CN101428852A - Method for producing ultra-dewatering titanium dioxide film with electrostatic spinning - Google Patents
Method for producing ultra-dewatering titanium dioxide film with electrostatic spinning Download PDFInfo
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- CN101428852A CN101428852A CNA2008102392628A CN200810239262A CN101428852A CN 101428852 A CN101428852 A CN 101428852A CN A2008102392628 A CNA2008102392628 A CN A2008102392628A CN 200810239262 A CN200810239262 A CN 200810239262A CN 101428852 A CN101428852 A CN 101428852A
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- polyvinylpyrrolidone
- nethike embrane
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- nano fiber
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Abstract
The invention relates to a method for preparing an ultrahydrophobic TiO2 film by electrostatic spinning. The method comprises the following steps: preparing coarse TiO2/PVP composite nanometer fiber film by electrostatic spinning; co-calcining the composite nanometer fiber film with a low-surface-energy material (such as polymethylsiloxane); and uniformly depositing a nanometer granular low-surface-energy material on the surface of the calcined TiO2 fiber film to obtain the composite nanometer fiber film, that is, the ultrahydrophobic TiO2 film, wherein, the film has a water contact angle of 150.4 to 154.5 DEG and a rolling angle less than 5 DEG.. The ultrahydrophobic TiO2 film can be used for the fields of waterproof fabrics, loss-free liquid transmission, microfluids, etc. The method can be achieved by simple equipment, and can be used for preparing large-area ultrahydrophobic TiO2 films. The adoption of the co-calcining process of the low-surface-energy material can obviate the hydrophobization step of the calcined TiO2.
Description
Technical field
The invention belongs to and prepare super dewatering titanium oxide (TiO in the chemical field
2) method of film, particularly electrostatic spinning prepares super-hydrophobic TiO
2The method of film.
Background technology
Wetting property is one of critical nature of solid surface, by contact angle (CA) sign of solid-liquid interface.The wetting property of solid surface is mainly determined jointly by its surperficial chemical constitution and structure and morphology.The free energy and the roughness that change solid surface all can change wetting property.In recent years, with the CA of water greater than 150 ° and roll angle less than 10 ° super hydrophobic material owing to, caused that people study interest greatly in field application prospects such as microfluid, bioanalysiss.Be subjected to the inspiration of lotus leaf automatically cleaning effect, people have prepared a series of bionical super hydrophobic surface.Studies show that super hydrophobic surface can obtain by two approach: the one, uneven surface modify the low surface energy material (Chen Su, Chen Li, Lu Zhen, Huang Xu, a kind of method of preparing super-hydrophobic silica by one-step process, CN101249963); The 2nd, make up on hydrophobic material surface coarse structure (Li Xinhong, Ma Yongmei, Wang Fosong, Jiang Lei, Zhao Hongzhi, super-hydrophobic cellular PVC film and preparation method thereof, CN1621434).Up to now, people have proposed many methods that prepare uneven surface, such as phase separation method (Han Zhewen, Wang Kang, the little reason of grain, Li Xinxin, Wei Haiyang, a kind of super hydrophobic material with roughened surface, CN101092289), etching method (Wu Xuedong, Zheng Lijun, Wu's dawn, a kind of preparation method of super-hydrophobic superfine structure surface, CN1613565), the template stamped method, plasma method (Liu Wei, Li Yan, He Tao, cross triumphant, Wang Dexin, Guo Ying, Yang Ping, Zhang Jing, super-hydrophobicity and Superhydrophilic titanium deoxid film etc. the prepared ex vivo method, CN101225510), and electrochemical deposition method (Zhou Zhiguo, Fu You, Huang Chunhui, Song Qunliang, super dewatering titanium oxide membrane and preparation method thereof, CN1654336) or the like.These methods can large-area preparation super hydrophobic surface.River thunder research group is a raw material with the polystyrene of cheapness, adopts simple electrostatic spinning technique, has prepared the based superhydrophobic thin films with porous microsphere and nanofiber composite structure.This method is considered to be a a progressive step aspect the promotion preparation big area super hydrophobic material.Because TiO
