CN114672889A - Core-shell structure piezoelectric fiber force-control coaxial electrostatic spinning process - Google Patents
Core-shell structure piezoelectric fiber force-control coaxial electrostatic spinning process Download PDFInfo
- Publication number
- CN114672889A CN114672889A CN202210288251.9A CN202210288251A CN114672889A CN 114672889 A CN114672889 A CN 114672889A CN 202210288251 A CN202210288251 A CN 202210288251A CN 114672889 A CN114672889 A CN 114672889A
- Authority
- CN
- China
- Prior art keywords
- core
- shell structure
- electrostatic spinning
- force
- coaxial
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 60
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000011258 core-shell material Substances 0.000 title claims abstract description 39
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 48
- 239000002033 PVDF binder Substances 0.000 claims abstract description 31
- 238000009987 spinning Methods 0.000 claims abstract description 28
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 239000012792 core layer Substances 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 44
- 239000007921 spray Substances 0.000 claims description 27
- 238000001523 electrospinning Methods 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920003082 Povidone K 90 Polymers 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 48
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 21
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 21
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 21
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229920000144 PEDOT:PSS Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Nonwoven Fabrics (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
A core-shell structure piezoelectric fiber force control coaxial electrostatic spinning process comprises the following steps: respectively adding a polyvinylidene fluoride solution serving as a shell layer spinning solution and a multi-wall carbon nanotube suspension serving as a core layer spinning solution into a force-controlled coaxial electrostatic spinning device, and independently controlling the propelling speed of the two spinning solutions by a propelling pump; a receiving plate is arranged below a nozzle of the force-controlled coaxial electrostatic spinning device and connected with a two-dimensional moving platform, the moving path of the two-dimensional moving platform is controlled by a controller, a preset motion track program is input into the controller of the two-dimensional moving platform, and the receiving plate is driven to move according to the preset motion track, so that the jet flow speed is matched with the moving speed of the receiving plate; and adjusting parameters of the force control coaxial electrostatic spinning device to carry out electrostatic spinning, so that the piezoelectric fibers of the core-shell structure are continuously and controllably deposited on the collecting plate to obtain a piezoelectric fiber array pattern of the core-shell structure, and the thickness degree of the fibers can be controlled by adjusting parameters such as voltage.
Description
Technical Field
The invention belongs to the technical field of electrostatic spinning, and particularly relates to a core-shell structure piezoelectric fiber force control coaxial electrostatic spinning process.
Background
The electrospinning method is currently considered to be a simple method for preparing ultrafine fibers or nanofibers, and the morphological structure or aggregation structure of the fibers can be conveniently changed or controlled by adjusting the electrospinning process parameters (such as solution concentration, solvent ratio, solution conductivity, voltage, flow rate, receiving distance, etc.). In the electrostatic spinning process, polymer jet flow is stretched and thinned by electric field force in a high-voltage electrostatic field, and simultaneously solvent is volatilized and solidified, finally fibers are formed and deposited on a receiving plate. The coaxial electrostatic spinning is a process method similar to the traditional electrostatic spinning, and adopts a coaxial nozzle to replace a single-shaft nozzle of the traditional electrostatic spinning. Coaxial electrostatic spinning is a simple and effective method, and is widely used for preparing core-shell structure micro-nano fibers, thereby being widely applied to the fields of batteries, gas sensors, photocatalysis, biomedicine, flexible electronics and the like.
The piezoelectric material is a crystal material with voltage appearing at two ends under the action of external force, and can realize mutual conversion between mechanical energy and electric energy. The characteristics of the piezoelectric material are utilized to manufacture various sensor elements and micro-nano energy devices. Compared with piezoelectric ceramics with larger brittleness, the polymer with more obvious piezoelectric effect, namely polyvinylidene fluoride (PVDF), has the advantages of better flexibility, impact resistance and friction resistance. These properties of PVDF will contribute to a great expansion of the application field of piezoelectric materials. The existing piezoelectric product taking polyvinylidene fluoride as a raw material is mainly a piezoelectric film prepared by adopting a tape casting method, and the oriented arrangement of high beta crystal form content and beta crystal form is realized by the methods of film stretching and polarization, but the preparation method has harsh conditions, more complex steps and higher requirements on equipment.
