CN111809266B - Composite nanowire and preparation method thereof - Google Patents

Composite nanowire and preparation method thereof Download PDF

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Publication number
CN111809266B
CN111809266B CN202010586886.8A CN202010586886A CN111809266B CN 111809266 B CN111809266 B CN 111809266B CN 202010586886 A CN202010586886 A CN 202010586886A CN 111809266 B CN111809266 B CN 111809266B
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ato
tio
nano
pvp
microfiber
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CN111809266A (en
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陈宇岳
杨熙
张庆军
林红
张德锁
张骜
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Jiangsu Wulong Knitting Co ltd
Suzhou University
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Jiangsu Wulong Knitting Co ltd
Suzhou University
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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
    • 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
    • D01D11/00—Other features of manufacture
    • D01D11/06—Coating with spinning solutions or melts
    • 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
    • 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
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The invention relates to a composite nanowire and a preparation method thereof, wherein a microfiber array comprises a plurality of nano microfiber units, each nano microfiber unit comprises a PVP (polyvinyl pyrrolidone) matrix and ATO @ TiO formed on the PVP matrix2Conductive powder, nano microfiber unit is ATO @ TiO2PVP microfiber, ATO @ TiO obtained by doping conductive powder2The conductive powder is TiO coated by ATO nano particles2A nanowire. The nano microfiber array prepared by the scheme of the invention has good orientation and good conductivity, and has good application prospects in various aspects such as antistatic property, electromagnetic shielding property, special conductivity and the like.

Description

Composite nanowire and preparation method thereof
Technical Field
The invention belongs to the technical field of conductive materials, and particularly relates to a composite nanowire and a preparation method thereof.
Background
The microfluid spinning technology is a technology for preparing micron-level fiber size by combining the laminar flow effect of the microfluid technology on the basis of the traditional wet spinning rapid forming. Compared with the traditional electrostatic spinning and wet spinning, the micro-flow spinning technology can carry out spinning in a normal environment without specific environment and other requirements, and the characteristic provides convenience for producing some special materials.
Polyvinylpyrrolidone (PVP) is an artificially synthesized flexible long-chain nonionic high polymer, has no irritation to human skin, toxicity or odor, has good compatibility with water, and has various advantages. Because PVP is an artificially synthesized high molecular polymer, the PVP is often blended with other high molecules to prepare composite fibers, so that the PVP can be better applied to the fields of medicine, biology and the like.
The traditional wet spinning, melt spinning, electrostatic spinning and other processes all need special environment and expensive special equipment, and the requirements on the processes, the equipment and the like are higher when the micro-fibers are prepared, so that the high production cost is caused, and meanwhile, the micro-fibers prepared by the related processes have insufficient quality formability due to the sensitivity of the related processes to control factors.
Disclosure of Invention
The composite nanowire and the preparation method thereof disclosed by the invention provide the conductive PVP composite nanowire and the preparation method thereof by adopting a microfluid spinning technology, the preparation efficiency is high, the forming effect is good, and therefore, the composite nanowire and the preparation method thereof have good universality and popularization performance.
The composite nanowire disclosed by the invention comprises a plurality of nano microfiber units, wherein each nano microfiber unit comprises a PVP (polyvinyl pyrrolidone) matrix and ATO @ TiO formed on the PVP matrix2Conductive powder, nano microfiber unit is ATO @ TiO2PVP microfiber, ATO @ TiO obtained by doping conductive powder2The conductive powder is TiO coated by ATO nano particles2A nanowire.
The invention discloses an improvement of a composite nanowire, wherein the content of ATO @ TiO2 conductive powder in a nano microfiber unit is 20-30 wt%.
The invention disclosesAn improvement of composite nanowire, ATO @ TiO2Coating of nano wire on TiO2The average thickness of the ATO nanoparticles of the nanowires is 3-10 nm.
The invention discloses an improvement of composite nano-wire, ATO @ TiO2Coating of nano wire on TiO2The average thickness of the ATO nanoparticles of the nanowires was 5 nm.
The invention discloses an improvement of composite nano-wire, ATO @ TiO2The mass ratio of Sn to Ti in the nano wire is 10-30%.
The invention discloses an improvement of a composite nanowire, wherein the mole ratio of Sb to Sn in ATO nanoparticles is 5-10%.
The invention discloses a preparation method of a composite nanowire, which comprises the following steps:
obtaining microfluid spinning slurry;
and controlling at least the following parameters of the advancing speed of an injection pump, the rotating speed of a motor and the translation speed of a stepping translation table in the microfluid spinning equipment to carry out microfluid spinning so as to obtain the composite nanowire.
The invention discloses an improvement of the preparation method of the composite nanowire, and the stepping translation speed is 1-8 mm/min.
The invention discloses an improvement of the preparation method of the composite nanowire, and the rotating speed of a motor for controlling the winding speed of a fiber collector is 50r/min-300 r/min. The equivalent winding speed is 2600mm-15600mm/min by taking a flat receiver with the width of 26mm as an example.
The invention discloses an improvement of a preparation method of a composite nanowire, wherein the propelling speeds of injection pumps are 0.1-1mL/h respectively.