2Light, heat and chemical stability and biocompatibility, be people's research focus in theory research and industrial applicability field always.The TiO that preparation has special surface character
2Material helps expanding TiO
2At self-cleaning surface, solar cell, the utilization of aspects such as bioanalysis.For wetting ability TiO
2Material has hydrothermal synthesis method, and etching method and sol-gel method etc.Though hydrothermal synthesis method can the super-hydrophobic TiO of step preparation
2Material (Xinjian Feng, Jin Zhai, Lei Jiang, The fabrication andswitchable superhydrophobilicity of TiO
2Nanorod films, Angew.Chem.Int.Ed.2005,44,5115～5118), but the synthetic method complexity is difficult to large-area preparation.Though etching method and sol-gel method method are simple, are easy to large-area preparation, all be to adopt calcining to obtain TiO
2After modify (Lin Changjian, Lai Yuekun, Sun Lan, the preparation method of the film of Nano tube array of titanium dioxide of super amphiphilic and super-hydrophobicity, CN1760113 with expensive low surface energy material again; Nakajima, A., Fujishima, A., Hashimoto, K., Watanabe, T., Preparation of transparent superhydrophobicboehmite and silica films by sublimation of aluminum acetylacetonate.Adv.Mater.1999,11,1365～1368).The present invention uses electrostatic spinning technique to construct uneven surface, re-uses cheap low surface energy material such as polymethyl siloxane and modifies the preparation roll angle synchronously less than 5 ° super-hydrophobic TiO in calcination process
2The surface.
Summary of the invention
The present invention is directed to the super-hydrophobic TiO of existing preparation
2The weak point of membrane method has proposed a kind of electrostatic spinning and has prepared super-hydrophobic TiO
2The method of film.
The method of producing ultra-dewatering titanium dioxide film with electrostatic spinning of the present invention may further comprise the steps:
(1) preparation of composite membrane
With polyvinylpyrrolidone (poly (vinyl pyrrolidone), PVP, Mw=900,000-1,300,000, Acros) and tetrabutyl titanate (Ti (OBu)
4) (the solvent volume ratio in the mixed solvent of v/v=4～10:1), is mixed with the precursor solution that contains 3～11wt.% (being preferably 4wt.%) polyvinylpyrrolidone and 10～40wt.% (being preferably 20wt.%) tetrabutyl titanate to be dissolved in ethanol and acetic acid; This precursor solution placed be equipped with the feeding device that diameter is the electrostatic spinning apparatus of 0.32～1.43mm (preferred diameter be 0.43mm) syringe needle, the feed speed of stoste is 10ml/h, adopts the operating voltage intensity (voltage strength=operating voltage/receiving range) of 1.5～2.5kV/cm (preferred 1.8kV/cm) to carry out electrostatic spinning; On the substrate of glass that moves, collect and obtain coarse polyvinylpyrrolidone and titanium dioxide (PVP/TiO
2) the composite nano fiber nethike embrane;
(2) calcining of composite membrane
On the nethike embrane of the substrate of glass of load polyvinylpyrrolidone that step (1) obtains and titanium dioxide composite nano fiber nethike embrane, the polyvinylpyrrolidone that obtains by every square decimeter of step (1) and the amount of titanium dioxide composite nano fiber nethike embrane, evenly apply 0.1～1g low surface energy material, then this polyvinylpyrrolidone is placed retort furnace (the Nabertherm LH15-13 of temperature programming with titanium dioxide composite nano fiber nethike embrane and this substrate of glass, Germany) in, rise to 450 ℃ with the heat-up rate of 1.5～3 ℃/min; Under this temperature, continue calcining 3～5 hours then, remove polyvinylpyrrolidone, TiO after calcining
2Fiber nethike embrane surface is deposit nanometric particles shape low surface energy material equably, prepares ultra-dewatering titanium dioxide film.