In the field of flexible electronics, T.Sharma and the like successfully prepare the core-shell structure piezoelectric nanofiber pressure sensor by using coaxial electrostatic spinning, and test results show that compared with common PVDF fibers, PVDF fiber signals of the core-shell structure are enhanced by 4.5 times, and the sensitivity is also obviously improved. However, coaxial electrostatic spinning is difficult to collect as common electrostatic spinning, and the fibers cannot be collected orderly and controllably, so that the application of the coaxial electrostatic spinning in the micro-nano field is limited.
Therefore, there is a need to provide a new electrospinning process, which can solve the problem of controllable deposition in coaxial electrospinning and prepare continuously controllable core-shell structure piezoelectric fibers.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a core-shell structure piezoelectric fiber force-control coaxial electrostatic spinning process with simple preparation process and low requirements on preparation conditions and equipment.
The technical scheme adopted by the invention is as follows:
a core-shell structure piezoelectric fiber force control coaxial electrostatic spinning process is characterized in that:
the device adopted by the device is a force-control coaxial electrostatic spinning device, the force-control coaxial electrostatic spinning device comprises a spray head, a receiving plate and a controller, the spray head comprises an inner spray nozzle and an outer spray nozzle which are sleeved inside and outside, and the controller can respectively control the jet speed of the inner spray nozzle and the jet speed of the outer spray nozzle of the spray head;
the receiving plate is arranged below the spray head and connected with a two-dimensional moving platform, and the two-dimensional moving platform is connected with the controller and controls the receiving plate to move on a two-dimensional plane through the controller;
the process comprises the following steps:
injecting a polyvinylidene fluoride solution serving as a shell layer spinning solution into an outer solution channel of an outer nozzle of a connection force control coaxial electrostatic spinning device, and injecting a multi-wall carbon nanotube suspension serving as a core layer spinning solution into an inner solution channel of an inner nozzle of the connection force control coaxial electrostatic spinning device;
inputting a preset motion track program into a controller of the two-dimensional moving platform, and controlling the receiving plate to move according to the preset motion track so that the jet flow speed is matched with the moving speed of the receiving plate; and adjusting parameters of the force-control coaxial electrostatic spinning device to carry out electrostatic spinning to obtain the piezoelectric fiber array pattern with the core-shell structure.
Preferably, the solution channel is provided with a propulsion pump controlled by the controller, and the propulsion pump respectively and independently controls the propulsion speed of the liquid in the inner solution channel and the propulsion speed of the liquid in the outer solution channel, so that the jet speed of the inner nozzle and the jet speed of the outer nozzle of the sprayer are controlled.
Preferably, the polyvinylidene fluoride solution used as the shell spinning solution uses polyvinylidene fluoride as a solute, DMF and acetone as solvents, and is stirred for four hours at 40 ℃ by using a magnetic stirrer and then stands until bubbles disappear; the multi-walled carbon nanotube suspension used as the core layer spinning solution uses multi-walled carbon nanotubes as solute, PVP K90 as dispersant and DMF (N, N-dimethylformamide) as solvent, is stirred for four hours at 40 ℃ by using a water bath heating stirrer, then is ultrasonically dispersed for 1 hour by using an ultrasonic disperser, and then is kept stand.
Preferably, the polyvinylidene fluoride concentration in the polyvinylidene fluoride solution is 20% by weight.
Preferably, the propelling speeds of the polyvinylidene fluoride solution and the multiwalled carbon nanotube suspension are 5-10 ml/h and 1ml/h respectively, and the flow speed precision is 0.1 ml/h.
Preferably, the parameters of the force-controlled coaxial electrospinning device are as follows:
the spinning voltage is 5-7 kv;
and the receiving distance between the spray head and the receiving plate of the coaxial electrostatic spinning device is 2-5 cm.
Preferably, the inner nozzle is connected with an inner coaxial needle, the outer nozzle is connected with an outer coaxial needle, the inner coaxial needle is longer than the outer coaxial needle, and the inner needle and the outer needle of the coaxial needle are 22/17G in size.