The invention discloses an improvement of a preparation method of a composite nanowire, wherein microfluid spinning slurry is a system taking ethanol as a dispersing solvent.
The invention discloses an improvement of the preparation method of the composite nanowire, wherein the concentration of PVP in microfluid spinning slurry is 10 wt% -15 wt%.
The invention discloses an improvement of a preparation method of a composite nanowire, namely ATO @ TiO in microfluid spinning slurry2The content of the conductive powder is 3 to 4.5 weight percent。
The scheme of the invention prepares ATO @ TiO by utilizing the micro-fluidic spinning technology2a/PVP blend fiber. The larger the speed of a rotating motor of the micro-fluid spinning machine is, the smaller the fiber diameter is, and the phenomena of fiber adhesion and fiber fracture can be generated when the speed is too high; the propelling speed of the injection pump has certain influence on the overall distribution effect of the fiber array; the larger the advancing speed, the more easily the problems of fiber doubling, adhesion, liquid residual glass slide side surface and the like occur; the larger the translation speed of the stepping translation table is, the larger the distance between the fibers is, the poorer the tightness degree of the fiber array is, and the like. Through better process discussion, ATO @ TiO prepared by using microfluid spinning machine2the/PVP blended fiber has uniform thickness and basically no adhesion and entanglement with each other, ATO @ TiO2The minimum resistivity of the/PVP blended fiber reaches 70K omega cm.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic diagram of a process for preparing composite nanowires according to the present application;
FIG. 2 shows ATO @ TiO in the composite nanowire of the present application2The change curve of the resistivity of the composite nanowire along with the Sn/Ti molar mass ratio;
FIG. 3 shows ATO @ TiO in the composite nanowire of the present application2The resistivity of the composite nanowire changes along with the Sb/Sn molar ratio;
FIG. 4 shows ATO @ TiO in the composite nanowire of the present application2The equivalent circuit schematic diagram of the composite nanowire is shown;
FIG. 5 shows ATO @ TiO in the composite nanowire of the present application2SEM pictures of one embodiment of composite nanowires, wherein (a) is PVP fiber; (b) is ATO @ TiO2PVP microfiber, PVP in ethanol solution mass fraction of 15%, injection pumpThe advancing speed is 0.1mL/h, the stepping translation speed is 4mm/min, the speed of a rotating motor is 200r/min, and the width of the coiled sheet is 26 mm.
Detailed Description
The present invention will be described in detail below with reference to various embodiments. The embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to the embodiments are included in the scope of the present invention.
In the examples shown below, when the corresponding mass or mass fraction is converted to a percentage, the remaining decimal point that is not divided is 1 digit.
The ultrasonic duration is 10-30 min when the absolute ethyl alcohol and the filler are used for preparing the suspension. In the following embodiments, when the winding is performed by taking a flat retractor having a winding width d of 26mm as an example, the actual winding speed is the rotation speed × 2 d.
Example 1
The composite nanowire comprises a plurality of nano microfiber units, wherein each nano microfiber unit comprises a PVP (polyvinyl pyrrolidone) matrix and ATO @ TiO formed on the PVP matrix2Conductive powder, nano microfiber unit is ATO @ TiO2PVP microfiber, ATO @ TiO obtained by doping conductive powder2The conductive powder is TiO coated by ATO nano particles2A nanowire. Wherein ATO @ TiO in nano microfiber unit2The content of the conductive powder was 20 wt%. ATO @ TiO2Coating of nano wire on TiO2The average thickness of the ATO nanoparticles of the nanowires was 8 nm. ATO @ TiO2The mass ratio of Sn to Ti in the nano wire is 10 percent. The Sb/Sn molar ratio in the ATO nanoparticles was 6%.
The composite nanowire of the present embodiment is prepared by the following method: obtaining microfluid spinning slurry; and controlling at least the following parameters of the advancing speed of an injection pump, the rotating speed of a motor and the translation speed of a stepping translation table in the microfluid spinning equipment to carry out microfluid spinning so as to obtain the composite nanowire. Specifically, 85g of absolute ethyl alcohol is taken, 3g of filler is added, the mixture is placed into an ultrasonic cleaning machine for ultrasonic treatment for 10min to enable the solution to become suspension, 12g of PVP solid powder is weighed and is continuously stirred and added into the absolute ethyl alcohol solution to promote the dissolution of the PVP solid powder, and 0.5g of deca-ethanol is addedAnd stirring the dialkyl sodium benzenesulfonate by using a magnetic stirrer until the solid powder is completely dissolved to prepare PVP ethanol solution with proper concentration. And (3) sucking a proper amount of prepared spinning solution by using an injector at normal temperature and normal pressure, mounting the injector on an injection pump, and setting parameters such as proper injection rate, injection amount and the like. Then, a polytetrafluoroethylene tube is connected with the injector and the micro-flow spinning machine, the distance between the spinning needle head and the receiver is adjusted, and the injection pump is started. The pinhole aperture of syringe needle is 0.65mm, and the spinning solution flows out by the syringe needle, sets up the rotation parameter of spinning machine, when the slide glass on the fibre connection receiver, can be under the effect of traction force, and continuous fibre is convoluteed in continuous drawing, in order to prevent piling up between the fibre, adjusts the step-by-step translation rate of spinning machine, can make the fibre take place the translation, just so can collect the parallel ATO @ TiO @ of equidistant2a/PVP microfilament array. Wherein the concentration of PVP in the microfluid spinning slurry is 12 wt%; ATO @ TiO in microfluid spinning slurry2The amount of the conductive powder is 3 wt%; the stepping translation speed is 1 mm/min; controlling the winding speed of the fiber collector to be 50 r/min; the syringe pump advance rates were 0.1mL/h, respectively. Here ATO @ TiO2The minimum resistivity of the/PVP blended fiber is 73K omega cm on average.
