CN114507942B - Preparation method of polyvinylidene fluoride nanofiber membrane regulated and controlled by mixed phase-change titanium dioxide - Google Patents
Preparation method of polyvinylidene fluoride nanofiber membrane regulated and controlled by mixed phase-change titanium dioxide Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43838—Ultrafine fibres, e.g. microfibres
Abstract
The invention discloses a preparation method of a polyvinylidene fluoride nano-fiber membrane regulated by mixed phase-change titanium dioxide, wherein anatase phase TiO is 2 And rutile phase TiO 2 Forming a semiconductor heterojunction structure, preparing tetrabutyl titanate precursor solution, and electrospinning to obtain nanofibers; calcining to obtain TiO with anatase and rutile mixed phase change 2 A nanofiber; grinding to obtain phase-changed TiO 2 A nanorod; transforming the phase into TiO 2 Adding the nanorods into a mixed solvent of DMF and acetone, performing ultrasonic treatment, adding PVDF powder, and performing magnetic stirring to obtain a PVDF precursor solution; electrospinning to obtain a nanofiber membrane; drying to obtain phase-change TiO 2 And regulating and controlling the PVDF nanofiber membrane. The PVDF fiber is regulated and controlled by the non-piezoelectric material, so that the beta polar phase of the PVDF fiber is greatly higher than that of other preparation methods for regulating and controlling the non-piezoelectric material, and the regulation and control effect can reach the regulation and control effect of the PVDF fiber by the piezoelectric material.
Description
Technical Field
The invention relates to the technical field of preparation of nanofiber membranes, in particular to mixed phase-change titanium dioxide (TiO) 2 Regulating and controlling a preparation method of a polyvinylidene fluoride (PVDF) nanofiber membrane.
Background
PVDF is a semi-crystalline polymer that has good mechanical stability under repeated mechanical stress compared to inorganic materials. Meanwhile, the crystal has the characteristics of low density, high flexibility and low cost, and comprises five crystal forms of alpha, beta, gamma, delta and epsilon. Since the beta phase can show the best piezoelectric, pyroelectric and ferroelectric properties, the preparation of the PVDF nanofiber membrane with high content of the beta phase is a hot spot of research work. At present, other crystalline phase to beta phase transformation is generally induced by mechanical stretching, thermal annealing or electric polarization methods. However, due to low conversion efficiency, ideal PVDF nanofiber membranes cannot be formed by these techniques.
The basic principle of preparing the nano-fiber by electrostatic spinning is that under the action of a high-voltage electric field, the electrostatic field force between a needle head and a collecting plate is greater than the surface tension of a solution, and the solution is stretched to form a Taylor cone which is collected on a grounded substrate to form a fiber. The electrostatic spinning is used as a main experimental method for preparing the nano fibers, the prepared nano fibers have the advantages of uniform diameter, large specific surface area, smooth surface, large length-diameter ratio and the like, and the prepared film has the advantages of high porosity, uniform thickness, large-area preparation and the like. As a low-cost, easy-to-operate and high-efficiency nano material preparation method, electrostatic spinning is favored by numerous research groups and enterprises. Particularly, the PVDF nanofiber is prepared by an electrostatic spinning method, mechanical stretching and electric polarization can be simultaneously carried out based on the action of an electrostatic field, so that molecular chain dipoles in the PVDF can be oriented, the alpha phase and the beta phase are converted, and the PVDF nanofiber membrane with high beta phase content is prepared. Compared with other methods such as 3D printing, screen printing, spin coating and the like for preparing PVDF film materials, the electrostatic spinning PVDF nanofiber film has better flexibility, wear resistance, air permeability and higher energy conversion efficiency.
Disclosure of Invention
The technical problem is as follows: the technical problem to be solved by the invention is as follows: the preparation method of the PVDF nanofiber membrane is provided, the problem of low content of beta polar phase in PVDF nanofibers is solved, and the problem of low output open-circuit voltage of a piezoelectric nano generator is solved.
The technical scheme is as follows: in order to solve the technical problems, a mixed phase change TiO is provided 2 Regulating and controlling the preparation method of the PVDF nanofiber membrane.