Described low surface energy material is a kind of in polymethyl siloxane (Mw=4,000～16,000), silicone oil, silicon fluoride or the depleted silicon rubber.
Substrate of glass described in the step (1) is the sheet glass of parcel one deck conduction Al paper tinsel; This sheet glass places on the running gear, can move around to collect PVP/TiO
2The composite nano fiber nethike embrane.
TiO described in the step (1)
2/ PVP composite nano fiber nethike embrane is to be that (preferred diameter is the composite nano fiber nethike embrane that 50～490nm) fibers weave formation mutually to 86～2700nm by diameter.
Described super-hydrophobic TiO
2The contact angle of film and water is 150.4～154.5 °, and roll angle is less than 5 °, and preferred roll angle is 2.1 °.
The present invention prepares coarse TiO by simple electrostatic spinning technique earlier
2/ PVP composite nano fiber nethike embrane; With the common calcining of composite nano fiber nethike embrane and low surface energy material (as polymethyl siloxane etc.), obtain the super-hydrophobic TiO of surface deposition nano particle (surface particles mainly is the degradation production of polymethyl siloxane, contains the hydrophobic substance of type siloxane) then
2Film.Super-hydrophobic TiO of the present invention
2Mould material can be designed to apply to waterproof fabric, free of losses transport of liquid, fields such as microfluid.The inventive method and equipment are simple, but the super-hydrophobic TiO of large-area preparation
2Film.
Method of the present invention compared with prior art excellent results is as follows:
1) with existing phase separation method, etching method, the template stamped method, electrochemical deposition methods etc. are compared, and the equipment simple cheap can the super-hydrophobic TiO of large-area preparation
2Film.
2) adopt cheap low surface energy material (as polymethyl siloxane etc.) and TiO
2/ PVP composite nano fiber nethike embrane is calcined jointly, does not need the TiO after the calcining
2Film is handled carrying out hydrophobization, and the contact angle that just can obtain with water is 150.4～154.5 °, and roll angle is less than 5 °, preferably the super-hydrophobic TiO of 2.1 ° of roll angles
2Film.
Description of drawings
PVP/TiO before the calcining of preparation in Fig. 1 a. embodiment of the invention 1
2The XPS spectrum figure of composite membrane.
The super-hydrophobic TiO that obtains after the calcining of preparation in Fig. 1 b. embodiment of the invention 1
2The XPS spectrum figure of film.
Fig. 2. the SEM photo in the embodiment of the invention 1 before and after the calcining of the composite membrane of preparation; Wherein:
PVP/TiO before a, the b calcining
2Composite cellulosic membrane; C, the d calcining super-hydrophobic TiO in back
2Film.
Fig. 3. the super-hydrophobic TiO of preparation in the embodiment of the invention 1
2The contact angle of film.
Fig. 4. the super-hydrophobic TiO of preparation in the embodiment of the invention 1
2The roll angle of film.
Embodiment
The present invention is described further below in conjunction with embodiment.
Sample topography adopts field emission scanning electron microscope (the Japanese JEOL 6700F FE-SEM of company) to characterize.The surface composition of film adopts x X-ray photoelectron spectroscopy X (XPS) test.Utilize contact angle measurement (the German Dataphysics OCA20 of company) at room temperature to carry out contact angle and roll angle and measure, used water droplet is 3 μ L, measures at 5 different positionss of sample, averages.Used substrate of glass is the sheet glass of parcel one deck conduction Al paper tinsel.
Embodiment 1.
