CN113622038A - Needle-free solution air spinning equipment and application thereof - Google Patents

Abstract

The invention discloses a pinless solution gas spinning device and application thereof, wherein the pinless solution gas spinning device comprises a gas supply unit, a continuous liquid supply unit and a collection unit, the gas supply unit comprises a compressed gas supply device and a gas injection device, the compressed gas supply device and the gas injection device are connected through a pipeline, and a pressure reducing valve is arranged on the pipeline; the continuous liquid supply unit comprises a solution tank, a spinning solution conveying device and a power rolling shaft, a supporting shaft is arranged in the solution tank, the spinning solution is contained in the solution tank, the supporting shaft is located below the liquid level of the spinning solution, the power rolling shaft is arranged above the solution tank, the power rolling shaft and the supporting shaft are in transmission connection through the spinning solution conveying device, the air injection device is arranged between the power rolling shaft and the supporting shaft, and the air injection direction of the air injection device faces towards the spinning solution conveying device; the collecting unit is arranged at the downstream of the air injection device. Therefore, the spinning equipment has the advantages of high spinning efficiency, wide application range, no needle blockage problem and the like.

Description

Needle-free solution air spinning equipment and application thereof

Technical Field

The invention belongs to the technical field of fiber spinning, and particularly relates to a needle-free solution gas spinning device and application thereof.

Background

The micro-nano fiber is a linear material with a diameter of micron or nanometer scale, a large length and a certain length-diameter ratio. The micro-nano fiber plays an important role in various novel functional materials due to the unique physical and chemical properties of the micro-nano fiber.

At present, common methods for preparing micro-nanofibers include wet spinning, melt-blown spinning, electrostatic spinning, solution gas spinning, centrifugal spinning and the like. Melt-blown spinning has the advantage of high production efficiency and is a widely used spinning method in industry. However, the fibers produced by melt-blown spinning have large diameters and very limited types of fibers are available. The electrostatic spinning is a simple and convenient method for preparing the micro-nano fiber at present, and has the advantages of wide application range, simple operation and the like. However, the electrostatic spinning production efficiency is low, and the solution is extruded through the spinning nozzle to form filaments, so that the spinning nozzle is easily blocked. Therefore, it is necessary to develop a spinning device with high spinning efficiency, wide application range and no needle blockage problem.

Disclosure of Invention

The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide the needle-free solution gas spinning equipment and the application thereof.

In one aspect of the invention, the invention provides a pinless solution air spinning apparatus. According to an embodiment of the present invention, the needle-less solution gas spinning apparatus comprises:

the gas supply unit comprises a compressed gas supply device and a gas injection device, the compressed gas supply device is connected with the gas injection device through a pipeline, and a pressure reducing valve is arranged on the pipeline;

the continuous liquid supply unit comprises a solution tank, a spinning solution conveying device and a power rolling shaft, a supporting shaft is arranged in the solution tank, the spinning solution is contained in the solution tank, the supporting shaft is located below the liquid level of the spinning solution, the power rolling shaft is arranged above the solution tank, the power rolling shaft is in transmission connection with the supporting shaft through the spinning solution conveying device, the air injection device is arranged between the power rolling shaft and the supporting shaft, and the air injection direction of the air injection device faces the spinning solution conveying device;

a collection unit disposed downstream of the air jet device.

According to the pinless solution gas spinning device provided by the embodiment of the invention, by opening the compressed gas supply device and the pressure reducing valve, gas can be supplied and the pressure and flow rate of the gas can be regulated, and then the gas is sprayed out of the gas spraying device in the form of gas flow; simultaneously, under the drive of power roller bearing and back shaft, spinning liquid conveyor realizes the reel-to-reel continuous motion, constantly carries the spinning liquid of splendid attire in the solution tank to air jet system department, and under the effect of high velocity air, the solution of adhesion on the spinning liquid conveyor is drafted and becomes the efflux to utilize the collection unit to collect and obtain micro-nanofiber. From this, the no syringe needle solution air spinning equipment application scope of this application is wide, can be used to produce various organic, inorganic micro-nanofiber and load particulate matter's micro-nanofiber material, in addition, compare in traditional electrostatic spinning production efficiency lower, and extrude solution filamentation through spinning nozzle, the condition that spinning nozzle blockked up appears easily, the no syringe needle solution air spinning equipment production efficiency of this application is high, has good scale production prospect, and need not to use the spinneret, the problem of solution stifled needle has been avoidd, be favorable to the popularization of industrialization.

In addition, the pinless solution air spinning device according to the above embodiment of the present invention may further have the following additional technical features:

in some embodiments of the present invention, the power roller is parallel to the support shaft, and the spinning solution feeding means is disposed vertically to a horizontal plane. Therefore, the spinning solution conveying device can realize reel-to-reel movement, so that the spinning solution in the solution tank is carried to the air injection device from the solution tank.

