阅读说明：本技术 复合纳米线及其制备方法 (Composite nanowire and preparation method thereof ) 是由 陈宇岳 杨熙 张庆军 林红 张德锁 张骜 于 2020-06-24 设计创作，主要内容包括：本发明复合纳米微纤阵列及其制备方法,其中微纤阵列包括若干纳米微纤单元,纳米微纤单元包括PVP基体以及形成于PVP基体上的ATO@TiO<Sub>2</Sub>导电粉,纳米微纤单元为ATO@TiO<Sub>2</Sub>导电粉掺杂获得的PVP微纤,ATO@TiO<Sub>2</Sub>导电粉为ATO纳米颗粒包覆TiO<Sub>2</Sub>纳米线。本发明方案制备的纳米微纤阵列,取向性好,且具有良好的导电性,在抗静电、电磁屏蔽、特种导电等多方面具有良好的应用前景。(The invention relates to a composite nanometer microfiber array and a preparation method thereof, wherein the microfiber array comprises a plurality of nanometer microfiber units, each nanometer microfiber unit comprises a PVP (polyvinyl pyrrolidone) matrix and ATO @ TiO (antimony tin oxide) formed on the PVP matrix 2 Conductive powder, nano microfiber unit is ATO @ TiO 2 PVP microfiber, ATO @ TiO obtained by doping conductive powder 2 The conductive powder is TiO coated by ATO nano particles 2 A 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.)

1. The composite nanometer microfiber array comprises a plurality of nanometer microfiber units, wherein each nanometer 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 particles₂A nanowire.

2. The composite nano-microfiber array according to claim 1, wherein the content of ATO @ TiO2 conductive powder in the nano microfiber unit is 20 to 30 wt%.

3. The composite Nanofibre array according to claim 1, wherein the ATO @ TiO₂Coating of nano wire on TiO₂The average thickness of the ATO nanoparticles of the nanowires is 3-10 nm.

4. The composite nano-microfiber array according to claim 3, wherein the composite nano-microfiber array is characterized in thatIn that the ATO @ TiO₂Coating of nano wire on TiO₂The average thickness of the ATO nanoparticles of the nanowires was 5 nm.

5. The composite Nanofibre array according to claim 1, wherein the ATO @ TiO₂The mass ratio of Sn to Ti in the nano wire is 10-30%.

6. The array of composite nano-and microfibers according to any of claims 1 to 4, wherein the molar ratio of Sb/Sn in the ATO nanoparticles is 5 to 10%.

7. The preparation method of the composite nanometer microfiber array 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 nanometer microfiber array.

8. The method for preparing the composite nano-microfiber array according to claim 7, wherein the step translation speed during microfluid spinning is 1 to 8 mm/min.

9. The method for preparing a composite nano-microfiber array according to claim 8, wherein a motor rotation speed of a winding speed of a fiber collector during micro-fluid spinning is 50r/min to 300 r/min.

10. The method for preparing a composite nano-microfiber array according to claim 9, wherein the injection pump advancing rate during microfluid spinning is 0.1 to 1mL/h, respectively.

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 invention discloses a composite nanowire and a preparation method thereof, and provides a conductive PVP composite nano microfiber array and a preparation method thereof by adopting a microfluid spinning technology, wherein the preparation efficiency is high, the forming effect is good, and therefore the composite nanowire and the preparation method have good universality and popularization performance.

The invention discloses a composite nanometer microfiber array, which comprises a plurality of nanometer microfiber units, wherein the nanometer microfiber units comprise PVPSubstrate and ATO @ TiO formed on PVP substrate₂Conductive 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 nanometer microfiber array, wherein the content of ATO @ TiO2 conductive powder in a nanometer microfiber unit is 20-30 wt%.

The invention discloses an improvement of a composite nanometer microfiber array, 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 a composite nanometer microfiber array, 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 a composite nanometer microfiber array, ATO @ TiO₂The mass ratio of Sn to Ti in the nano wire is 10-30%.

The invention discloses an improvement of a composite nanometer microfiber array, wherein the molar ratio of Sb to Sn in ATO nanometer particles is 5-10%.

The invention discloses a preparation method of a composite nanometer microfiber array, 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 nanometer microfiber array.

The invention discloses an improvement of a preparation method of a composite nanometer microfiber array, wherein the stepping translation speed is 1-8 mm/min.

The invention discloses an improvement of a preparation method of a composite nanometer microfiber array, wherein 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 nanometer microfiber array, wherein the propelling speed of an injection pump is 0.1-1mL/h respectively.

The invention discloses an improvement of a preparation method of a composite nano microfiber array, wherein microfluid spinning slurry is a system taking ethanol as a dispersing solvent.

The invention discloses an improvement of a preparation method of a composite nano microfiber array, wherein the concentration of PVP in microfluid spinning slurry is 10-15 wt%.

The invention discloses an improvement of a preparation method of a composite nano microfiber array, namely ATO @ TiO in microfluid spinning slurry₂The amount of the conductive powder is 3-4.5 wt%.

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 a composite nano-microfiber array according to the present application;

FIG. 2 shows ATO @ TiO in the composite nanofiber array of the present application₂Resistivity of composite nanowire with Sn/Ti a change curve of the molar mass ratio;

FIG. 3 shows ATO @ TiO in the composite nanofiber array 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 nanofiber array of the present application₂The equivalent circuit schematic diagram of the composite nanowire is shown;

FIG. 5 shows ATO @ TiO in the composite nanofiber array of the present application₂SEM pictures of one embodiment of composite nanowires, wherein (a) is PVP fiber; (b) is ATO @ TiO₂The PVP microfiber, the mass fraction of the PVP in the ethanol solution is 15%, the propelling speed of the injection pump is 0.1mL/h, the stepping translation speed is 4mm/min, the speed of the rotating motor is 200r/min, and the width of the coiled plate 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.