Preferably, the dispersant PVP (polyvinylpyrrolidone) in the multi-wall carbon nanotube suspension should be in a suitable range to make the multi-wall carbon nanotubes well dispersed in DMF (N, N-dimethylformamide) solution, so that the multi-wall carbon nanotube suspension has both a certain viscosity and a good conductivity.
Preferably, the moving speed range of the two-dimensional moving platform is 150-250 mm/s.
Preferably, an aluminum foil for collecting the piezoelectric fibers of the core-shell structure is adhered to the receiving plate.
Preferably, the two-dimensional moving platform comprises an X-direction moving platform and a Y-direction moving platform.
The invention has the following beneficial effects: the utility model provides a coaxial electrostatic spinning technology of core shell structure piezoelectric fiber power control has reduced the process that the efflux whiped among the traditional electrostatic spinning process for the continuous controllable deposit of core shell structure piezoelectric fiber has following advantage in this method compared with traditional electrostatic spinning on the collecting plate: (1) time is saved: the method can realize the simultaneous preparation of the conductive core and the piezoelectric shell layer, solves the problem that a vinylidene fluoride (PVDF) fiber electrode is difficult to integrate in one step, and does not need to spend a large amount of time on designing the electrode; (2) customizing: by introducing a force-controlled electrostatic spinning technology, electrostatic spinning fibers can be orderly deposited on a receiving plate, and a reasonable fiber array pattern can be designed according to the application scene of the fibers; (3) controllability: the thickness degree of the fiber can be controlled by adjusting parameters such as voltage, two-dimensional platform speed and the like, and the method is suitable for different application scenes.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a structural view of a force-controlled coaxial electrospinning apparatus;
FIG. 2 is a graph of the morphology of a core-shell structure piezoelectric fiber produced by force-controlled coaxial electrospinning;
FIG. 3 is a diagram of the jet flow pattern during force-controlled coaxial electrospinning;
FIG. 4 is an image of a fiber array grid prepared using force-controlled coaxial electrospinning;
fig. 5 shows that in example 1, aluminum foil is used as a collecting plate, polyvinylidene fluoride (PVDF) is used as a shell spinning solution, and conductive ink Pedot: pss is a core layer spinning solution, and force-controlled coaxial electrostatic spinning is carried out to obtain a transmission electron microscope image;
FIG. 6 is a graph of the morphology of fibers obtained by force-controlled coaxial electrospinning in example 2 using aluminum foil as a collecting plate, polyvinylidene fluoride (PVDF) as a shell layer spinning solution, and multi-walled carbon nanotubes (MWCNT) as a core layer spinning solution;
FIG. 7 is a schematic view of a zigzag spinning path;
FIG. 8 is a block diagram of a homemade sensor utilizing core-shell structured piezoelectric fibers prepared in accordance with the present invention;
FIG. 9 is a test stimulus for the preparation of fiber arrays using force-controlled coaxial electrospinning.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
The terms of direction and position of the present invention, such as "up", "down", "front", "back", "left", "right", "inside", "outside", "top", "bottom", "side", etc., refer to the direction and position of the attached drawings. Accordingly, the use of directional and positional terms is intended to illustrate and understand the present invention and is not intended to limit the scope of the present invention.
The invention provides a core-shell structure piezoelectric fiber force-control coaxial electrostatic spinning process, which is characterized by comprising the following steps of:
the device adopted by the method is a force-control coaxial electrostatic spinning device, as shown in figure 1, the force-control coaxial electrostatic spinning device comprises a spray head 1, a receiving plate 3 and a controller, wherein the spray head 1 comprises an inner spray nozzle and an outer spray nozzle which are sleeved inside and outside, and the controller respectively controls the jet velocity of the inner spray nozzle and the outer spray nozzle of the spray head 1;
the receiving plate 3 is arranged below the spray head 1, the receiving plate 3 is connected with a two-dimensional moving platform, and the two-dimensional moving platform is connected with a controller and controls the two-dimensional moving platform to move on a two-dimensional plane through the controller;
the process comprises the following steps:
injecting a polyvinylidene fluoride solution serving as a shell layer spinning solution into an outer solution channel of an outer nozzle of a nozzle 1 of a connection force control coaxial electrostatic spinning device, and injecting a multi-walled carbon nanotube suspension serving as a core layer spinning solution into an inner solution channel of an inner nozzle of the nozzle 1 of the connection force control coaxial electrostatic spinning device;
inputting a preset motion track program into a controller of the two-dimensional moving platform, and controlling the receiving plate 3 to move according to the preset motion track, so that the jet flow speed is matched with the moving speed of the receiving plate 3; and adjusting parameters of the force-control coaxial electrostatic spinning device to carry out electrostatic spinning to obtain the piezoelectric fiber array pattern with the core-shell structure.