In some embodiments of the present invention, the air blowing direction of the air blowing device is perpendicular to the spinning solution conveying device. Therefore, the air flow sprayed by the air spraying device can spray and draw the solution carried by the spinning solution conveying device.

In some embodiments of the invention, the gas injection device is a hollow tube or an air knife.

In some embodiments of the invention, the spinning fluid delivery device is a single wire, a plurality of wires, or a mesh. The spinning solution can thus be transported from the solution tank to the gas jet by adhesion of the spinning solution to the material.

In some embodiments of the present invention, the spinning solution conveying device is a plurality of threads which are disposed on the power roller and the support shaft at intervals, and the air injection device is a plurality of hollow tubes or air knives which are located inside a space surrounded by the plurality of threads, air outlets of a plurality of air holes of the plurality of hollow tubes are respectively directed toward a single thread of the plurality of threads, and air outlets of the air knives are directed toward the plurality of threads. Thus, the spinning solution adhering to the plurality of threads can be spun at the same time, and the spinning efficiency is further improved.

In some embodiments of the present invention, the spinning solution conveying device is a mesh, the air jet device is an air knife, the air knife is located inside a space surrounded by the mesh, and an air outlet direction of the air knife is perpendicular to the mesh. Therefore, the spinning solution adhered to the screen cloth can be spun simultaneously, and the spinning efficiency can be further improved.

In some embodiments of the invention, the diameter of the single wire and the plurality of wires is 0.1 to 0.5 mm. Therefore, the spinning efficiency is high, and the prepared micro-nano fibers are good in quality.

In some embodiments of the present invention, the mesh number of the mesh cloth is 10-800 mesh. Therefore, the spinning efficiency is high, and the prepared micro-nano fibers are good in quality.

In some embodiments of the present invention, the continuous liquid supply unit further comprises a driven roller cooperating with the power roller to press the spinning liquid feeding device. Therefore, on one hand, the friction force can be increased through extrusion, and the transmission of the spinning solution conveying device is facilitated; on the other hand, the spinning solution feeding device may be made to continue the roll-to-roll motion along a predetermined trajectory.

In a second aspect of the invention, the invention provides a method for spinning by using the needle-free solution gas spinning device. According to an embodiment of the invention, the method comprises:

(1) opening the compressed gas supply device and the pressure reducing valve so as to enable the gas spraying device to spray gas flow;

(2) the spinning solution conveying device conveys the spinning solution contained in the solution tank to the air jet device under the driving of the power roller and the supporting shaft, and the air flow carries out blowing and drafting on the solution carried by the spinning solution conveying device and is collected by the collecting unit to obtain the micro-nano fibers.

According to the method for spinning by using the pinless solution gas spinning device, disclosed by the embodiment of the invention, by opening the compressed gas supply device and the pressure reducing valve, gas can be supplied and the pressure and the flow rate of the gas can be regulated, and then the gas is sprayed out of the gas spraying device in the form of gas flow; simultaneously, under the drive of power roller bearing and back shaft, spinning liquid conveyor realizes the reel-to-reel continuous motion, constantly carries the spinning liquid of splendid attire in the solution tank to air jet system department, and under the effect of high velocity air, the solution of adhesion on the spinning liquid conveyor is drafted and becomes the efflux, utilizes the collection unit to collect and obtains micro-nanofiber. Therefore, the spinning method is wide in application range, can be used for producing various organic and inorganic micro-nano fibers and micro-nano fiber materials loaded with particles, is low in production efficiency compared with the traditional electrostatic spinning, and can be used for extruding solution to form yarns through spinning nozzles, so that the condition that the spinning nozzles are blocked is easy to occur.

In addition, the method for spinning by using the pinless solution gas spinning device according to the above embodiment of the present invention may further have the following additional technical features:

in some embodiments of the present invention, in the step (2), the spinning solution includes a polymer solution or a mixed solution containing a polymer and an inorganic precursor.

In some embodiments of the present invention, the polymer material in the polymer solution or the mixed solution containing a polymer and an inorganic precursor includes at least one of polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polyvinyl butyral, polyethylene glycol, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyvinylidene fluoride, polystyrene, polyurethane, polymethyl methacrylate, polylactic acid, polycaprolactone, polyether sulfone, polyimide, polyamide, cellulose acetate, methyl cellulose, carboxymethyl cellulose, polyaniline, and polycarbonate.