TiO 2 The material is an indirect band gap semiconductor material with a wider forbidden band, and has excellent thermal stability and chemical stability. More particularly, tiO 2 Can be used as a nucleating agent of PVDF to realize performance regulation and control on PVDF doping, because TiO 2 The dipole moment is large, about 6.33D. TiO 2 2 The content of the electroactive beta phase in the PVDF can be improved through dipole-dipole interaction, so that the piezoelectric property of the PVDF film can be enhanced; on the other hand, high-temperature calcination is carried out to obtain anatase and rutile mixed phase-change TiO 2 Nano-fiber, mixed phase transition TiO 2 Having a semiconductor heterojunction energy bandThe potential barrier property, the built-in electric field generated enhances the dipole moment, and the piezoelectric property of the PVDF film is enhanced.
Preparation of TiO by electrospinning 2 The nano-fiber realizes the regulation and control of the content of the beta polar phase in the PVDF nano-fiber, thereby achieving the purpose of enhancing the piezoelectric property of the PVDF film, improving the open-circuit output voltage of the piezoelectric nano-generator, enabling the piezoelectric nano-generator to be applied to the field of nano-power generation, achieving the purpose of improving the output voltage and current efficiency of an energy collecting device, and meeting the application requirements on energy conversion and related motion signal detection.
The invention relates to mixed phase change TiO 2 Method for preparing PVDF nanofiber membrane regulated and controlled, wherein anatase phase TiO 2 And rutile phase TiO 2 A semiconductor heterojunction structure is formed, and the content of an electroactive beta phase in the PVDF is improved through dipole-dipole interaction and coupling regulation of a semiconductor heterojunction energy band barrier; realizing TiO non-piezoelectric material 2 The PVDF fiber is regulated and controlled to have a beta polar phase which is greatly higher than that of other preparation methods for regulating and controlling non-piezoelectric materials, and the regulating and controlling effect can reach the regulating and controlling effect of the piezoelectric materials on the PVDF fiber. The preparation method is to prepare anatase and rutile mixed phase change TiO 2 A nanorod; mixing anatase and rutile to form TiO phase 2 Adding the nano-rods into a mixed solvent of N-N dimethylformamide DMF and acetone, performing ultrasonic treatment, adding PVDF powder, and stirring by using a magnetic stirrer to obtain a PVDF precursor solution required by electrostatic spinning; performing electrospinning by using a PVDF precursor solution to obtain a nanofiber membrane, and drying in a drying oven to obtain phase-change TiO 2 And regulating and controlling the PVDF nanofiber membrane.
Further, the mixed phase-change TiO of the invention 2 The preparation method for regulating and controlling the PVDF nanofiber membrane specifically comprises the following steps:
step 6, transferring the PVDF precursor solution obtained in the step 5 into a glass injector, then placing the glass injector into an electrostatic spinning machine fixture, adjusting electrospinning parameters, and carrying out electrospinning to obtain a nanofiber membrane;
step 7, drying the nanofiber membrane obtained in the step 6 in a vacuum drying oven at the temperature of 80 ℃ for 0.5 hour to obtain mixed phase-change TiO 2 A regulated PVDF nanofiber membrane.
Further, the concentration of tetrabutyl titanate in the tetrabutyl titanate precursor solution obtained in the step 1 is 24%, and the ratio of PVP concentration to ethanol concentration is = 1: 16.
Further, the glass syringe in step 2 was equipped with a stainless steel needle having an inner diameter of 0.4mm and an outer diameter of 0.7mm.
Further, in the step 2, the distance between the needle head of the glass injector and the collecting plate is 13cm, the voltage applied between the needle head and the collecting plate is 13kv, and the electrostatic spinning environment temperature is controlled at 37 ℃.
Furthermore, the high-temperature calcination time in the step 3 is 2 hours, and the heating rate is controlled at 2.7 ℃/min.
Further, in the step 5, the concentration of DMF and the concentration of acetone are = 3: 2, and the concentration of the phase-change titanium dioxide solution obtained after the phase-change titanium dioxide is added is 4%.
Further, the PVDF solution obtained by adding PVDF in the step 5 has a concentration of 10%.
Further, the glass syringe of step 6 was equipped with a stainless steel needle having an inner diameter of 0.6mm and an outer diameter of 0.9mm.