The solution channel is provided with a propulsion pump controlled by the controller, and the propulsion pump respectively and independently controls the propulsion speed of liquid in the inner solution channel and the outer solution channel, so that the jet speed of the inner nozzle and the outer nozzle of the sprayer 1 is controlled.
The polyvinylidene fluoride solution used as the shell spinning solution uses polyvinylidene fluoride as a solute, and DMF (N, N-dimethylformamide) and acetone as solvents; the multi-walled carbon nanotube suspension used as the core layer spinning solution uses multi-walled carbon nanotubes as solute, PVP K90 as dispersant and DMF (N, N-dimethylformamide) as solvent.
The weight percentage concentration of polyvinylidene fluoride in the polyvinylidene fluoride solution is 20%.
The propelling speeds of the polyvinylidene fluoride solution and the multiwalled carbon nanotube suspension are 5-10 ml/h and 1ml/h respectively, and the flow speed precision is 0.1 ml/h.
The parameters of the force-controlled coaxial electrostatic spinning device are as follows:
the spinning voltage is 5-7 kv;
and the receiving distance between the spray head 1 and the receiving plate 3 of the coaxial electrostatic spinning device is 2-5 cm.
The interior nozzle is connected with interior coaxial syringe needle, outer nozzle is connected with outer coaxial syringe needle, interior coaxial syringe needle is good at outer coaxial syringe needle, the interior outer needle size of coaxial syringe needle is 22/17G.
The moving speed range of the two-dimensional moving platform is 150-250 mm/s.
And an aluminum foil 2 for collecting the piezoelectric fibers of the core shell structure is adhered on the receiving plate.
The two-dimensional moving platform comprises an X-direction moving platform 5 and a Y-direction moving platform 4.
The dispersant PVP (polyvinylpyrrolidone) in the multiwall carbon nanotube suspension is in a suitable range interval, so that the multiwall carbon nanotubes can be well dispersed in a DMF (N, N-dimethylformamide) solution, and the multiwall carbon nanotube suspension has certain viscosity and good conductivity, and the range interval of the dispersant PVP (polyvinylpyrrolidone) adopted in the embodiment of the invention is shown in Table 1:
TABLE 1 MWCNT/PVP suspensions parameters
The morphology of the core-shell structure piezoelectric fiber of the sample prepared by configuring the solution according to the range interval shown in table 1 and carrying out force-controlled coaxial electrospinning is shown in fig. 2.
As shown in FIG. 2, the morphology of fiber samples obtained by nine different MWCNT/PVP parameter ratios can be obtained, and the dispersion degree of MWCNT (multi-walled carbon nanotube) is important for forming a good core-shell structure piezoelectric fiber. As can be seen from the images of numbers 2, 5, and 8 in fig. 2, the MWCNT (multi-walled carbon nanotube) formed a good structure in PVDF (polyvinylidene fluoride). In addition, although the dispersant PVP (polyvinylpyrrolidone) can enhance the viscosity of the MWCNT suspension and make it easier to spin, the dispersant PVP (polyvinylpyrrolidone) has a great influence on the conductivity of the MWCNT suspension, so the ratio of MWCNT to PVP must be in a proper ratio range. For this purpose, the resistance value of the individual piezoelectric fibers was measured: and taking down the piezoelectric fibers with the length of 20mm, placing the piezoelectric fibers on copper metal at two ends, coating conductive silver adhesive at the two ends, standing and air-drying, and measuring the resistance values at the two ends by using a universal meter. From the appearance and the actually measured resistance of the fiber, when the content of PVP (polyvinylpyrrolidone) is 0.2-0.3 g and the content of MWCNT (multi-walled carbon nanotube) is 0.3-0.4 g, the core-shell structure piezoelectric fiber with good deposition effect can be obtained.