Example 2
The composite nanowire comprises a plurality of nano microfiber units, wherein each nano microfiber unit comprises a PVP (polyvinyl pyrrolidone) matrix and ATO @ TiO formed on the PVP matrix2Conductive powder, nano microfiber unit is ATO @ TiO2PVP microfiber, ATO @ TiO obtained by doping conductive powder2The conductive powder is TiO coated by ATO nano particles2A nanowire. Wherein ATO @ TiO in nano microfiber unit2The content of the conductive powder was 22 wt%. ATO @ TiO2Coating of nano wire on TiO2The average thickness of the ATO nanoparticles of the nanowires was 7 nm. ATO @ TiO2The mass ratio of Sn to Ti in the nano wire is 30 percent. The Sb/Sn molar ratio in the ATO nanoparticles was 8%.
The composite nanowire of the present embodiment is prepared by the following method: obtaining microfluid spinning slurry; controlling at least the following parameters of the advancing speed of an injection pump and the rotating speed of a motor in a microfluid spinning deviceAnd stepping the translation speed of the translation stage to carry out microfluid spinning to obtain the composite nanowire. Specifically, 85g of absolute ethyl alcohol is taken, 3.3g of filler is added, the mixture is placed into an ultrasonic cleaning machine for ultrasonic treatment for 30min to enable the solution to become a suspension, 11.7 g of PVP solid powder is weighed and continuously stirred and added into the absolute ethyl alcohol solution to promote the dissolution of the PVP solid powder, 0.5g of sodium dodecyl benzene sulfonate is added, a magnetic stirrer is used for stirring until the solid powder is completely dissolved, and the PVP ethyl alcohol solution with proper concentration is prepared. And (3) sucking a proper amount of prepared spinning solution by using an injector at normal temperature and normal pressure, mounting the injector on an injection pump, and setting parameters such as proper injection rate, injection amount and the like. Then, a polytetrafluoroethylene tube is connected with the injector and the micro-flow spinning machine, the distance between the spinning needle head and the receiver is adjusted, and the injection pump is started. The pinhole aperture of syringe needle is 0.85mm, and the spinning solution flows out by the syringe needle, sets up the rotation parameter of spinning machine, when the slide glass on the fibre connection receiver, can be under the effect of traction force, and continuous fibre is convoluteed in continuous drawing, in order to prevent piling up between the fibre, adjusts the step-by-step translation rate of spinning machine, can make the fibre take place the translation, just so can collect the parallel ATO @ TiO @ of equidistant2a/PVP microfilament array. Wherein the concentration of PVP in the microfluid spinning slurry is 11.7 wt%; ATO @ TiO in microfluid spinning slurry2The amount of the conductive powder is 3.3 wt%; the stepping translation speed is 2 mm/min; controlling the rotating speed of a motor for controlling the winding speed of the fiber collector to be 100 r/min; the syringe pump advance rates were 0.5mL/h, respectively. Here ATO @ TiO2The minimum resistivity of the/PVP blended fiber is 75K omega cm on average.
Example 3
The composite nanowire comprises a plurality of nano microfiber units, wherein each nano microfiber unit comprises a PVP (polyvinyl pyrrolidone) matrix and ATO @ TiO formed on the PVP matrix2Conductive powder, nano microfiber unit is ATO @ TiO2PVP microfiber, ATO @ TiO obtained by doping conductive powder2The conductive powder is TiO coated by ATO nano particles2A nanowire. Wherein ATO @ TiO in nano microfiber unit2The content of the conductive powder was 25 wt%. ATO @ TiO2Coating of nano wire on TiO2Average thickness of ATO nanoparticles of nanowiresThe degree was 10 nm. ATO @ TiO2The mass ratio of Sn to Ti in the nanowire is 15%. The molar ratio of Sb/Sn in the ATO nanoparticles was 10%.