In some embodiments of the present invention, the solvent of the spinning dope includes at least one of water, methanol, ethanol, N-butanol, N-propanol, isopropanol, hexafluoroisopropanol, t-butanol, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetone, acetylacetone, butanone, N-hexane, cyclohexane, N-heptane, acetonitrile, dichloromethane, chloroform, carbon tetrachloride, toluene, xylene, formic acid, and tetrahydrofuran.

In some embodiments of the invention, the inorganic precursor comprises ethyl orthosilicate, methyl orthosilicate, aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum isopropoxide, aluminum acetylacetonate, tetrabutyl titanate, isobutyl titanate, titanium isopropoxide, zirconium oxychloride, zirconium acetate, zirconium n-propoxide, zirconium n-butoxide, zirconium hydroxide, zirconium acetylacetonate, yttrium nitrate, yttrium acetate, copper chloride, copper acetate, hafnium tetrachloride, hafnium sulfate, hafnium n-butoxide, hafnium ethoxide, hafnium hydroxide, hafnium oxychloride, hafnium oxynitrate, barium acetate, tin chloride, tantalum pentachloride, cobalt acetate, zinc acetate, nickel acetate, titanium isopropoxide, cerium nitrate, magnesium acetate, zinc nitrate, silver nitrate, tantalum isopropoxide, niobium acetate, iron chloride, iron citrate, germanium isopropoxide, manganese acetate, indium nitrate, polycarbosilane, chromium nitrate, chromium chloride, tungsten isopropoxide, magnesium nitrate, iron nitrate, silver nitrate, tantalum isopropoxide, niobium nitrate, iron nitrate, germanium isopropoxide, manganese acetate, indium nitrate, chromium chloride, tungsten isopropoxide, magnesium nitrate, iron nitrate, aluminum titanate, isobutyl titanate, titanium isopropoxide, hafnium nitrate, or a salt, At least one of manganese chloride and cobalt nitrate;

in some embodiments of the invention, the polymer solution has particulates dispersed therein.

In some embodiments of the invention, the particulate matter comprises at least one of silica, alumina, titania, zirconia, ceria, vanadia, chromia, manganese dioxide, triiron tetroxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, and yttrium oxide.

In some embodiments of the invention, the gas stream has a gauge pressure of 0.01 to 0.5 MPa. Therefore, under the action of high-speed airflow, the solution adhered to the spinning solution conveying device is drawn into jet flow, and continuous, uniform and high-quality micro-nano fibers are obtained.

In some embodiments of the present invention, in the step (2), the speed of the spinning solution conveying device is 0.5 to 10 cm/s. Therefore, by adopting the speed of the spinning solution conveying device, on one hand, the spinning solution on the spinning solution conveying device can be prevented from drying up; on the other hand, the method is beneficial to obtaining high-quality micro-nano fibers.

In some embodiments of the present invention, the distance between the spinning solution conveying device and the air injection device is 2-10 mm. From this, adopt the distance of the spinning liquid conveyor of this application and air jet system, be favorable to micro-nanofiber's formation, can avoid air jet system to be polluted by the spinning liquid simultaneously.

In a third aspect of the present invention, the present invention provides a micro-nanofiber. According to the embodiment of the invention, the micro-nano fiber is prepared by using the device or the method. Therefore, the micro-nano fiber is small and uniform in diameter and wide in variety.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Drawings

The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

fig. 1 is a schematic configuration diagram of an air supply unit according to an embodiment of the present invention;

FIG. 2 is a schematic structural view of a continuous liquid supply unit according to an embodiment of the present invention;

FIG. 3 is a schematic structural view of a needle-less solution air spinning apparatus according to one embodiment of the present invention;

FIG. 4 is a schematic structural view of a needle-less solution air spinning apparatus according to yet another embodiment of the present invention;

FIG. 5 is a schematic structural view of a needle-less solution air spinning apparatus according to still another embodiment of the present invention;

FIG. 6 is a schematic structural view of a needle-less solution air spinning apparatus according to still another embodiment of the present invention;

FIG. 7 is a schematic structural view of a needle-less solution air spinning apparatus according to still another embodiment of the present invention;

FIG. 8 is a schematic structural view of a needle-less solution air spinning apparatus according to still another embodiment of the present invention;

FIG. 9 is a schematic flow diagram of a method for spinning using a pinless solution gas spinning apparatus according to an embodiment of the present invention;

FIG. 10 is an SEM image of the micro-nanofiber prepared in example 1;

fig. 11 a is an XRD pattern of the micro-nanofiber prepared in example 2; b in fig. 11 is an SEM image of the micro-nanofiber prepared in example 2; c and D in fig. 11 are EDS diagrams of the micro-nanofiber prepared in example 2;

FIG. 12 is an SEM image of the micro-nanofiber prepared in example 3;

fig. 13 is an SEM image of the micro-nanofiber prepared in example 4.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.