In some embodiments of the invention, the jet is depicted in fig. 3; a fiber array grid was prepared using the method described above and the image is shown in fig. 4. In order to make the objects, technical solutions and advantages of the present invention more apparent, some specific embodiments of the present invention will be described in detail.
Example 1:
a: preparing a PVDF (polyvinylidene fluoride) solution with the weight percentage concentration of 20%, stirring for 4 hours at 40 ℃ by using a magnetic stirrer, and standing until bubbles disappear; the preparation weights are 5g DMF (N, N-dimethylformamide), 0.2g PVP (polyvinylpyrrolidone), 1.6g Pedot: pedot for Pss: pss (Pedot: Pss is composed of PEDOT and PSS, PEDOT is a polymer of EDOT (3, 4-ethylene dioxythiophene monomer), PSS is polystyrene sulfonate.) mixed solution, and is stirred for 4 hours at 40 ℃ by using a water bath heating stirrer;
b: mixing the above Pedot: the Pss mixed solution and the PVDF (polyvinylidene fluoride) solution are respectively injected into solution channels of inner and outer nozzles of a nozzle of a connecting force control coaxial electrostatic spinning device, the inner diameter and the outer diameter of a coaxial needle are 22/17G, the receiving distance is 4cm, a receiving plate is fixed on a two-dimensional moving platform, a controller of the two-dimensional moving platform controls the receiving plate to move according to a specified track at the speed of 150mm/s, and 6kv voltage is applied for spinning.
The material prepared in this example is shown in fig. 5, conductive ink PEDOT: PSS is used as the core spinning solution, and PVP K90 is used as the dispersant, so that the mass ratio of PEDOT: (ii) conductivity of PSS. And measuring the resistance values of the two ends of the piezoelectric fiber by using a multimeter, wherein the resistance values exceed the maximum range of a common multimeter, so that the conductive ink PEDOT: PSS is not suitable for being used as a conductive core to prepare the core-shell structure piezoelectric fiber.
Example 2:
a: preparing a PVDF (polyvinylidene fluoride) solution with the weight percentage concentration of 20%, stirring for 4 hours at 40 ℃ by using a magnetic stirrer, and standing until bubbles disappear; preparing mixed solution of WMCNT (multi-walled carbon nanotube) with the weight of 10g of DMF (N, N-dimethylformamide), 0.2g of MWCNT (multi-walled carbon nanotube) and 0.2g of PVP (polyvinylpyrrolidone), stirring for 4 hours at 40 ℃ by using a water bath heating stirrer, and then placing into an ultrasonic dispersion instrument for dispersion for 1 hour;
b: respectively injecting an upper WMCNT (multi-walled carbon nanotube) mixed solution and a PVDF (polyvinylidene fluoride) solution into solution channels of an inner nozzle and an outer nozzle of a connecting force control coaxial electrostatic spinning device, wherein the inner diameter and the outer diameter of a coaxial needle are 22/17G, the receiving distance is 4cm, and a receiving plate is fixed on a two-dimensional moving platform; the controller of the two-dimensional moving platform controls the receiving plate to move according to a specified track at the speed of 200mm/s, and 6kv of voltage is applied for spinning;
as shown in fig. 6, the material prepared in this example uses MWCNTs (multi-walled carbon nanotubes) with excellent conductivity as the conductive core, and effectively reduces the electrical resistance of the core-shell structure piezoelectric fiber. Compared with the conductive ink PEDOT: PSS for spinning, MWCNT (multi-walled carbon nanotube) is smoother and controllable during electrostatic spinning, and PVDF (polyvinylidene fluoride) is not solidified.