The composite nanowire of the present embodiment is prepared by the following method: obtaining microfluid spinning slurry; and controlling at least the following parameters of the advancing speed of an injection pump, the rotating speed of a motor and the translation speed of a stepping translation table in the microfluid spinning equipment to carry out microfluid spinning so as to obtain the composite nanowire. Specifically, 85g of absolute ethyl alcohol is taken, 3.75 g of filler is added, the mixture is placed into an ultrasonic cleaning machine for ultrasonic treatment for 15min to enable the solution to become a suspension, 11.25 g of PVP solid powder is weighed and continuously stirred and added into the absolute ethyl alcohol solution to promote the dissolution of the PVP solid powder, 0.5g of sodium dodecyl benzene sulfonate is added, a magnetic stirrer is used for stirring until the solid powder is completely dissolved, and the PVP ethyl alcohol solution with proper concentration is prepared. And (3) sucking a proper amount of prepared spinning solution by using an injector at normal temperature and normal pressure, mounting the injector on an injection pump, and setting parameters such as proper injection rate, injection amount and the like. Then, a polytetrafluoroethylene tube is connected with the injector and the micro-flow spinning machine, the distance between the spinning needle head and the receiver is adjusted, and the injection pump is started. The pinhole aperture of syringe needle is 0.75mm, and the spinning solution flows out by the syringe needle, sets up the rotation parameter of spinning machine, when the slide glass on the fibre connection receiver, can be under the effect of traction force, and continuous fibre is convoluteed in continuous drawing, in order to prevent piling up between the fibre, adjusts the step-by-step translation rate of spinning machine, can make the fibre take place the translation, just so can collect the parallel ATO @ TiO @ of equidistant2a/PVP microfilament array. Wherein the concentration of PVP in the microfluid spinning slurry is 11.25 wt%; ATO @ TiO in microfluid spinning slurry2The amount of the conductive powder is 3.75 wt%; the stepping translation speed is 4 mm/min; controlling the winding speed of the fiber collector to be 200 r/min; the syringe pump advance rates were 0.75mL/h, respectively. Here ATO @ TiO2The minimum resistivity of the/PVP blended fiber is 73K omega cm on average.
Example 4
The composite nanowire comprises a plurality of nano microfiber units, wherein each nano microfiber unit comprises a PVP (polyvinyl pyrrolidone) matrix and ATO @ TiO formed on the PVP matrix2Conducting electricityThe nano microfiber unit of the powder is ATO @ TiO2PVP microfiber, ATO @ TiO obtained by doping conductive powder2The conductive powder is TiO coated by ATO nano particles2A nanowire. Wherein ATO @ TiO in nano microfiber unit2The content of the conductive powder was 30 wt%. ATO @ TiO2Coating of nano wire on TiO2The average thickness of the ATO nanoparticles of the nanowires was 3 nm. ATO @ TiO2The mass ratio of Sn to Ti in the nanowire is 25%. The molar ratio of Sb/Sn in the ATO nanoparticles was 5%.
The composite nanowire of the present embodiment is prepared by the following method: obtaining microfluid spinning slurry; and controlling at least the following parameters of the advancing speed of an injection pump, the rotating speed of a motor and the translation speed of a stepping translation table in the microfluid spinning equipment to carry out microfluid spinning so as to obtain the composite nanowire. Specifically, 85g of absolute ethyl alcohol is taken, 4.5g of filler is added, the mixture is placed into an ultrasonic cleaning machine for ultrasonic treatment for 25min to enable the solution to become suspension, 9.9g of PVP solid powder is weighed and continuously stirred and added into the absolute ethyl alcohol solution to promote the dissolution of the PVP solid powder, 0.5g of sodium dodecyl benzene sulfonate is added, a magnetic stirrer is used for stirring until the solid powder is completely dissolved, and the PVP ethanol solution with proper concentration is prepared. And (3) sucking a proper amount of prepared spinning solution by using an injector at normal temperature and normal pressure, mounting the injector on an injection pump, and setting parameters such as proper injection rate, injection amount and the like. Then, a polytetrafluoroethylene tube is connected with the injector and the micro-flow spinning machine, the distance between the spinning needle head and the receiver is adjusted, and the injection pump is started. The pinhole aperture of syringe needle is 0.5mm, and the spinning solution flows by the syringe needle, sets up the rotation parameter of spinning machine, when the slide glass on the fibre connection receiver, can be under the effect of traction force, and continuous fibre is convoluteed in continuous drawing, in order to prevent piling up between the fibre, adjusts the step-by-step translation rate of spinning machine, can make the fibre take place the translation, just so can collect the parallel ATO @ TiO @ of equidistant2a/PVP microfilament array. Wherein the concentration of PVP in the microfluid spinning slurry is 10 wt%; ATO @ TiO in microfluid spinning slurry2The amount of the conductive powder is 4.5 wt%; the stepping translation speed is 8 mm/min; controlling the rotating speed of a motor for controlling the winding speed of the fiber collector to be 300 r/min; the advancing rate of the injection pump is respectivelyIs 1 mL/h. Here ATO @ TiO2The minimum resistivity of the/PVP blended fiber is 77 omega cm on average.
Example 5
The composite nanowire comprises a plurality of nano microfiber units, wherein each nano microfiber unit comprises a PVP (polyvinyl pyrrolidone) matrix and ATO @ TiO formed on the PVP matrix2Conductive powder, nano microfiber unit is ATO @ TiO2PVP microfiber, ATO @ TiO obtained by doping conductive powder2The conductive powder is TiO coated by ATO nano particles2A nanowire. Wherein ATO @ TiO in nano microfiber unit2The content of the conductive powder was 23.1 wt%. ATO @ TiO2Coating of nano wire on TiO2The average thickness of the ATO nanoparticles of the nanowires was 5 nm. ATO @ TiO2The mass ratio of Sn to Ti in the nanowire is 20%. The Sb/Sn molar ratio in the ATO nanoparticles was 7%.
