-creating agent innovatively, rarely has in the literature report, belongs to originality invention.Be distributed in titania precursor liquid system because polyvinylpyrrolidone can be the reticulated structure interweaving, can effectively improve the film forming properties of colloidal sol, prevent film cracking; And the hole that polyvinylpyrrolidone pyrolytic decomposition is formed is uniformly distributed.Prepared film integral surfacing flawless, porous membrane aperture and even density, hole dimension and distribution density can regulate (as more in polyvinylpyrrolidone addition according to the addition of polyvinylpyrrolidone, aperture is larger, and hole density is also large).The present invention, by adjusting the proportioning of the each material of precursor liquid, has obtained forming best proportioning and the condition of the thin film of titanium oxide of high permeability.In addition, for obtaining high transmission rate, super hydrophilic porous film, adjustment aperture and hole density are most important, except polyvinylpyrrolidone, the present invention has also used polyvinyl alcohol, by the two ratio of suitable adjusting, to effectively control aperture and hole density, reach best result of use.Vesicular structure can allow light multiple reflections or refraction make full use of in hole, thereby has improved sunlight utilization ratio, and has increased to a great extent the transmitance of film integral.Film, under illumination and under lucifuge condition, all presents super hydrophily, has good anti-fogging ability, as is applied to glass for vehicle window or rear vision mirror, can greatly improve winter driving person's safety coefficient; Thin film composition is mainly the anatase octahedrite of highlight catalytic active, and vesicular structure greatly increased specific surface area, thereby photochemical catalysis is more effective.Porous surface structure can reduce the adsorptive power of dust and film surface by reducing contact area, is very easily washed away by surperficial moisture film (as rainwater), thereby reaches antidusting to a certain extent, automatically cleaning object; This preparation method cost low (the few and film forming of raw material consumption and equipment cost are low), technique environmental protection (advantages of nontoxic raw materials or micro-poison; production process is discharged without harmful waste liquid); the more important thing is be produced on a large scale (technique is simple, and equipment requirements is low).
The present invention is the preparation method who has developed a kind of simple, effective novel super hydrophilic porous thin film of titanium oxide; this synthetic method and comparing of reporting, have consuming time short, cost is low, equipment is simple, productive rate is high and pattern is controlled and the advantage such as easy large-scale production.Prepared nano-porous film hole density is adjustable, hole dimension also can regulate between 50 to 200 nanometers, this structure has not only increased specific surface area effectively, increase transmittance and the light utilising efficiency of thin film of titanium oxide, and reduced to a certain extent the adsorptive power of subparticle to film surface.In addition greatly improved, the wetting ability of titanium oxide by wicking action.Super hydrophilic porous thin film of titanium oxide provided by the present invention can be widely used in the fields such as self-cleaning glass, photochemical catalysis, photoelectric commutator and various sensor and solar cell.
Brief description of the drawings
Fig. 1 is at the scanning electron microscope (SEM) photograph that adds the nanometer porous titanium oxide film preparing after the polyvinylpyrrolidone of different mass mark based on preparation method provided by the present invention;
Fig. 2 is the method flow schematic diagram of preparing porous titania thin films provided by the present invention;
Fig. 3 be the porous titania thin films for preparing based on preparation method provided by the present invention on light path affect schematic diagram with and corresponding film at the transmittance curve in ultraviolet-visible light region;
Fig. 4 be the porous titania thin films for preparing based on preparation method provided by the present invention under light and under lucifuge condition with the contact angle optical microscopy map of water;
Fig. 5 is the X-ray diffractogram of the porous titania thin films for preparing based on preparation method provided by the present invention;
Fig. 6 is the porous titania thin films for preparing based on preparation method provided by the present invention resistance schematic diagram and the actual contrast experiment's photo to dust.
Embodiment
The invention provides a kind of simple, fast and the chemical preparation process of the cheap novel nano porous titania thin films structured material of expense.
Specific as follows:
The preparation (as shown in Figure 2) of the first step, titania precursor thing
1) diethanolamine is dropwise joined in the ethanol in stirring, mol ratio is diethanolamine: ethanol=1:31.2, and 40 DEG C of lower seals stir 10-20 minute, obtain solution A.
2) butyl (tetra) titanate is dropwise joined in above-mentioned solution, mol ratio is butyl (tetra) titanate: diethanolamine=1:1.62, continues 40 DEG C of lower seals and stirs 100-150 minute, obtains solution B.
3) in above-mentioned system, slowly drip deionized water, mol ratio is butyl (tetra) titanate: water=1:1.26, and sealing stir about 30-40 minute, obtains light yellow transparent precursor solution C.