Example 3:
a: preparing a PVDF (polyvinylidene fluoride) solution with the weight percentage concentration of 20%, stirring for 4 hours at 40 ℃ by using a magnetic stirrer, and standing until bubbles disappear; preparing mixed solution of WMCNT (multi-walled carbon nanotube) with the weight of 10g of DMF (N, N-dimethylformamide), 0.2g of MWCNT (multi-walled carbon nanotube) and 0.2g of PVP (polyvinylpyrrolidone), stirring for 4 hours at 40 ℃ by using a water bath heating stirrer, and then placing into an ultrasonic dispersion instrument for dispersion for 1 hour;
b: respectively injecting the WMCNT (multi-walled carbon nanotube) mixed solution and PVDF (polyvinylidene fluoride) solution into solution channels of inner and outer nozzles of a nozzle of a connecting force control coaxial electrostatic spinning device, wherein the inner diameter and the outer diameter of a coaxial needle 5 are 22/17G, the receiving distance is 4cm, and a receiving plate is fixed on a two-dimensional moving platform; the controller of the two-dimensional moving platform controls the receiving plate to move at the speed of 150mm/s according to the track, and the voltage of 6kv is applied to spin.
In addition, in order to test the practicability of the core-shell structure piezoelectric fiber prepared by the process flow, a zigzag spinning path and a self-made sensor shown in fig. 7 are designed, so that the piezoelectric fiber is deposited on the aluminum foils, then the aluminum foils are kept stand, and parts of the piezoelectric fiber are cut off and are respectively placed on two aluminum foils which must have a certain interval. The fibers at both ends of the aluminum foil were covered with conductive silver paste, dried, left to stand, and then a PDMS insulation layer was attached thereto, and a schematic view of the entire sensor is shown in fig. 8.
The sensor is vertically fixed, a vibration exciter is used for carrying out excitation experiments according to different frequencies and amplitudes,
the performance output graphs of the sensors under two different test parameters are selected, as shown in fig. 9, the set parameter is 10hz 5vpp, the output curves of the self-made sensor and the standard sensor are compared, the follow-up performance and the sensitivity of the sensor are good, and the potential of the process in the battery field, the gas sensor field, the photocatalysis field, the biomedical field and the flexible electronic field is proved.
The above embodiments only provide illustrative steps, wherein the concentration, voltage, coaxial needle size, and moving platform speed can be selected according to the experimental situation.
It will be understood by those skilled in the art that all or part of the steps in the method for implementing the above embodiments may be implemented by relevant hardware instructed by a program, and the program may be stored in a computer-readable storage medium, such as ROM/RAM, a magnetic disk, an optical disk, etc.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. A core-shell structure piezoelectric fiber force control coaxial electrostatic spinning process is characterized in that:
the device is a force-control coaxial electrostatic spinning device, the force-control coaxial electrostatic spinning device comprises a spray head (1), a receiving plate (3) and a controller, the spray head (1) comprises an inner spray nozzle and an outer spray nozzle which are sleeved inside and outside, and the controller can respectively control the jet velocity of the inner spray nozzle and the outer spray nozzle of the spray head (1);
the receiving plate (3) is arranged below the spray head (1), the receiving plate (3) is connected with a two-dimensional moving platform, and the two-dimensional moving platform is connected with a controller and controls the two-dimensional moving platform to move on a two-dimensional plane through the controller;
the process comprises the following steps:
injecting a polyvinylidene fluoride solution serving as a shell layer spinning solution into an outer solution channel of an outer nozzle of a nozzle (1) of a connection force control coaxial electrostatic spinning device, and injecting a multi-wall carbon nanotube suspension serving as a core layer spinning solution into an inner solution channel of an inner nozzle of the nozzle (1) of the connection force control coaxial electrostatic spinning device;
inputting a preset motion track program into a controller of the two-dimensional moving platform, and controlling the receiving plate (3) to move according to the preset motion track, so that the jet flow speed is matched with the moving speed of the receiving plate (3); and adjusting parameters of the force-control coaxial electrostatic spinning device to carry out electrostatic spinning to obtain the piezoelectric fiber array pattern with the core-shell structure.
2. The core-shell structure piezoelectric fiber force-control coaxial electrospinning process according to claim 1, wherein: the solution channel is provided with a propulsion pump controlled by the controller, and the propulsion pump respectively and independently controls the propulsion speed of the liquid in the inner solution channel and the outer solution channel.
