阅读说明：本技术 微流纺丝浆料及其应用 (Micro-flow spinning slurry and application thereof ) 是由 张庆军 杨熙 张骜 张德锁 林红 陈宇岳 于 2020-06-24 设计创作，主要内容包括：本发明微流纺丝浆料及其应用,其中微流纺丝浆料为在有机溶剂中分散有PVP、填料以及分散剂并形成均匀体系,其中PVP在该体系的含量为10wt％-15wt％；填料在该体系中的含量为3wt％-4.5wt％；分散剂在该体系中的含量为0.48wt％-0.5wt％。本发明方案浆料在制备的纳米微纤中成型性好,产品具有较高的取向性,操作便利,生产高效。(The invention relates to micro-flow spinning slurry and application thereof, wherein the micro-flow spinning slurry is formed by dispersing PVP, a filler and a dispersing agent in an organic solvent to form a uniform system, wherein the content of the PVP in the system is 10-15 wt%; the content of the filler in the system is 3-4.5 wt%; the content of the dispersant in the system is 0.48 wt% to 0.5 wt%. The slurry prepared by the scheme of the invention has good formability in the prepared nano microfiber, and the product has higher orientation, is convenient to operate and has high production efficiency.)

1. The micro-flow spinning slurry is formed by dispersing PVP, a filler and a dispersing agent in an organic solvent to form a uniform system, wherein the content of the PVP in the system is 10-15 wt%; the content of the filler in the system is 3-4.5 wt%; the content of the dispersant in the system is 0.48 wt% to 0.5 wt%.

2. The micro-spinning slurry according to claim 1, wherein the organic solvent is an alcohol solvent of C1-6.

3. The micro-spinning slurry according to claim 2, wherein the organic solvent is one or a mixture of ethanol, propanol, 1, 3-propanediol, and methyl glycol.

4. The micro-spinning slurry of claim 3, wherein said organic solvent is ethanol.

5. Micro-flow spinning slurry according to claim 1, characterised in that said filler is ATO @ TiO₂A nanowire.

6. Micro-flow spinning slurry according to claim 5, characterised in that said ATO @ TiO₂The mass ratio of Sn to Ti in the nano wire is 10-30%.

7. Micro-flow spinning slurry according to claim 5, characterised in that said ATO @ TiO₂The mol ratio of Sb/Sn in the ATO nano particles coated on the nano wire is 5-10%.

8. The micro-flow spinning slurry of claim 7, wherein said ATO @ TiO₂The average coating thickness of the ATO nanoparticles on the nanowires is 3-10 nm.

9. The micro-flow spinning slurry of claim 8, wherein said ATO @ TiO₂The average coating thickness of the ATO nanoparticles on the nanowires was 5 nm.

10. The application of the micro-flow spinning slurry in the preparation of nano micro-fiber.

Technical Field

The invention belongs to the technical field of nano material processing and preparation, and particularly relates to micro-flow spinning slurry and application 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 spinning method thereof provided by the invention have the advantages that the spinning slurry technology is adopted, the preparation efficiency is high, the forming effect is good, and the composite nanowire and the spinning method thereof are good in forming process.

The invention discloses a microflow spinning slurry, which is formed by dispersing PVP, a filler and a dispersant in an organic solvent to form a uniform system, wherein the content of the PVP in the system is 10-15 wt%; the content of the filler in the system is 3-4.5 wt%; the content of the dispersant in the system is 0.48 wt% to 0.5 wt%.

The invention discloses an improvement of micro-flow spinning slurry, wherein the organic solvent is an alcohol solvent of C1-6.

The invention discloses an improvement of micro-flow spinning slurry, wherein an organic solvent is one or a mixture of ethanol, propanol, 1, 3-propylene glycol and methyl glycol. Further preferably, the organic solvent is ethanol.

The invention discloses an improvement of microflow spinning slurry, wherein the filler is ATO @ TiO₂A nanowire.

The invention discloses an improvement of microflow spinning slurry, ATO @ TiO₂The mass ratio of Sn to Ti in the nano wire is 10-30%.

The invention discloses an improvement of microflow spinning slurry, ATO @ TiO₂The mol ratio of Sb/Sn in the ATO nano particles coated on the nano wire is 5-10%.

The invention discloses an improvement of microflow spinning slurry, ATO @ TiO₂The average coating thickness of the ATO nanoparticles on the nanowires is 3-10 nm. Further preferred, ATO @ TiO₂The average coating thickness of the ATO nanoparticles on the nanowires was 5 nm.

The invention discloses application of micro-flow spinning slurry in preparation of nano micro-fibers. In particular to the preparation of ATO @ TiO by the microfluid spinning technology₂Use of/PVP blend fibres or arrays thereof.

The invention discloses a spinning method of micro-flow spinning slurry, which comprises the following steps:

obtaining microfluid spinning slurry;

and controlling at least the following parameters of the propelling 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 microfluid spinning slurry.

The invention discloses an improvement of a spinning method of micro-flow spinning slurry, wherein the micro-flow spinning slurry is a system taking ethanol as a dispersing solvent.

The invention discloses an improvement of a spinning method of micro-flow spinning slurry, and the stepping translation speed is 1-8 mm/min.

The invention discloses an improvement of a spinning method of micro-flow spinning slurry, 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 spinning method of micro-flow spinning slurry, and the propelling speeds of injection pumps are 0.1-1mL/h respectively.

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 view of a spinning process for microfluid spinning slurries of the present application;

FIG. 2 is a drawing of ATO @ TiO in a micro-flow spinning dope of the present application₂The change curve of the resistivity of the composite nanowire along with the Sn/Ti molar mass ratio;

FIG. 3 is a view of the microfluid spinning of the present applicationATO @ TiO in slurry₂The resistivity of the composite nanowire changes along with the Sb/Sn molar ratio;

FIG. 4 is a drawing of ATO @ TiO in a micro-flow spinning dope of the present application₂The equivalent circuit schematic diagram of the composite nanowire is shown;

FIG. 5 is a drawing of ATO @ TiO in a micro-flow spinning dope 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.