The composite nanowire of the present embodiment is prepared by the following method: obtaining microfluid spinning slurry; and controlling at least the following parameters of the advancing speed of an injection pump, the rotating speed of a motor and the translation speed of a stepping translation table in the microfluid spinning equipment to carry out microfluid spinning so as to obtain the composite nanowire. Specifically, 83.8g of absolute ethyl alcohol is taken, 4.5g of filler is added, the mixture is placed into an ultrasonic cleaning machine for ultrasonic treatment for 13min to enable the solution to become suspension, 15.8g of PVP solid powder is weighed and continuously stirred and added into the absolute ethyl alcohol solution to promote the dissolution of the PVP solid powder, 0.5g of sodium dodecyl benzene sulfonate is added, a magnetic stirrer is used for stirring until the solid powder is completely dissolved, and the PVP ethanol solution with proper concentration is prepared. And (3) sucking a proper amount of prepared spinning solution by using an injector at normal temperature and normal pressure, mounting the injector on an injection pump, and setting parameters such as proper injection rate, injection amount and the like. Then, a polytetrafluoroethylene tube is connected with the injector and the micro-flow spinning machine, the distance between the spinning needle head and the receiver is adjusted, and the injection pump is started. The pinhole aperture of syringe needle is 1.0mm, and the spinning solution flows by the syringe needle, sets up the rotation parameter of spinning machine, when the slide glass on the receiver is connected to the fibre, can be under the effect of traction force, and continuous fibre is convoluteed in continuous drawing, in order to prevent piling up between the fibre, adjusts the step-by-step translation rate of spinning machine, can make the fibre take place the translation, just so can be with regard toTo collect parallel ATO @ TiO ions at equal intervals2a/PVP microfilament array. Wherein the concentration of PVP in the microfluid spinning slurry is 15 wt%; ATO @ TiO in microfluid spinning slurry2The amount of the conductive powder is 4.5 wt%; the stepping translation speed is 4 mm/min; controlling the winding speed of the fiber collector to be 200 r/min; the syringe pump advance rates were 0.5mL/h, respectively. ATO @ TiO prepared by using microfluid spinning machine2the/PVP blended fiber has an average diameter of about 5 μm, uniform thickness, and substantially no adhesion and entanglement with each other. Here ATO @ TiO2The minimum resistivity of the/PVP blended fiber is 70K omega cm on average.
The schematic structural diagram of the microfluidic spinning device is shown in fig. 1, and the microfluidic spinning device mainly comprises a microfluidic injection pump 1 with stable propelling speed and a fiber receiving platform, and mainly comprises the following components: the device comprises a double-channel injection pump, an injector (a needle tube), a polytetrafluoroethylene tube, a needle head (the aperture of a needle hole is 0.5-1.0 mm), a flat receiver (a glass slide) 2, a rotating motor, a stepping translation table 3, a control panel and the like. The double-channel injection pump can respectively and independently control the propelling speed of the injectors of the two channels, and all the components of the microfluid spinning device are connected through polytetrafluoroethylene tubes.
In the following research, 85g of absolute ethyl alcohol is taken, a certain amount of filler is added, the mixture is placed into an ultrasonic cleaning machine for ultrasonic treatment for a period of time, the solution is made into turbid liquid, a certain amount of PVP solid powder is weighed, the PVP solid powder is continuously stirred and added into the absolute ethyl alcohol solution to promote the dissolution of the PVP solid powder, a small amount of sodium dodecyl benzene sulfonate is added, a magnetic stirrer is used for stirring until the solid powder is completely dissolved, and the PVP ethyl alcohol solution with proper concentration is prepared. And (3) sucking a proper amount of prepared spinning solution by using an injector at normal temperature and normal pressure, mounting the injector on an injection pump, and setting parameters such as proper injection rate, injection amount and the like. Then, a polytetrafluoroethylene tube is connected with the injector and the micro-flow spinning machine, the distance between the spinning needle head and the receiver is adjusted, and the injection pump is started. The spinning solution flows out from the needle head, the rotation parameters of the spinning machine are set, when the fiber is connected with the glass slide on the receiver, the continuous fiber can be continuously drawn and wound under the action of traction force, and in order to prevent the fiber from being separated from each otherThe fibers can be translated by adjusting the stepping translation speed of the spinning machine, so that the ATO @ TiO with equal spacing and parallel can be collected2a/PVP microfilament array.