4) to the polyvinylpyrrolidone (molecular weight Mw=55000) that adds certain mass mark in light yellow transparent precursor obtained above, sealing is stirred to dissolves completely, and static ageing 5 to 20 hours, obtains solution D.
Second step, film and aftertreatment
5) substrate is cleaned each 5 minutes with acetone, ethanol, deionized water successively under ultrasonication.
6) adopt rotation, printing or method of pulling up in substrate surface film the titania precursor thing preparing.
7) at approximately 100 DEG C, dry 15-30 minute by being coated with membrane sample in 6.
8) sample of oven dry is heat-treated to two hours in 550 DEG C of pipe type stoves or retort furnace after take out, cool to room temperature.
The present invention, when above-mentioned preparation method is provided, also provides a kind of thin film of titanium oxide preparing based on preparation method described above.
Referring to Fig. 1, under the add-on of different polyvinylpyrrolidones, ageing 8 hours, 5000 revs/min of lower spin coatings 1 minute, and the scanning electron microscope (SEM) photograph of the porous titania thin films that obtains after two hours of 550 DEG C of thermal treatment: wherein, (A) 0.5wt% polyvinylpyrrolidone, hole mean sizes is about 70 nanometers; (B) 1.0wt% polyvinylpyrrolidone, hole mean sizes is about 100 nanometers; (C) 1.5wt% polyvinylpyrrolidone, hole mean sizes is about 125 nanometers; (D) 2.0wt% polyvinylpyrrolidone, hole mean sizes is about 150 nanometers.
Referring to Fig. 2, prepare the method flow schematic diagram (lexicographic order and synthesis step are same) of porous titania thin films: first diethanolamine is dropwise joined in ethanol, 40 DEG C of lower seals stir and within 10-20 minute, obtain solution A.Again butyl (tetra) titanate is dropwise joined in solution A, continue 40 DEG C of lower seals and stir 100-150 minute, obtain solution B.Then in solution B, slowly drip deionized water, sealing is stirred after 30-40 minute and is obtained solution C.In the most backward solution C, add polyvinylpyrrolidone (Mw=55000), sealing seals static ageing after being stirred to and dissolving completely, obtains solution D.To after solution D film thermal treatment, obtain porous titania thin films.
Referring to Fig. 3, (A) porous titania thin films affects schematic diagram to light path: the light entering in hole increases transmitance by hole inwall multiple reflections and refraction; (B) thin film of titanium oxide of atresia and by adding the porous titania thin films of different hole dimensions that the polyvinylpyrrolidones of different amounts obtain and density at the transmittance curve in ultraviolet-visible light region: porous improves 15-20% than atresia thin film of titanium oxide in the transmitance in ultraviolet-visible light region; (C) atresia, porous titania thin films sample photo: 1. titanium oxide nonporous film cover glass, be 2. mixed with 1.0wt% polyvinylpyrrolidone porous titania thin films cover glass.
Referring to Fig. 4, porous titania thin films under illumination and under lucifuge condition with the optical microscopy map of the contact angle of water, contact angle is all tending towards zero degree, is super-hydrophilic film structure.
Referring to Fig. 5, the X-ray diffractogram of porous titania thin films: main component is the Anatase with high light catalytic activity, and rutile composition accounts for small part.
Referring to Fig. 6, resistance schematic diagram and the actual contrast experiment photo of porous titania thin films to dust: the photo (dust small part is residual) when schematic diagram when water droplet is flow through on the common substrate surface of (A) having adsorbed dust and the surface of ordinary glass of (B) having adsorbed dust flow through 0.5 ml water; (C) photo (the basic noresidue of dust) when 0.5 ml water is flow through on schematic diagram when water droplet is flow through on the porous titania thin films surface of having adsorbed dust and the porous titania thin films surface of (D) having adsorbed dust.
Below, in connection with embodiment, method provided by the present invention is elaborated:
1,3g diethanolamine is dropwise joined in the ethanol of 41 milliliters in stirring, 40 DEG C of lower seals stir 10 minutes, obtain solution A.6g butyl (tetra) titanate is dropwise joined in solution A, continue 40 DEG C of lower seals and stir 120 minutes, obtain solution B.In solution B, slowly drip 0.4 ml deionized water again, sealing is stirred 30 minutes, obtains light yellow transparent liquid, is solution C.In the most backward solution C, add 0.5g polyvinylpyrrolidone (Mw=55000), sealing seals static ageing 8 hours after being stirred to and dissolving completely, obtains solution D (approximately 50 milliliters of cumulative volumes).
2, the sheet glass of 2.5cm*2.5cm is cleaned after each 5 minutes with acetone, ethanol, deionized water successively under ultrasound condition, get approximately 10 microlitre solution D and drip in sheet glass central authorities, use spin coating instrument 5000 revs/min of lower spin coatings 1 minute.Sample good spin coating is dried in 100 DEG C of baking ovens, after about 15 minutes, transfer to thermal treatment under 550 DEG C of retort furnaces and take out after two hours, be cooled to room temperature for subsequent use.