Further, in the step (6), the distance between the needle and the collecting plate is 17cm, the distance between the needle and the collecting plate is 17kv, and the temperature of the electrostatic spinning environment is controlled at 37 ℃.
Further, the advancing speed of the syringe pump in step 6 was controlled to 1ml/h.
Has the beneficial effects that: compared with the prior art, the preparation method has the following beneficial effects:
firstly, preparing anatase and rutile mixed phase change TiO by a high-temperature calcination method at 450-850 DEG C 2 A nanorod;
second, by doping anatase and rutile mixed phase-change TiO in PVDF nano-fiber 2 Nanorods of anatase phase TiO 2 And rutile phase TiO 2 A semiconductor heterojunction structure is formed, and the content of an electroactive beta phase in the PVDF is improved through dipole-dipole interaction and coupling regulation of a semiconductor heterojunction energy band barrier; realizing TiO serving as non-piezoelectric material 2 The PVDF fiber is regulated and controlled to have a beta polar phase which is greatly higher than that of other preparation methods for regulating and controlling non-piezoelectric materials, and the regulating and controlling effect can reach the regulating and controlling effect of the piezoelectric materials on the PVDF fiber.
Thirdly, the invention provides a method for preparing mixed phase-change TiO 2 The method for regulating and controlling the PVDF nanofiber membrane can realize large-area controllable preparation, and obtain nanofibers with uniform diameters and nanofiber membranes with uniform thicknesses. Meanwhile, the experimental method used by the invention is simple, the preparation scheme is novel, and the popularization and the application in a large range can be realized.
Drawings
FIG. 1 is a diagram of TiO prepared in an example of the present invention 2 Regulating and controlling an experimental flow chart of the PVDF nanofiber membrane;
FIG. 2 shows the present invention450 ℃ to TiO prepared in the examples 2 Scanning electron microscope images of the nanorods;
FIG. 3 shows 650 deg.C-TiO prepared in the example of the present invention 2 Scanning electron microscope images of the nanorods;
FIG. 4 shows 850 deg.C-TiO prepared in the example of the present invention 2 Scanning electron microscope images of the nanorods;
FIG. 5 shows PVDF/TiO prepared in the example of the present invention 2 Scanning electron microscope images of the composite nanofibers;
FIG. 6 shows the different temperatures of the calcined TiO obtained in the examples of the invention 2 Regulating and controlling the content of a beta polar phase of the PVDF nano fiber;
FIG. 7 shows PVDF/TiO prepared in the example of the present invention 2 Digital image of composite nanofiber membrane.
Detailed Description
The invention is further illustrated by the following examples:
example 1
Mixed phase-change TiO 2 The preparation method of the PVDF nanofiber membrane comprises the following steps:
(1) Adding PVP into the mixture containing tetrabutyl titanate and CH 3 CH 2 Stirring the OH mixed solution for 7 hours by using a magnetic stirrer to obtain tetrabutyl titanate electrostatic spinning precursor solution with the solution concentration of 24 percent;
(2) Transferring the tetrabutyl titanate precursor electro-spinning solution obtained in the step (1) into a 5ml glass syringe with a No. 22 stainless steel needle, placing the glass syringe into an electrostatic spinning machine fixture, adjusting the distance between the needle and a collecting plate to be 13cm, the high-voltage to be 13kv and the temperature of an electrostatic spinning chamber to be 37 ℃ during electrostatic spinning, and carrying out electro-spinning;
(3) Transferring the nano-fibers obtained in the step (2) into quartz ceramics, placing the quartz ceramics in a tube furnace, calcining the quartz ceramics for 2 hours at a high temperature of 450 ℃, and naturally cooling the quartz ceramics to obtain anatase phase TiO 2 Then adding anatase phase TiO 2 Transferring the nano-fiber into an agate mortar for grinding to obtain anatase-phase TiO 2 Nanorods, as shown in FIG. 2.