In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the invention.

In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.

In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.

In a first aspect of the invention, the invention provides a pinless solution air spinning apparatus. According to an embodiment of the present invention, referring to fig. 1 to 3, the pinless solution gas spinning apparatus includes: a gas supply unit 100, a continuous liquid supply unit 200, and a collection unit 300.

According to an embodiment of the present invention, referring to fig. 1, the gas supply unit 100 includes a compressed gas supply device 1 and a gas injection device 4, the compressed gas supply device 1 and the gas injection device 4 are connected by a pipeline 2, and a pressure reducing valve 3 is provided on the pipeline 2. Specifically, by opening the compressed gas supply device 1 and the pressure reducing valve 3, the compressed gas in the compressed gas supply device 1 reaches the pressure reducing valve 3 through the pipe 2, and after the pressure and the flow rate of the gas are adjusted by the pressure reducing valve 3, the gas reaches the gas injection device 4 through the pipe 2 and is injected from the gas injection device 4 in the form of a gas flow. It should be noted that, a person skilled in the art may select specific types of the compressed gas supply device 1, the pressure reducing valve 3, the pipeline 2 and the air injection device 4 according to actual needs as long as the above functions can be achieved, for example, the compressed gas supply device 1 is a high-pressure gas cylinder or an air compressor; the pipeline 2 is a plastic pipe or a metal pipe; the air injection device 4 is a hollow tube or an air knife. It should be noted that the specific type of the hollow tube is not particularly limited, and those skilled in the art can select the hollow tube according to the actual requirement as long as the function of blowing gas can be achieved, for example, the hollow tube may be a hollow circular tube or a duckbill nozzle.

Further, when the air injection device 4 is a hollow round pipe, the inner diameter of the air injection device is preferably 4-10 mm; when the air injection device 4 is an air knife, a person skilled in the art can select the width of the air knife according to actual needs, as long as the above functions can be achieved, and for example, the width of the air knife can be 1 to 10 cm. According to some embodiments of the present invention, the surface pressure of the air flow ejected by the air ejection device 4 is 0.01 to 0.5 MPa. In addition, the type of the compressed gas is not particularly limited, and those skilled in the art can select the compressed gas according to actual needs, as long as the compressed gas is safe and environment-friendly and does not react with the spinning solution.

According to the embodiment of the present invention, referring to fig. 2, the continuous liquid supply unit 200 includes a solution tank 8, a spinning solution delivery device 7, and a power roller 6, wherein a support shaft 9 is provided in the solution tank 8 and adapted to support the spinning solution delivery device 7 tightly, the solution tank 8 contains the spinning solution, the support shaft 9 is located below the liquid level of the spinning solution, the power roller 6 is provided above the solution tank 8, the power roller 6 and the support shaft 9 are in transmission connection through the spinning solution delivery device 7, and the air injection device 4 is provided between the power roller 6 and the support shaft 9, and the air injection direction of the air injection device 4 faces the spinning solution delivery device 7. Preferably, the air jet direction of the air jet device 4 is perpendicular to the dope delivery device 7, for example, the air jet direction of the air jet device 4 is perpendicular to the plane of the dope delivery device 7.

Specifically, the power roller 6 rotates under the drive of the motor, and under the drive of the power roller 6 and the support shaft 9, the spinning solution conveying device 7 realizes reel-to-reel movement, and constantly carries the spinning solution contained in the solution tank 8 to the air jet device 4, and under the action of high-speed airflow, the solution adhered to the spinning solution conveying device 7 is drafted into jet flow. According to some embodiments of the present invention, the speed of the spinning solution conveying device 7 is 0.5 to 10cm/s, and the distance between the spinning solution conveying device 7 and the air injection device 4 is 2 to 10 mm. It should be noted that, a person skilled in the art can select specific types of the solution tank 8, the spinning solution delivery device 7, the power roller 6 and the support shaft 9 according to actual needs as long as the above functions can be achieved, for example, the material of the solution tank 8 may include at least one of metal, ceramic, glass and plastic as long as the solution tank is not corroded by the spinning solution; the material of the spinning solution delivery device 7 may include at least one of cotton, nylon, copper, and stainless steel, and may be closed into a ring by spot welding or the like; the support shaft 9 may be a roller or a fixed shaft.