Effect of PVP solution concentration on fiber formation
The microfluid spinning is carried out at normal temperature and normal pressure, and the spinning solution is guided by the gravity of the spinning solution except the reasoning of an injection pump in the whole continuous spinning process, so that the spinning solution is smoothly sprayed out from a needle head, and the finding of a proper solution concentration is very important for ensuring that the spinning solution can continuously carry out spinning. The PVP ethanol solution itself has a certain viscosity and the viscosity rises continuously with increasing concentration. When the concentration of the PVP ethanol solution is too low, the spinning is not easy to form, and when the concentration of the PVP ethanol solution is too high, the spinning solution with too high viscosity is easy to block a narrow spinning channel, so that the spinning is influenced. The four PVP ethanol solutions with the concentrations of 10 wt%, 15 wt%, 20 wt% and 25 wt% are respectively prepared by setting the equipment parameters of the micro-flow spinning machine to be 0.5ml/h of the propelling speed of an injection pump, 200r/min of the speed of a rotating motor and 4mm/min of stepping translation speed, and observing the prepared fiber morphology through a super-depth-of-field microscope. In the process, when the concentration of the PVP ethanol solution is 10 wt%, continuous microfibers are difficult to form due to the fact that the liquid is too thin and the viscosity is extremely poor; when the concentration of the PVP ethanol solution is 15 wt%, the orientation degree of the whole microfiber array is extremely high, the fibers are symmetrically spaced, the whole array is consistent and attractive, and the fiber forming effect is good; when the concentration of the PVP ethanol solution is 20 wt%, the uniformity of the fiber spacing is reduced, the fiber array is irregular, the fibers are too coarse or the inter-fiber connection is generated, and the attractiveness of the fibers is influenced; when the concentration of the PVP ethanol solution is 25 wt%, the viscosity of PVP is high, so that a needle head is easy to block, a spinning solution channel is poor in flowing, and spinning is difficult to perform. From this, the 15 wt% PVP ethanol solution concentration is the most suitable for micro-fluid spinning of the four concentrations selected.
Effect of rotating Electrical machine Rate on fiber formation
The winding speed of the fiber collector is controlled by the winding speed of the rotating motor, and the speed of the rotating motor has great influence on the interval between fibers, the thickness of the fibers and the like. The equipment parameters of the micro-flow spinning machine are set to be the propelling speed of an injection pump of 0.5ml/h, the concentration of PVP ethanol solution of 15 wt% and the stepping translation rate of 4mm/min at four different rotating speeds of a rotating motor of 50r/min, 100r/min, 200r/min and 300r/min, and the appearance of the manufactured fiber is observed through a super depth of field microscope. When the speed of the rotating motor is 50r/min, the traction drawing force of the collector is small due to the low rotating speed, and the fiber forming difficulty is large; when the speed of a rotating motor is 100r/min, the orientation degree of the whole microfiber array is obviously improved, the fibers are uniformly spaced, and the average thickness of the fibers is about 10 micrometers by random sampling measurement; when the speed of the rotating motor is 200r/min, the fiber space is uniform, the fiber array is regular, and the average diameter of the fibers is about 5 micrometers by random sampling measurement; when the speed of the rotating motor is 300r/min, the orientation degree of the fiber array is reduced, the fiber spacing is small, a single fiber is very thin, but the problem of adhesion among fibers is serious and the filamentation difficulty is high due to the fact that the spinning solution is high in viscosity and high in rotating speed. Therefore, when the speed of the rotary motor is 200r/min, the PVP microfiber array has uniform and neat fiber arrangement and distribution, the phenomenon of adhesion and yarn breakage is minimal, and the overall appearance is simple and attractive.
Effect of step translation speed on fiber formation
The function of the stepping translation stage is mainly to move in parallel to avoid mutual stacking of fibers when the fibers are collected, so that a regular and ordered fiber array is collected on a glass slide. The step translation speed directly affects the size of the space between fibers. In four different stepping translation speeds of 1mm/min, 2mm/min, 4mm/min and 8mm/min, the equipment parameters of the micro-flow spinning machine are set as the propelling speed of an injection pump of 0.5ml/h, the concentration of PVP ethanol solution is 15 wt% and the speed of a rotating motor is 200r/min, and the appearance of the manufactured fiber is observed by a super depth of field microscope.
When the stepping translation speed is 1mm/min, the fiber intervals are too dense, and the stacking phenomenon occurs, so that most fibers are adhered and compounded; when the stepping translation speed is 2mm/min, the whole microfiber array has high orientation degree, and the average spacing between fibers is about 135 micrometers; when the stepping translation speed is 4mm/min, the average spacing is about 155 micrometers, the fibers are uniformly distributed, and the integral compactness of the fiber array is moderate; when the stepping translation speed is 8mm/min, the stepping translation speed is too high, the integral orientation degree of the fibers is poor, the average spacing is about 260 micrometers, the fibers are sparsely distributed, the integral fiber array is not compact, and the distribution effect is poor. Therefore, when the stepping translation speed of the PVP microfiber array is 4mm/min, the fibers are uniformly and tidily arranged and distributed, and the overall appearance is concise and attractive.
Influence of the speed of the injection pump on the formation of fibres
The speed of the syringe pump is directly influenced by the flow rate of the spinning solution and thus the extrusion speed of the spinning solution at the spinning tip, and in order to achieve the best microfiber array distribution, the speed of the syringe pump should be matched with the rotation speed of the slide. Therefore, PVP ethanol solution with the concentration of 25 wt% is selected, the speed of a rotating motor is uniformly set to be 200r/min, the stepping translation speed is 4mm/min, the propelling speed of an injection pump is respectively 0.1mL/h, 0.5mL/h and 1mL/h, and the arrangement distribution condition of the fibers is observed through a 3D super-depth-of-field microscope.