With polyvinylpyrrolidone (poly (vinyl pyrrolidone), PVP, Mw=1,300,000, Acros) and tetrabutyl titanate (Ti (OBu)
4) (ethanol/acetate solvate volume ratio in mixed solvent v/v=4:1), is mixed with the precursor solution that contains 4wt.% polyvinylpyrrolidone and 20wt.% tetrabutyl titanate to be dissolved in ethanol and acetic acid; This precursor solution placed be equipped with the electrostatic spinning apparatus feeding device that diameter is the 0.43mm syringe needle, the feed speed of stoste is 10ml/h, adopts the operating voltage intensity (voltage strength=operating voltage/receiving range) of 1.8kV/cm to carry out electrostatic spinning under 25 ℃ of room temperatures; At distance syringe needle 10cm place, collect coarse PVP/TiO on the substrate of glass that moves
2The composite nano fiber nethike embrane;
At the above-mentioned PVP/TiO of load
2On the nethike embrane of the substrate of glass of composite nano fiber nethike embrane, evenly apply polymethyl siloxane (Mw=4,000, coated weight is every square decimeter of PVP/TiO
2The composite nano fiber nethike embrane applies 1g); Then with PVP/TiO
2Composite nano fiber nethike embrane and substrate of glass place temperature programming retort furnace (Nabertherm LH15-13, Germany) in, rise to 450 ℃ with the heat-up rate of 1.5/min; Under this temperature, continue calcining 3 hours then, remove polyvinylpyrrolidone, prepare super-hydrophobic TiO
2Film.
Prepared PVP/TiO
2Composite nano fiber nethike embrane and super-hydrophobic TiO
2The XPS figure of film is respectively shown in Fig. 1 a and 1b.By Fig. 1 b as can be seen, fiber surface N element fignal center disappears, and fiber surface is mainly by C, O, and Ti and Si are elementary composition.This is explanation just, and calcination process has been removed PVP, has prepared the surperficial super-hydrophobic TiO that contains Si and C
2Film.Therefore, we calcine polymethyl siloxane and PVP/TiO synchronously by electrostatic spinning
2The method of composite membrane has prepared the super-hydrophobic TiO that polymethyl siloxane pyrolytic decomposition thing is modified
2Film.
Prepared PVP/TiO
2Composite nano fiber nethike embrane and super-hydrophobic TiO
2The SEM figure of film is respectively as Fig. 2 a, and b and 2c are shown in the d.The PVP/TiO of Fig. 2 a and the preparation of 2b explanation electrostatic spinning
2The composite nano fiber nethike embrane has the structure of fibrous web-like.Can not see tangible fiber net structure among Fig. 2 c, only visible particulate state uneven surface.SEM Fig. 2 d after Fig. 2 c amplifies clearly illustrates that then bottom is TiO
2Fibrous reticular structure, upper strata are that the spherical particle accumulation of particle diameter 0.023～1.7 μ m forms, and form the particulate state uneven surface.The result shows, adopts electrostatic spinning technique can prepare the nanofiber nethike embrane in substrate.Sintering process is not destroyed fibrous reticular structure, and while roughening web surface.
To TiO
2The surface wettability characterization result of fiber nethike embrane as shown in Figure 3 and Figure 4.Fig. 3 is the TiO of water droplet at the finishing polydimethylsiloxane
2The photo on nanofiber nethike embrane surface shows that contact angle is 154.5 ± 1.7 °, shows significant superhydrophobic characteristic.The roll angle that roll angle table with test results open fire drops on the nanofiber nethike embrane is 2.1 ° (Fig. 4), shows the super-hydrophobicity of low viscous force.Like this, we have just prepared and have had super-hydrophobicity, with the CA of water be 154.5 °, roll angle is 2.1 ° a super hydrophobic surface.
Embodiment 2.