Further, the spinning liquid feeding device 7 may be a single wire, a plurality of wires (as shown in fig. 4 and 7), or a mesh (as shown in fig. 5 and 8). The inventor finds that when the spinning solution conveying device is a plurality of threads or screen cloth, more spinning solution can be adhered to a single thread, so that more spinning solution can be subjected to drafting spinning simultaneously, and the spinning efficiency is improved. Further, when the spinning solution feeding device 7 is a single thread or a plurality of threads, the diameter of the single thread or the plurality of threads is 0.1 to 0.5mm, and may be, for example, 0.1mm, 0.2mm, 0.3mm, 0.4mm, or 0.5 mm. The inventor finds that if the diameter of the thread is too large, the thread carries too much solution, so that liquid drops are easily formed, and the fiber quality is influenced; if the diameter of the yarn is too small, the amount of the spinning solution carried on the yarn is too small, which affects the spinning efficiency. Therefore, the diameter of the yarn is adopted, the spinning efficiency is high, and the prepared micro-nano fiber is good in quality. Meanwhile, when the spinning solution conveying device 7 is a mesh fabric, the mesh number of the mesh fabric is 10 to 800 meshes, for example, 20 meshes, 50 meshes, 80 meshes, 100 meshes, 200 meshes, 400 meshes, 600 meshes, 800 meshes, or the like. The inventor finds that if the mesh number of the screen cloth is too small, the spinning efficiency is low; if the mesh number of the screen cloth is too large, the spinning solution beams are easy to interfere with each other, and the spinning quality is affected. Therefore, by adopting the mesh number of the mesh cloth, the spinning efficiency is high, and the prepared micro-nano fibers are good in quality.

According to some embodiments of the invention, the spinning liquid delivery device 7 is a single wire and the air jet device 4 is a hollow tube, the direction of air outlet on the hollow tube being towards the single wire. Therefore, spinning can be performed on the spinning solution adhered to a single wire, and uniform micro-nano fibers can be obtained.

According to some embodiments of the present invention, referring to fig. 4 and 7, the spinning solution feeding means 7 is a plurality of lines spaced apart on the power roller 6 and the support shaft 9, and the air blowing means 4 is a plurality of hollow tubes or air knives located inside a space surrounded by the plurality of lines. When the air injection device 4 is a plurality of hollow pipes, the air outlet directions of a plurality of air holes of the plurality of hollow pipes respectively face to a single line of the plurality of lines; when the air injection device 4 is an air knife, the air outlet direction of the air knife faces to the plurality of wires. Therefore, spinning can be simultaneously carried out on the spinning solution adhered to a plurality of threads, the spinning efficiency is further improved, and uniform micro-nano fibers are obtained.

According to some embodiments of the present invention, referring to fig. 5 and 8, the spinning solution feeding device 7 is a web, the gas spraying device 4 is an air knife, the air knife is located inside a space surrounded by the web, and a gas outlet direction of the air knife is perpendicular to the web. Therefore, spinning can be simultaneously carried out on the spinning solution adhered to the screen cloth, so that the spinning efficiency can be further improved, and uniform micro-nano fibers can be obtained.

According to some embodiments of the present invention, the above-mentioned continuous liquid supply unit 200 further comprises a driven roller 5 (see fig. 6 to 8), the driven roller 5 cooperating with the power roller 6 to extrude the spinning solution feeding means 7, and adapted to increase friction force by extrusion, to drive the spinning solution feeding means, and to continuously perform a roll-to-roll motion of the spinning solution feeding means 7 according to a predetermined trajectory. It should be noted that a person skilled in the art can select a specific type of the driven roller 5 according to actual needs, as long as the above-mentioned function can be achieved.

The specific type of the spinning solution is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the spinning solution includes a polymer solution or a mixed solution containing a polymer and an inorganic precursor. Specifically, the polymer material in the polymer solution or the mixed solution containing the polymer and the inorganic precursor includes at least one of polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyvinyl butyral, polyethylene glycol, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyvinylidene fluoride, polystyrene, polyurethane, polymethyl methacrylate, polylactic acid, polycaprolactone, polyether sulfone, polyimide, polyamide, cellulose acetate, methyl cellulose, carboxymethyl cellulose, polyaniline, and polycarbonate; the solvent of the spinning solution includes at least one of water, methanol, ethanol, N-butanol, N-propanol, isopropanol, hexafluoroisopropanol, t-butanol, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetone, acetylacetone, butanone, N-hexane, cyclohexane, N-heptane, acetonitrile, dichloromethane, chloroform, carbon tetrachloride, toluene, xylene, formic acid, and tetrahydrofuran; the inorganic precursor comprises tetraethoxysilane, methyl orthosilicate, aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum isopropoxide, aluminum acetylacetonate, tetrabutyl titanate, isobutyl titanate, titanium isopropoxide, zirconium oxychloride, zirconium acetate, zirconium n-propoxide, zirconium n-butoxide, zirconium hydroxide, zirconium acetylacetonate, yttrium nitrate, yttrium acetate, copper chloride, copper acetate, hafnium tetrachloride, hafnium sulfate, hafnium n-butoxide, hafnium ethoxide, hafnium hydroxide, hafnium oxychloride, at least one of hafnium oxide nitrate, barium acetate, tin chloride, tantalum pentachloride, cobalt acetate, zinc acetate, nickel acetate, titanium isopropoxide, cerium nitrate, magnesium acetate, zinc nitrate, silver nitrate, tantalum isopropoxide, niobium acetate, ferric chloride, ferric citrate, germanium isopropoxide, manganese acetate, indium nitrate, polycarbosilane, chromium nitrate, chromium chloride, tungsten isopropoxide, magnesium nitrate, ferric nitrate, manganese chloride, and cobalt nitrate.