(4) The anatase phase TiO obtained in the step (3) 2 Adding the nano-rods into a mixed solvent of DMF and acetone, carrying out ultrasonic treatment for 20 minutes, adding PVDF powder, and stirring for 15 hours by using a magnetic stirrer to obtain a PVDF precursor solution required by electrostatic spinning;
(5) The TiO containing anatase phase obtained in the step (4) 2 Transferring the PVDF precursor solution into a 10ml glass injector with a No. 20 stainless steel needle, placing the glass injector in an electrostatic spinning machine fixture, adjusting the distance between the needle and a collecting plate to be 17cm and the high-voltage to be 17kv during electrostatic spinning, adjusting the temperature of an electrostatic spinning chamber to be 37 ℃, and the propelling speed of an injection pump to be 1ml/h, and carrying out electrospinning to obtain a nanofiber membrane;
(6) Drying the nanofiber membrane obtained in the step (5) in a vacuum drying oven at the temperature of 80 ℃ for 0.5 hour to obtain anatase phase TiO 2 A regulated PVDF nanofiber membrane.
Example 2
Mixed phase-change TiO 2 The preparation method for regulating and controlling the PVDF nanofiber membrane is shown in figure 1, and the preparation process comprises the following steps:
(1) Adding PVP into the mixture containing tetrabutyl titanate and CH 3 CH 2 Stirring the OH mixed solution for 7 hours by using a magnetic stirrer to obtain tetrabutyl titanate electrostatic spinning precursor solution with the solution concentration of 24%;
(2) Transferring the tetrabutyl titanate precursor electro-spinning solution obtained in the step (1) into a 5ml glass syringe with a No. 22 stainless steel needle, placing the glass syringe into an electrostatic spinning machine fixture, adjusting the distance between the needle and a collecting plate to be 13cm, the high-voltage to be 13kv and the temperature of an electrostatic spinning chamber to be 37 ℃ during electrostatic spinning, and carrying out electro-spinning;
(3) Transferring the nano-fiber obtained in the step (2) into quartz ceramic, placing the quartz ceramic in a tube furnace, calcining the quartz ceramic for 2 hours at a high temperature of 650 ℃, and naturally cooling to obtain anatase and rutile mixed phase TiO 2 Then mixing anatase and rutile phase TiO 2 Transferring the nano-fiber into an agate mortar for grinding to obtain anatase and rutile mixed phase TiO 2 Nano meterA bar as shown in fig. 3.
(4) Mixing TiO of anatase and rutile obtained in the step (3) 2 Adding the nanorods into a mixed solvent of DMF and acetone, performing ultrasonic treatment for 20 minutes, adding PVDF powder, and stirring for 15 hours by using a magnetic stirrer to obtain a precursor solution required by electrostatic spinning;
(5) TiO with anatase and rutile mixed phase obtained in the step (4) 2 Transferring the PVDF precursor solution into a 10ml glass injector with a No. 20 stainless steel needle, placing the glass injector in an electrostatic spinning machine clamp, adjusting the distance between the needle and a collecting plate to be 17cm and the high-voltage to be 17kv during electrostatic spinning, adjusting the temperature of an electrostatic spinning chamber to be 37 ℃, and the propelling speed of an injection pump to be 1ml/h, and carrying out electrospinning;
(6) Placing the nanofiber membrane obtained in the step (5) in a vacuum drying oven at 80 ℃ for drying for 0.5 hour to obtain anatase and rutile mixed phase TiO 2 The controlled PVDF nanofiber membrane, as shown in FIG. 5, is PVDF/TiO 2 Scanning Electron microscope image of the composite nanofiber, as shown in FIG. 7, is PVDF/TiO 2 Digital image of composite nanofiber membrane.
Example 3
Mixed phase-change TiO 2 The preparation method for regulating and controlling the PVDF nanofiber membrane comprises the following steps:
(1) Adding PVP into the mixture containing tetrabutyl titanate and CH 3 CH 2 Stirring the OH mixed solution for 7 hours by using a magnetic stirrer to obtain tetrabutyl titanate electrostatic spinning precursor solution with the solution concentration of 24 percent;
(2) Transferring the tetrabutyl titanate precursor electrospinning solution obtained in the step (1) into a 5ml glass syringe with a No. 22 stainless steel needle, placing the glass syringe in an electrostatic spinning machine fixture, adjusting the distance between the needle and a collecting plate to be 13cm, the high-voltage to be 13kv and the temperature of an electrostatic spinning chamber to be 37 ℃ during electrostatic spinning, and carrying out electrospinning to obtain nanofibers;
(3) Transferring the nano-fiber obtained in the step (2) into quartz ceramic, placing the quartz ceramic in a tube furnace, calcining the quartz ceramic for 2 hours at the high temperature of 850 ℃, and naturally calcining the quartz ceramicCooling to obtain rutile phase TiO 2 Then the rutile phase TiO is added 2 Transferring the nano-fiber into an agate mortar for grinding to obtain rutile phase TiO 2 Nanorods, as shown in fig. 4.