It is observed that when the push rate of the injection pump is 0.1mL/h, the spun fibers are not continuous due to the low push rate, and the fibers are thin and easy to break; when the propelling speed of the injection pump is 0.5mL/h, the fiber forming effect is good, the fiber orientation degree is high, the fiber distribution is relatively neat and uniform, the intervals among the fibers are slightly large, the average diameter of the fibers measured by random sampling (5 fibers) is about 3 micrometers, and the overall fiber arrangement effect is good; when the propelling speed of the injection pump is 1mL/h, the propelling speed of the liquid is not matched with the rotating speed of the glass slide due to the fact that the extruding speed of the liquid is too high, liquid drops at the needle head are lumpy, the fiber array is locally seriously adhered and broken, the doubling phenomenon is caused, the integral arrangement effect of the fibers is poor, and more liquid is remained at two sides of the glass slide in reality, so that the propelling speed is not proper. Therefore, the change of the advancing speed of the injection pump does not have great influence on the thickness of the fibers, but has great influence on the overall arrangement effect of the fiber array, the phenomena of doubling, fiber adhesion and yarn breakage can be more serious when the speed is too high, and 0.5mL/h is the most suitable for preparing the PVP microfiber array in the four advancing speeds.
Effect of Filler addition on fiber formation
ATO@TiO2Filler (i.e. ATO @ TiO)2Conductive powder) has certain influence on the overall structure of the PVP fiber, so ATO @ TiO2The addition amount of the filler directly affects the moldability of the blended fiber. Therefore, PVP ethanol solution with the concentration of 25 wt% is selected as spinning solution, the advancing speed of an annotation pump is uniformly set to be 0.5mL/h, the stepping translation speed is 4mm/min, the speed of a rotating motor is 200r/min, and ATO @ TiO is adopted2The crystal whisker addition amounts are 3.5 wt%, 4.5 wt% and 5.5 wt%, spinning is carried out, and ATO @ TiO is carried out by a 3D super depth of field microscope after spinning2And observing and comparing the appearance of the/PVP blended fiber. When ATO @ TiO2When the adding amount of the crystal whisker is 3.5 wt%, the fiber forming is not influenced, the formed fibers have uniform thickness, are not tangled with each other, and have better dispersibility. When ATO @ TiO2When the adding amount of the whiskers is 4.5 wt%, the fiber forming is influenced, the fiber forming is basically smooth, and the thickness and the fiber array arrangement of the fibers are reduced by a certain length. When ATO @ TiO2When the amount of the whisker is 5.5 wt%, the fiber is difficult to form, the gel is difficult to extrude from the needle head, and the formed fiber has poor continuity, is intermittent, is easy to have defects and has poor spinnability.
In order to further observe the surface morphology of the PVP fiber, the optimal process conditions are selected, the mass fraction of the PVP ethanol solution is 15%, the propelling speed of an injection pump is 0.1mL/h, the stepping translation speed is 4mm/min, and the speed of a rotating motor is 200r/min to prepare ATO @ TiO2the/PVP blend fiber was subjected to SEM testing. A part of PVP fiber is selected by tweezers, adhered to a conductive adhesive, subjected to gold spraying for 60s under the condition of 90mA, and then tested under the conditions that the voltage is 3KV and the current is 10 mA.
FIG. 5 shows ATO @ TiO prepared by micro-fluid spinning2SEM picture of/PVP blend fiber, and observation of FIG. 5(a) shows that the prepared PVP fiber has uniform size and thickness, about 3 μm fiber diameter and regular shape. Viewing FIG. 5(b), the ATO @ TiO prepared2the/PVP blend fiber had a varying surface roughness of about 5 microns in diameter and was analyzed as a fillingThe addition of the material has certain influence on the internal structure of the PVP fiber, and causes the change of the surface of the fiber.
Because of pure TiO2The nanowire is not conductive, so the addition of the coating agent ATO in the experiment provides a necessary condition for the generation of the conductive layer, wherein the mass ratio of Sn/Ti determines the mass ratio of ATO in TiO2The coating condition of the surface and the thickness of the formed film, and the completeness of the conductive layer directly determines the conductivity of the composite whisker. According to theoretical analysis, ATO @ TiO2The content of ATO in the composite whisker has a percolation threshold, and before the threshold is reached, a conductive network in the material cannot be formed, and the resistivity cannot be obviously changed along with the increase of the content of ATO. When the content reaches the threshold, the resistivity starts to drop rapidly. FIG. 2 shows the effect of Sn/Ti mass ratio on the conductivity of whiskers, ATO @ TiO when the ATO addition is small, i.e., the Sn/Ti mass ratio is small2The electrical resistivity of the composite whisker is very large; when the mass ratio of Sn/Ti is 10-15%, the ATO nano-particles are arranged more and more closely and begin to be piled up continuously, and the conductive path is converted to the conductive network, so that the resistivity of the composite crystal whisker is reduced rapidly. However, when the resistivity of the alloy reaches a certain proportion of 20%, the resistivity of the alloy slowly rises, and the analysis reason is that ATO @ TiO2The content of ATO in the composite whisker has a threshold value, and after the threshold value is reached, the thickness of the film is continuously increased, so that more and more crystal interfaces are needed to pass through by current carriers in the transmission process, and the conduction is not facilitated. Therefore, the Sn/Ti mass ratio is not as high as possible in view of the cost of raw materials.