Further, the polymer solution may have particles dispersed therein. It should be noted that the specific type of the particulate matter is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the particulate matter includes at least one of silica, alumina, titania, zirconia, ceria, vanadia, chromia, manganese dioxide, triiron tetroxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, and yttrium oxide.

According to an embodiment of the present invention, referring to fig. 3 to 8, a collecting unit 300 is disposed downstream of the air injection device 4 and is adapted to collect micro-nanofibers. It should be noted that, a person skilled in the art may select the specific material of the collecting unit 300 according to actual needs as long as the above-mentioned function can be achieved, for example, the material of the collecting unit 300 may include at least one of glass, metal, ceramic and plastic. According to some embodiments of the present invention, the collecting unit 300 is provided with a collecting device (not shown) inside, specifically, the collecting device may be a mesh, a hollow cage or a roller, and is suitable for obtaining the bulk or film-shaped micro-nanofibers.

The inventors found that by opening the compressed gas supply means and the pressure reducing valve, it is possible to supply the gas and adjust the pressure and flow rate of the gas, and then the gas is ejected from the gas ejecting means in the form of a gas flow; simultaneously, under the drive of power roller bearing and back shaft, spinning liquid conveyor realizes the reel-to-reel continuous motion, constantly carries the spinning liquid of splendid attire in the solution tank to air jet system department, and under the effect of high velocity air, the solution of adhesion on the spinning liquid conveyor is drafted and becomes the efflux to utilize the collection unit to collect and obtain micro-nanofiber. From this, the no syringe needle solution air spinning equipment application scope of this application is wide, can be used to produce various organic, inorganic micro-nanofiber and load particulate matter's micro-nanofiber material, in addition, compare in traditional electrostatic spinning production efficiency lower, and extrude solution filamentation through spinning nozzle, the condition that spinning nozzle blockked up appears easily, the no syringe needle solution air spinning equipment production efficiency of this application is high, has good scale production prospect, and need not to use the spinneret, the problem of solution stifled needle has been avoidd, be favorable to the popularization of industrialization.

In a second aspect of the invention, the invention provides a method for spinning by using the needle-free solution gas spinning device. Referring to fig. 9, the method includes, according to an embodiment of the present invention:

s100: opening compressed gas supply device and pressure reducing valve

In this step, the compressed gas supply device and the pressure reducing valve are opened to allow the gas jet device to jet a gas flow. Specifically, by opening the compressed gas supply device and the pressure reducing valve, the compressed gas in the compressed gas supply device reaches the pressure reducing valve through a pipeline, the pressure and the flow rate of the gas are regulated by the pressure reducing valve, then the gas reaches the gas injection device through the pipeline, and the gas is injected from the gas injection device in the form of gas flow.

Further, the surface pressure of the air flow discharged from the air jet device is 0.01 to 0.5MPa, and specifically, may be 0.01MPa, 0.05MPa, 0.1MPa, 0.2MPa, 0.3MPa, 0.4MPa, or 0.5 MPa. The inventors found that if the gauge pressure is too low, the spinning solution cannot be sufficiently drawn by the air flow, and it is difficult to form fibers; if the surface pressure is too high, the spinning solution jet is easily broken by high-speed airflow, and a continuous, uniform and high-quality fiber material cannot be obtained. Therefore, the air flow meter pressure is beneficial to obtaining continuous, uniform and high-quality micro-nano fibers.

S200: under the drive of the power roller and the support shaft, the spinning solution conveying device conveys the spinning solution contained in the solution tank to the air injection device, the air flow performs injection and drafting on the solution carried by the spinning solution conveying device, and the solution is collected by the collecting unit to obtain the micro-nano fibers

In this step, power roller bearing rotates under the drive of motor, and under the drive of power roller bearing and back shaft, spinning liquid conveyor realizes the reel-to-reel motion, constantly carries the spinning liquid of splendid attire in the solution tank to air jet system department, and under the effect of high velocity air, the solution of adhesion is drawn and becomes the efflux on the spinning liquid conveyor to utilize the collection unit to collect and obtain micro-nanofiber. It should be noted that the specific type of the above spinning solution is the same as that described above, and is not described herein again.