The preparation-obtained this super hydrophilic porous thin film of titanium oxide material of the present invention can be mainly used in following several field:
1. self-cleaning glass: super hydrophilic porous thin film of titanium oxide on glass can be effectively anti-fog (have light unglazed under have Superhydrophilic), oil rub resistance (degradation of organic substances under light).This type of vesicular structure has not only increased reaction area greatly, improve the transmitance of film, and realized effective utilization of light by multipath reflection utilization, and reduce adsorptive power by reducing with the contact area of particulate state dust, reach certain antidusting.Therefore this super hydrophilic porous thin film of titanium oxide material can improve anti-fog, oil rub resistance, the antidusting ability of glass effectively.
2. sterilization and disinfection product: under sunlight, because vesicular structure has greatly increased surface reaction area, can constantly decompose efficiently the obnoxious flavoures such as formaldehyde that organic coating volatilizes, benzene, ammonia; The smell that various bacteriums in room air and virus and smoking etc. bring of killing and degrade, purifies air effectively, reduces and pollutes.Can be used for medical field and Green Home product product, realize the cleaning action to room air and tap water.
3. photocatalyst material: titanium oxide porous membrane, in photocatalysis field, has greatly increased reaction area, thereby has greatly improved light utilising efficiency to a certain extent; And this type of mould material is constructed at substrate surfaces such as glass, can effectively overcome nano-powder and be difficult to reclaim and can cause the drawback of secondary pollution, thereby reduce costs, be beneficial to environmental protection.
4. solar cell: titanium oxide porous membrane, by electrode of solar battery plate being reduced to reflection, increasing transmission, can effectively reduce the reflection loss of optical radiation at battery surface, improves light utilization efficiency, thereby improves solar cell properties.
Claims (5)
1. a preparation method for thin film of titanium oxide, is characterized in that: said method comprising the steps of:
1) preparation of titania precursor thing:
1.1) diethanolamine is dropwise joined in the ethanol in stirring, 40 DEG C of lower seal stir abouts obtain solution A to mixing in 10-20 minute;
1.2) butyl (tetra) titanate is dropwise joined to step 1.1) in the solution A that obtains, continue to stir 100-150 minute at 40 DEG C of lower seals, obtain solution B;
1.3) to step 1.2) slowly drip deionized water in the solution B that obtains, 30-40 minute is stirred in sealing, obtains light yellow transparent precursor solution C;
1.4) to step 1.3) in to add the white proportion by subtraction of weight in the light yellow transparent precursor solution C that obtains be the polyvinylpyrrolidone of 0-6.0%, sealing is stirred to dissolves completely, static ageing 5 to 20 hours, obtains solution D; Described solution D is titania precursor thing; The molecular weight Mw of described polyvinylpyrrolidone is 55000 dalton;
2) film and aftertreatment:
2.1) substrate is cleaned 5 minutes respectively with acetone, ethanol and deionized water successively under ultrasonication;
2.2) by step 1) preparation-obtained titania precursor thing adopts rotation, printing or method of pulling up in step 2.1) in the substrate obtaining of processing carry out surface coatings, obtain being coated with membrane sample;
2.3) by step 2.2) the painting membrane sample that obtains dries at 100 DEG C, 15-30 minute;
2.4) by step 2.3) in sample after drying take out heat-treat two hours in 550 DEG C of pipe type stoves or retort furnace after, cool to room temperature, obtains thin film of titanium oxide.
2. the preparation method of thin film of titanium oxide according to claim 1, is characterized in that: described step 1.1) in, the mol ratio of diethanolamine and ethanol is 1:31.2.
3. the preparation method of thin film of titanium oxide according to claim 2, is characterized in that: described step 1.2) in, the mol ratio of butyl (tetra) titanate and diethanolamine is 1:1.62.
4. the preparation method of thin film of titanium oxide according to claim 3, is characterized in that: described step 1.3) in, the mol ratio of butyl (tetra) titanate and deionized water is 1:1.26.
5. the thin film of titanium oxide that the preparation method based on thin film of titanium oxide as claimed in claim 4 prepares.
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| CN107720818A (en) * | 2017-10-24 | 2018-02-23 | 宝鸡市铭坤有色金属有限公司 | A kind of preparation method of titanium deoxid film |
| CN109987856A (en) * | 2019-03-21 | 2019-07-09 | 天津城建大学 | One kind having hydrophilic TiO2The preparation method of/FeOOH laminated film |
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Application publication date: 20141210 |