Due to SnO2The conductivity of the material is poor, and the material needs to be doped to improve the performance. The influence of the molar ratio of Sb to Sn on the conductivity of the composite whisker is mainly realized by influencing the doping effect of ATO. As can be seen from fig. 3, the electrical resistivity of the whiskers decreased rapidly with increasing Sb to Sn molar ratio, followed by a slow increase. Because the element radius of Sb5+ is less than Sn4+ when the addition amount of Sb is increased and is within 5 percent, the Sb is easily doped into Sn02 crystal lattices after high-temperature calcination, and SnO is changed2The band structure of (2) obtains more conductive carriers, greatly improves the conductivity of ATO. With followingThe continuous increase of the addition amount of Sb can form more and more electron donors, the carrier concentration is increased along with the increase of Sb addition amount, and the resistivity is continuously reduced. When the amount of Sb added increases to 7%, a significant tendency to rise begins to appear again, which may be attributed to the upper limit of Sb doping in Sn 02. When Sb is too much, lattice distortion may occur, so that doping efficiency may be lowered, which is not favorable for crystal conduction.
As shown in FIG. 4, ATO @ TiO2The conductive whiskers are taken as the core part of the conductive fiber, and the content of the conductive whiskers is an essential factor for determining the conductive performance of the PVP fiber. With ATO @ TiO2The content is increased, and the conductivity of the fiber is also increased. ATO @ TiO2The conductive principle of the/PVP blended fiber is that a conductive filler is added, and the conductive filler ATO @ TiO2The whiskers are structurally communicated in the PVP fiber to form a power-on network, and theoretically, the added conductive filler ATO @ TiO2The more whiskers, the easier the formation of the electrified network, and the more electrified networks can form a plurality of parallel circuits, and the increase of the parallel circuits can effectively reduce the total resistance of the fibers, thereby achieving the effect of reducing the resistivity of the fibers. When considering the influence of two factors, namely resistivity and spinnability, as ATO @ TiO2When the addition amount is 4.5 wt%, the average resistivity of the fiber is 70K omega cm, and ATO @ TiO is continuously increased2The spinnability is rapidly reduced by the addition amount of the whiskers. So when ATO @ TiO2When the addition amount is 4.5 wt%, the minimum resistivity of the blend fiber is 70K omega cm on average.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (5)

1. The preparation method of the composite nanometer microfiber array comprises the following steps:
obtaining microfluid spinning slurry;
controlling at least the following parameters of the advancing speed of an injection pump, the rotating speed of a motor and the translation speed of a stepping translation table in microfluid spinning equipment, and performing microfluid spinning to obtain a composite nano-microfiber array, wherein the stepping translation speed in the microfluid spinning is 1-8mm/min, and the motor rotating speed of the winding speed of a fiber collector in the microfluid spinning is 50r/min-300 r/min:
the prepared composite nano microfiber array comprises a plurality of nano microfiber units, wherein each nano microfiber unit comprises a PVP (polyvinyl pyrrolidone) matrix and ATO @ TiO (antimony tin oxide) formed on the PVP matrix2The nanometer microfiber unit is ATO @ TiO2PVP microfiber obtained by doping conductive powder, ATO @ TiO2The conductive powder is TiO coated by ATO nano particles2Nanowire, said ATO @ TiO2The mass ratio of Sn/Ti in the nano-wire is 10-30%, the molar ratio of Sb/Sn in the ATO nano-particles is 5-10%, and the propelling speed of an injection pump during microfluid spinning is 0.1-1 mL/h.
2. The composite nano-microfiber array prepared according to the method of claim 1, comprising a plurality of nano-microfiber units, wherein the nano microfiber units comprise a PVP matrix and ATO @ TiO formed on the PVP matrix2The nanometer microfiber unit is ATO @ TiO2PVP microfiber obtained by doping conductive powder, ATO @ TiO2The conductive powder is TiO coated by ATO nano particles2Nanowire, said ATO @ TiO2The mass ratio of Sn/Ti in the nano wire is 10-30%, and the molar ratio of Sb/Sn in the ATO nano particles is 5-10%.
3. The array of composite nano-microfibers according to claim 2, wherein the nano-microfibers are ATO @ TiO units2The content of the conductive powder is 20-30 wt%.
4. The composite nano-microfiber array according to claim 2, wherein said ATO @ TiO2Coating of nano wire on TiO2The average thickness of the ATO nanoparticles of the nanowires is 3-10 nm.
5. The composite Nanofibre array according to claim 4, wherein said ATO @ TiO2Coating of nano wire on TiO2The average thickness of the ATO nanoparticles of the nanowires was 5 nm.
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