Further, the speed of the spinning solution conveying device is 0.5-10 cm/s, specifically 0.5cm/s, 2cm/s, 4cm/s, 6cm/s, 8cm/s or 10 cm/s. The inventor finds that the spinning solution carried on the spinning solution conveying device is easy to dry up if the speed of the spinning solution conveying device is too low; if the speed of the spinning solution conveying device is too high, too much spinning solution is carried by the conveying device, and large liquid drops are easily formed in the spinning process, so that the fiber quality is influenced. Therefore, by adopting the speed of the spinning solution conveying device, on one hand, the spinning solution on the spinning solution conveying device can be prevented from drying up; on the other hand, the method is beneficial to obtaining high-quality micro-nano fibers.

Further, the distance between the spinning solution conveying device and the air injection device is 2-10 mm, specifically, the distance can be 2mm, 4mm, 6mm, 8mm or 10 mm. The inventor finds that when the distance between the spinning solution conveying device and the air injection device is too small, the spinning solution is easy to touch and pollute the air injection device; if the distance between the spinning solution conveying device and the air injection device is too large, the air flow dissipation is large, and the spinning solution cannot be sufficiently drawn to form jet flow. From this, adopt the distance of the spinning liquid conveyor of this application and air jet system, be favorable to micro-nanofiber's formation, can avoid air jet system to be polluted by the spinning liquid simultaneously.

In a third aspect of the present invention, the present invention provides a micro-nanofiber. According to the embodiment of the invention, the micro-nanofiber is prepared by using the device or the method. Therefore, the micro-nano fiber is small and uniform in diameter and wide in variety. It should be noted that the features and advantages described above for the pinless solution air spinning device and the method for spinning by using the same are also applicable to the micro-nanofibers, and are not described herein again.

The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.

Example 1

Spinning was carried out using a pinless solution gas spinning apparatus as shown in FIG. 6:

(1) preparing a polyvinylpyrrolidone solution: adding 5g of polyvinylpyrrolidone into 45g of absolute ethyl alcohol, stirring and dissolving for 2h at 80 ℃ and at the rotating speed of 800rpm to obtain an ethanol solution of polyvinylpyrrolidone with the mass concentration of 10 wt%;

(2) adding an ethanol solution of polyvinylpyrrolidone into an acrylic solution tank, and conveying the ethanol solution of polyvinylpyrrolidone to the front end (the distance between an air jet device and a spinning solution conveying device is 4mm) of an air jet device (a hollow round pipe, the outer diameter is 6mm, and the inner diameter is 4mm) at the speed of 2cm/s by using the spinning solution conveying device (a single nylon wire with the diameter of 0.4 mm);

(3) and (3) starting a compressed gas supply device (an air compressor), adjusting through a pressure reducing valve, and drafting the ethanol solution of the polyvinylpyrrolidone by using high-speed airflow with the pressure of 40kPa to obtain the polyvinylpyrrolidone nanofibers in the hollow cage-shaped collecting device.

The average diameter of the obtained polyvinylpyrrolidone nanofibers was 274nm, as shown in fig. 10.

Example 2

Spinning was carried out using a pinless solution gas spinning apparatus as shown in FIG. 7:

(1) preparing a polyvinylpyrrolidone/aluminum chloride mixed solution: adding 5g of polyvinylpyrrolidone into a mixed solvent of 22.5g of absolute ethyl alcohol and 22.5g of deionized water, and stirring and dissolving at 80 ℃ at a rotating speed of 800rpm for 2 hours to obtain a polyvinylpyrrolidone solution with a mass concentration of 10 wt%; adding 10g of aluminum chloride hexahydrate into a polyvinylpyrrolidone solution, stirring and dissolving for 1h at the rotating speed of 800rpm under the normal temperature condition to obtain a polyvinylpyrrolidone/aluminum chloride mixed solution;

(2) adding a polyvinylpyrrolidone/aluminum chloride mixed solution into an acrylic solution tank, and conveying the mixed solution to the front end of an air jet device (an air knife with the width of 30 mm) at the speed of 2cm/s (the distance between the air jet device and a spinning solution conveying device is 6mm) by using the spinning solution conveying device (a plurality of nylon wires with the diameter of 0.4 mm);

(3) and (3) starting a compressed gas supply device (a high-pressure gas cylinder), adjusting by using a pressure reducing valve, and drafting the polyvinylpyrrolidone/aluminum chloride mixed solution by using high-speed airflow with the pressure of 80kPa to obtain the composite fiber on a reticular collecting device. And raising the temperature of the obtained composite fiber from room temperature to 600 ℃ at the speed of 5 ℃/min, preserving the heat for 1h, raising the temperature to 1100 ℃ at the speed of 2 ℃/min, preserving the heat for 1h, and reducing the temperature to room temperature to obtain the alumina fiber.