(4) The rutile phase TiO obtained in the step (3) 2 Adding the nano-rods into a mixed solvent of DMF and acetone, carrying out ultrasonic treatment for 20 minutes, adding PVDF powder, and stirring for 15 hours by using a magnetic stirrer to obtain a precursor solution required by electrostatic spinning;
(5) The rutile phase-containing TiO obtained in the step (4) 2 Transferring the PVDF precursor solution into a 10ml glass injector with a No. 20 stainless steel needle, placing the glass injector in an electrostatic spinning machine fixture, adjusting the distance between the needle and a collecting plate to be 17cm and the high-voltage to be 17kv during electrostatic spinning, adjusting the temperature of an electrostatic spinning chamber to be 37 ℃, and the propelling speed of an injection pump to be 1ml/h, and carrying out electrospinning to obtain a nanofiber membrane;
(6) Drying the nanofiber membrane obtained in the step (5) in a vacuum drying oven at the temperature of 80 ℃ for 0.5 hour to obtain rutile phase TiO 2 A regulated PVDF nanofiber membrane.
By comparing the three examples and the experimental results shown in FIG. 6, it can be proved that the TiO with anatase and rutile mixed phase transition is obtained by calcining at the temperature of 450-850 ℃ in the invention 2 And the content of the beta polar phase of the PVDF nano fiber can be effectively regulated and controlled. The foregoing shows and describes the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are intended to further illustrate the principles and operation of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and the invention is to be limited to the embodiments described above. The scope of the invention is defined by the claims and their equivalents.
Claims (9)
1. The preparation method of the polyvinylidene fluoride nanofiber membrane regulated and controlled by mixed phase-change titanium dioxide is characterized by preparing anataseMixed phase change TiO of ore and rutile 2 Nanorods of anatase phase TiO 2 And rutile phase TiO 2 Forming a semiconductor heterostructure to convert the mixed phase into TiO 2 Adding the nano-rods into a mixed solvent of N-N dimethylformamide DMF and acetone, performing ultrasonic treatment, adding PVDF powder, and stirring by using a magnetic stirrer to obtain a PVDF precursor solution required by electrostatic spinning; performing electrospinning by using a PVDF precursor solution to obtain a nanofiber membrane, and drying in a drying oven to obtain phase-change TiO 2 Regulating and controlling a PVDF nanofiber membrane; the content of the electroactive beta phase in the PVDF nano-fiber membrane is improved; the method specifically comprises the following steps:
step 1, adding polyvinylpyrrolidone PVP into a mixture containing tetrabutyl titanate and ethanol CH 3 CH 2 Stirring in the OH mixed solution by using a magnetic stirrer to obtain tetrabutyl titanate precursor solution required by electrostatic spinning;
step 2, transferring the tetrabutyl titanate precursor electrospinning solution obtained in the step 1 into a glass injector, then placing the glass injector into an electrostatic spinning machine fixture, adjusting electrospinning parameters, and carrying out electrospinning to obtain nanofibers;
step 3, transferring the nano-fibers obtained in the step 2 into quartz ceramics, placing the quartz ceramics in a tube furnace or a box furnace, and respectively calcining at high temperature of 450-850 ℃ to obtain anatase and rutile mixed phase-change TiO 2 A nanofiber;
step 4, the phase-change TiO obtained in the step 3 is treated 2 Transferring the nano-fiber into an agate mortar for grinding to obtain the phase-changed TiO 2 A nanorod;
step 5, the phase-change TiO obtained in the step 4 is treated 2 Adding the nanorods into a mixed solvent of N-N dimethylformamide DMF and acetone, performing ultrasonic treatment, adding PVDF powder, and stirring with a magnetic stirrer to obtain a PVDF precursor solution required by electrostatic spinning;
step 6, transferring the PVDF precursor solution obtained in the step 5 into a glass injector, then placing the glass injector into an electrostatic spinning machine fixture, adjusting electrospinning parameters, and carrying out electrospinning to obtain a nanofiber membrane;
in the step 7, the step of,drying the nanofiber membrane obtained in the step 6 in a drying oven to obtain phase-change TiO 2 And regulating and controlling the PVDF nanofiber membrane.