With polyvinylpyrrolidone (poly (vinyl pyrrolidone), PVP, Mw=1,300,000, Acros) and tetrabutyl titanate (Ti (OBu)
4) (the solvent volume ratio in mixed solvent v:v=10:1), is mixed with the precursor solution that contains 3wt.% polyvinylpyrrolidone and 10wt.% tetrabutyl titanate to be dissolved in ethanol and acetic acid; This precursor solution placed be equipped with the electrostatic spinning apparatus feeding device that diameter is the 0.32mm syringe needle, the feed speed of stoste is 10ml/h, adopts the operating voltage intensity (voltage strength=operating voltage/receiving range) of 1.5～2.5kV/cm (preferred 1.8kV/cm) to carry out electrostatic spinning; On the substrate of glass that moves, collect and obtain coarse PVP/TiO
2The composite nano fiber nethike embrane; This composite nano fiber nethike embrane has the structure of fibrous web-like;
At the above-mentioned PVP/TiO of load
2On the nethike embrane of the substrate of glass of composite nano fiber nethike embrane, evenly apply polymethyl siloxane (Mw=16,000, coated weight is every square decimeter of PVP/TiO
2The composite nano fiber nethike embrane applies 0.1g); Then with PVP/TiO
2Composite nano fiber nethike embrane and substrate of glass place temperature programming retort furnace (Nabertherm LH15-13, Germany) in, rise to 450 ℃ with the heat-up rate of 3 ℃/min; Under this temperature, continue calcining 5 hours then, remove polyvinylpyrrolidone, prepare super-hydrophobic TiO
2Film.This super-hydrophobic TiO
2The CA of film and water is 150.5 °, and roll angle is 3.5 °.
Embodiment 3.
With polyvinylpyrrolidone (poly (vinyl pyrrolidone), PVP, Mw=1,300,000, Acros) and tetrabutyl titanate (Ti (OBu)
4) (the solvent volume ratio in mixed solvent v/v=10:1), is mixed with the precursor solution that contains 11wt.% polyvinylpyrrolidone and 40wt.% tetrabutyl titanate to be dissolved in ethanol and acetic acid; This precursor solution placed be equipped with the electrostatic spinning apparatus feeding device that diameter is the 1.43mm syringe needle, the feed speed of stoste is 10ml/h, adopts the operating voltage intensity (voltage strength=operating voltage/receiving range) of 2.5kV/cm to carry out electrostatic spinning; On the substrate of glass that moves, collect and obtain coarse PVP/TiO
2The composite nano fiber nethike embrane; This composite nano fiber nethike embrane has the structure of fibrous web-like;
At the above-mentioned PVP/TiO of load
2On the nethike embrane of the substrate of glass of composite nano fiber nethike embrane, evenly apply polymethyl siloxane (Mw=12,000, coated weight is every square decimeter of PVP/TiO
2The composite nano fiber nethike embrane applies 0.8g); Then with PVP/TiO
2The composite nano fiber nethike embrane with substrate of glass place temperature programming retort furnace (Nabertherm LH15-13, Germany) in, rise to 450 ℃ with the heat-up rate of 2 ℃/min; Under this temperature, continue calcining 4 hours then, remove polyvinylpyrrolidone, prepare super-hydrophobic TiO
2Film.This super-hydrophobic TiO
2The CA of film and water is 152.1 °, and roll angle is 3.0 °.
Embodiment 4.