3. The core-shell structure piezoelectric fiber force-control coaxial electrospinning process according to claim 1, wherein: the polyvinylidene fluoride solution used as the shell spinning solution uses polyvinylidene fluoride as a solute and DMF and acetone as solvents; the multi-walled carbon nanotube suspension used as the core layer spinning solution uses multi-walled carbon nanotubes as a solute, PVP K90 as a dispersant and DMF as a solvent.
4. The core-shell structure piezoelectric fiber force-control coaxial electrospinning process according to claim 1, wherein: the weight percentage concentration of polyvinylidene fluoride in the polyvinylidene fluoride solution is 20%.
5. The core-shell structure piezoelectric fiber force-control coaxial electrospinning process according to claim 1, wherein: the propelling speeds of the polyvinylidene fluoride solution and the multiwalled carbon nanotube suspension are 5-10 ml/h and 1ml/h respectively, and the flow speed precision is 0.1 ml/h.
6. The core-shell structure piezoelectric fiber force-control coaxial electrospinning process according to claim 1, wherein: the parameters of the force control coaxial electrostatic spinning device are as follows:
the spinning voltage is 5-7 kv;
and the receiving distance between the spray head (1) and the receiving plate (3) of the coaxial electrostatic spinning device is 2-5 cm.
7. The core-shell structure piezoelectric fiber force-control coaxial electrospinning process according to claim 1, wherein: the interior nozzle is connected with interior coaxial syringe needle, outer nozzle is connected with outer coaxial syringe needle, interior coaxial syringe needle is good at outer coaxial syringe needle, the interior outer needle size of coaxial syringe needle is 22/17G.
8. The core-shell structure piezoelectric fiber force-control coaxial electrospinning process according to claim 1, wherein: the moving speed range of the two-dimensional moving platform is 150-250 mm/s.
9. The core-shell structure piezoelectric fiber force-control coaxial electrospinning process according to claim 1, wherein: and an aluminum foil (2) for collecting the piezoelectric fibers of the core shell structure is adhered to the receiving plate.
10. The core-shell structure piezoelectric fiber force-control coaxial electrospinning process according to claim 1 or 8, wherein: the two-dimensional moving platform comprises an X-direction moving platform (5) and a Y-direction moving platform (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210288251.9A CN114672889A (en) | 2022-03-22 | 2022-03-22 | Core-shell structure piezoelectric fiber force-control coaxial electrostatic spinning process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210288251.9A CN114672889A (en) | 2022-03-22 | 2022-03-22 | Core-shell structure piezoelectric fiber force-control coaxial electrostatic spinning process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114672889A true CN114672889A (en) | 2022-06-28 |
Family
ID=82073331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210288251.9A Pending CN114672889A (en) | 2022-03-22 | 2022-03-22 | Core-shell structure piezoelectric fiber force-control coaxial electrostatic spinning process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114672889A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140162521A1 (en) * | 2012-12-10 | 2014-06-12 | Taipei Medical University | Electrospinning apparatus with a sideway motion device and a method of using the same |
| CN105671685A (en) * | 2016-01-18 | 2016-06-15 | 东华大学 | Electrospinning skin-core single fiber with axially equivalent piezoelectric property as well as preparation method and application thereof |
| CN108374238A (en) * | 2018-03-16 | 2018-08-07 | 中国科学院广州能源研究所 | A kind of phase-change thermal storage fabric prepared using coaxial electrostatic spinning technology |
| CN108950703A (en) * | 2018-09-18 | 2018-12-07 | 西安交通大学 | The device and method of piezopolymer MEMS structure is prepared based on one step chemical industry skill of near field electrostatic spinning |
| CN109321987A (en) * | 2018-10-29 | 2019-02-12 | 厦门大学 | A kind of electrospinning direct-writing exchange microcontroller device and method thereof |
| CN109853054A (en) * | 2019-02-27 | 2019-06-07 | 上海交通大学医学院附属第九人民医院 | A kind of device and building method of coaxial electrostatic spinning 3 D-printing biological support |
| CN110387588A (en) * | 2019-08-15 | 2019-10-29 | 吉林大学 | A method of preparing the micro nanometer fiber film of core-shell structure using Janus syringe needle electrostatic spinning arranged side by side |