2. The method for preparing a mixed phase-change titanium dioxide-controlled polyvinylidene fluoride nanofiber membrane according to claim 1, wherein the concentration of tetrabutyl titanate in the tetrabutyl titanate precursor solution obtained in the step 1 is 24%, and the PVP concentration: ethanol concentration = 1: 16.
3. The method for preparing a mixed phase-change titanium dioxide-regulated polyvinylidene fluoride nanofiber membrane as claimed in claim 1, wherein the stainless steel needle provided in the glass injector in the step 2 has an inner diameter of 0.4mm and an outer diameter of 0.7mm.
4. The preparation method of the polyvinylidene fluoride nanofiber membrane controlled by the mixed phase-change titanium dioxide as claimed in claim 1, wherein in the step 2, the distance between the needle head of the glass injector and the collecting plate is 13cm, the voltage applied between the needle head and the collecting plate is 13kv, and the electrostatic spinning environmental temperature is controlled at 37 ℃.
5. The preparation method of the polyvinylidene fluoride nanofiber membrane controlled by the mixed phase-change titanium dioxide as claimed in claim 1, wherein the high-temperature calcination time in step 3 is 2 hours, and the temperature rise rate is controlled at 2.7 ℃/min.
6. The method for preparing a polyvinylidene fluoride nanofiber membrane controlled by mixed phase-change titanium dioxide as claimed in claim 1, wherein in the step 5, the ratio of DMF concentration to acetone concentration is = 3: 2, and the concentration of the phase-change titanium dioxide solution obtained after adding the phase-change titanium dioxide is 4%.
7. The method for preparing a mixed phase-change titanium dioxide-regulated polyvinylidene fluoride nanofiber membrane according to claim 1, wherein the concentration of the PVDF solution obtained by adding PVDF in the step 5 is 10%.
8. The method for preparing a mixed phase-change titanium dioxide regulating polyvinylidene fluoride nanofiber membrane as claimed in claim 1, wherein the stainless steel needle provided in the glass syringe in the step 6 has an inner diameter of 0.6mm and an outer diameter of 0.9mm.
9. The method for preparing a polyvinylidene fluoride nanofiber membrane controlled by mixed phase-change titanium dioxide as claimed in claim 1, wherein in the step 6, the distance between the needle head and the collecting plate is 17cm, the distance between the needle head and the collecting plate is 17kv, and the temperature of an electrostatic spinning environment is controlled at 37 ℃.
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| CN115948859A (en) * | 2017-12-25 | 2023-04-11 | 天津理工大学 | Preparation method of high-voltage polyvinylidene fluoride composite material |
| CN108251970A (en) * | 2018-01-23 | 2018-07-06 | 苏州大学 | TiO2The preparation method of/PAN nanofiber membrane |
| CN108325564B (en) * | 2018-04-03 | 2020-10-30 | 青岛大学 | Flexible TiO with visible light catalytic performance2/PVDF@MoS2Composite nanofiber and preparation method thereof |
| CN108755102B (en) * | 2018-06-20 | 2020-05-22 | 西安交通大学 | Burred carbon composite titanium dioxide nano fiber and preparation method and application thereof |
| CN109112728B (en) * | 2018-08-03 | 2023-11-17 | 东华大学 | Preparation method of flexible titanium dioxide/carbon composite porous nanofiber membrane material |
| CN111850740B (en) * | 2020-06-08 | 2022-11-29 | 国网浙江省电力有限公司双创中心 | Anatase TiO 2 Rutile TiO 2 /ZnTiO 3 Preparation method of three-phase heterogeneous mesoporous nanofiber |
| CN112481832B (en) * | 2020-12-18 | 2022-07-19 | 四川大学 | Preparation method of P (VDF-TrFE) tree-shaped micro-nano fiber piezoelectric film |
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