With polyvinylpyrrolidone (poly (vinyl pyrrolidone), PVP, Mw=900,000, Acros) and tetrabutyl titanate (Ti (OBu)
4) (ethanol/acetate solvate volume ratio in mixed solvent v/v=4:1), is mixed with the precursor solution that contains 9wt.% polyvinylpyrrolidone and 30wt.% tetrabutyl titanate to be dissolved in ethanol and acetic acid; This precursor solution placed be equipped with the electrostatic spinning apparatus feeding device that diameter is the 0.56mm syringe needle, the feed speed of stoste is 10ml/h, adopts the operating voltage intensity (voltage strength=operating voltage/receiving range) of 1.8kV/cm to carry out electrostatic spinning under 25 ℃ of room temperatures; At distance syringe needle 10cm place, collect coarse PVP/TiO on the substrate of glass that moves
2The composite nano fiber nethike embrane; This composite nano fiber nethike embrane has the structure of fibrous web-like;
At the above-mentioned PVP/TiO of load
2On the nethike embrane of the substrate of glass of composite nano fiber nethike embrane, evenly apply silicone oil (Mw=12,000, coated weight is every square decimeter of PVP/TiO
2The composite nano fiber nethike embrane applies 1g); Then with PVP/TiO
2Composite nano fiber nethike embrane and substrate of glass place temperature programming retort furnace (Nabertherm LH15-13, Germany) in, rise to 450 ℃ with the heat-up rate of 1.5/min; Under this temperature, continue calcining 3 hours then, remove polyvinylpyrrolidone, prepare super-hydrophobic TiO
2Film.This super-hydrophobic TiO
2The CA of film and water is 150.4 °, and roll angle is 2.6 °.
Claims (10)
1. the method for a producing ultra-dewatering titanium dioxide film with electrostatic spinning is characterized in that, this method may further comprise the steps:
(1) preparation of composite membrane
Polyvinylpyrrolidone and tetrabutyl titanate are dissolved in the mixed solvent of ethanol and acetic acid, are mixed with the precursor solution that contains 3～11wt.% polyvinylpyrrolidone and 10～40wt.% tetrabutyl titanate; This precursor solution placed be equipped with the feeding device that diameter is the electrostatic spinning apparatus of 0.32～1.43mm syringe needle, adopt the operating voltage intensity of 1.5～2.5kV/cm to carry out electrostatic spinning; On the substrate of glass that moves, collect and obtain coarse polyvinylpyrrolidone and titanium dioxide composite nano fiber nethike embrane;
(2) calcining of composite membrane
On the nethike embrane of the substrate of glass of load polyvinylpyrrolidone that step (1) obtains and titanium dioxide composite nano fiber nethike embrane, the polyvinylpyrrolidone that obtains by every square decimeter of step (1) and the amount of titanium dioxide composite nano fiber nethike embrane evenly apply 0.1～1g low surface energy material; Then this polyvinylpyrrolidone is placed retort furnace with titanium dioxide composite nano fiber nethike embrane with substrate of glass, rise to 450 ℃ with the heat-up rate of 1.5～3 ℃/min; Under this temperature, continue calcining 3～5 hours then, remove polyvinylpyrrolidone, prepare ultra-dewatering titanium dioxide film;
Described low surface energy material is a kind of in polymethyl siloxane, silicone oil, silicon fluoride or the depleted silicon rubber.
2. method according to claim 1 is characterized in that: contain the 4wt.% polyvinylpyrrolidone in the described precursor solution.
3. method according to claim 1 is characterized in that: described polyvinylpyrrolidone and titanium dioxide composite nano fiber nethike embrane are to be that 86～2700nm fiber weaves the composite nano fiber nethike embrane that constitutes mutually by diameter.
4. according to claim 1,2 or 3 described methods, it is characterized in that: the Mw=900 of described polyvinylpyrrolidone, 000～1,300,000.
5. method according to claim 1 and 2 is characterized in that: contain the 20wt.% tetrabutyl titanate in the described precursor solution.
6. method according to claim 1 is characterized in that: the volume ratio of ethanol and acetic acid is 4～10:1 in the mixed solvent of described ethanol and acetic acid.
7. method according to claim 1 is characterized in that: the Mw=4 of described polymethyl siloxane, 000～16,000.
8. method according to claim 1 is characterized in that: described substrate of glass is the sheet glass of parcel one deck conduction Al paper tinsel.
9. method according to claim 1 is characterized in that: described super-hydrophobic TiO
2The contact angle of film and water is 150.4～154.5 °, and roll angle is less than 5 °.
10. method according to claim 9 is characterized in that: described roll angle is 2.1 °.
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