-
2022
- 2022-03-22 CN CN202210288251.9A patent/CN114672889A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140162521A1 (en) * | 2012-12-10 | 2014-06-12 | Taipei Medical University | Electrospinning apparatus with a sideway motion device and a method of using the same |
| CN105671685A (en) * | 2016-01-18 | 2016-06-15 | 东华大学 | Electrospinning skin-core single fiber with axially equivalent piezoelectric property as well as preparation method and application thereof |
| CN108374238A (en) * | 2018-03-16 | 2018-08-07 | 中国科学院广州能源研究所 | A kind of phase-change thermal storage fabric prepared using coaxial electrostatic spinning technology |
| CN108950703A (en) * | 2018-09-18 | 2018-12-07 | 西安交通大学 | The device and method of piezopolymer MEMS structure is prepared based on one step chemical industry skill of near field electrostatic spinning |
| CN109321987A (en) * | 2018-10-29 | 2019-02-12 | 厦门大学 | A kind of electrospinning direct-writing exchange microcontroller device and method thereof |
| CN109853054A (en) * | 2019-02-27 | 2019-06-07 | 上海交通大学医学院附属第九人民医院 | A kind of device and building method of coaxial electrostatic spinning 3 D-printing biological support |
| CN110387588A (en) * | 2019-08-15 | 2019-10-29 | 吉林大学 | A method of preparing the micro nanometer fiber film of core-shell structure using Janus syringe needle electrostatic spinning arranged side by side |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Spraying functional fibres by electrospinning | |
| CN100572619C (en) | A kind of apparatus and method that prepare regular arranged macromolecular nano-fibre | |
| US9644295B2 (en) | Centrifugal electrospinning apparatus and methods and fibrous structures produced therefrom | |
| CN106835304B (en) | A kind of electrostatic spinning-electrical painting device and its application | |
| CN105908490B (en) | A kind of preparation method of multifunctional nano paper/electrospun fibers flexible compound membrane structure | |
| CN102719927B (en) | Preparation method of polyvinylidene fluoride (PVDF)/carbon nanotube composite nanofibers | |
| Pan et al. | Near-field electrospinning enhances the energy harvesting of hollow PVDF piezoelectric fibers | |
| CN102206878B (en) | Device for electrospinning three-dimensional controlled structure of nanofibers | |
| CN106450101A (en) | Method for preparing novel lithium battery diaphragm by coaxial electrostatic spinning | |
| CN104153128A (en) | Method for manufacturing flexible stretchable device based on ordered arrangement torsion structure | |
| CN108221175A (en) | A kind of preparation method of high-voltage electricity polyvinylidene fluoride composite material | |
| Liu et al. | Influence of electrohydrodynamic jetting parameters on the morphology of PCL scaffolds | |
| CN106848314A (en) | The method that lithium-sulfur cell prepares positive electrode with the preparation method of double-layer porous carbon nano-fiber and using it | |
| US20090115286A1 (en) | Electrically conductive thin film formed from an ionic liquid and carbon nanotubes having a high aspect ratio, and actuator element comprising the thin film | |
| CN109468686A (en) | Electrostatic spinning apparatus, the porous Gr/PAN composite nano fiber of orientation and preparation method thereof | |
| CN109468701A (en) | Electrostatic spinning apparatus, orientation Fe3O4/ Gr/PAN composite conducting nanofiber and preparation method thereof | |
| CN108842195A (en) | A kind of electrostatic spinning apparatus and method based on bernoulli principle | |
| CN108411383B (en) | Porous spherical electrostatic spinning nozzle and spinning method thereof | |
| CN106012099A (en) | Conductive PAN/rGO coaxial nanofiber and preparation method thereof | |
| CN101275299A (en) | Thermal bubble spinning method and device for nano-fiber production | |
| CN105506783A (en) | Preparation method for barium titanate nanofiber arrayed in orientation mode | |
| CN108385201A (en) | A kind of compound stretchable conductive fiber of graphene/polyurethane and preparation method thereof | |
| CN107164820A (en) | A kind of highly oriented composite conducting nanofiber | |
| Wang et al. | Structural design of electrospun nanofibers for electrochemical energy storage and conversion | |
| Yan et al. | Smoothening electrospinning and obtaining high-quality cellulose acetate nanofibers using a modified coaxial process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220628 |