XRD of the resulting alumina fiber is shown as a in fig. 11; SEM is shown as B in fig. 11; EDS is shown as C and D in fig. 11.

Example 3

Spinning was carried out using a pinless solution gas spinning apparatus as shown in FIG. 8:

(1) preparing N, N-dimethylformamide solution of polyacrylonitrile: adding 6g of polyacrylonitrile into 44g N, N-dimethylformamide, stirring and dissolving for 2 hours at the temperature of 60 ℃ at the rotating speed of 800rpm to obtain an N, N-dimethylformamide solution of polyacrylonitrile with the mass concentration of 12 wt%;

(2) adding N, N-dimethylformamide solution of polyacrylonitrile into a stainless steel solution tank, and conveying the solution to the front end of an air jet device (an air knife with the width of 30 mm) (the distance between the air jet device and a spinning solution conveying device is 2mm) at the speed of 2cm/s by using the spinning solution conveying device (a wire mesh with the mesh number of 80 and the width of 1 cm);

(3) and (3) starting a compressed gas supply device (an air compressor), adjusting by using a pressure reducing valve, and drafting the N, N-dimethylformamide solution of polyacrylonitrile by using high-speed airflow with the pressure of 80kPa to obtain the polyacrylonitrile fibers in a roller collection device.

The polyacrylonitrile fiber obtained had an average diameter of 265nm as shown in FIG. 12.

Example 4

Spinning was carried out using a pinless solution gas spinning apparatus as shown in FIG. 6:

(1) preparing an N, N-dimethylformamide solution of polyacrylonitrile dispersed with silica particles: adding 6g of polyacrylonitrile into 44g N, N-dimethylformamide, stirring and dissolving for 2 hours at the temperature of 60 ℃ at the rotating speed of 800rpm to obtain an N, N-dimethylformamide solution of polyacrylonitrile with the mass concentration of 12 wt%; adding 3g of silicon dioxide nano particles into the obtained solution, and stirring for 2 hours at the rotating speed of 800rpm under the condition of normal temperature to obtain a polyacrylonitrile solution dispersed with silicon dioxide particles;

(2) adding the mixed solution into a stainless steel solution tank, and conveying the solution to the front end (the distance between the air injection device and the spinning solution conveying device is 8mm) of an air injection device (a hollow round pipe, the outer diameter is 6mm, and the inner diameter is 4mm) at the speed of 2cm/s by using the spinning solution conveying device (a single nylon wire with the diameter of 0.4 mm);

(3) and (3) starting a compressed gas supply device (a high-pressure gas cylinder), regulating by a pressure reducing valve, drafting the mixed solution by utilizing high-speed airflow with the pressure of 40kPa, and obtaining the polyacrylonitrile fiber loaded with the silicon dioxide particles in a hollow cage-shaped collecting device.

The SEM of the resultant silica particle-supporting polyacrylonitrile fiber is shown in fig. 13.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A pinless solution air spinning device is characterized by comprising:

the gas supply unit comprises a compressed gas supply device and a gas injection device, the compressed gas supply device is connected with the gas injection device through a pipeline, and a pressure reducing valve is arranged on the pipeline;

the continuous liquid supply unit comprises a solution tank, a spinning solution conveying device and a power rolling shaft, a supporting shaft is arranged in the solution tank, the spinning solution is contained in the solution tank, the supporting shaft is located below the liquid level of the spinning solution, the power rolling shaft is arranged above the solution tank, the power rolling shaft is in transmission connection with the supporting shaft through the spinning solution conveying device, the air injection device is arranged between the power rolling shaft and the supporting shaft, and the air injection direction of the air injection device faces the spinning solution conveying device;

a collection unit disposed downstream of the air jet device.

2. The pinless solution gas spinning apparatus of claim 1, wherein said power roller is parallel to said support shaft and said spinning solution delivery means is disposed vertically horizontal.

3. The pinless solution gas spinning apparatus according to claim 1 or 2, wherein the gas jet direction of the gas jet means is perpendicular to the spinning liquid feeding means.

4. The needle-free solution gas spinning apparatus according to claim 1, wherein said gas injection means is a hollow tube or an air knife.

5. The pinless solution gas spinning apparatus of claim 4, wherein the spinning solution delivery means is a single thread, a plurality of threads or a mesh;

optionally, the spinning solution conveying device is a plurality of threads which are arranged on the power roller and the support shaft at intervals, the air injection device is a plurality of hollow tubes or air knives which are positioned in a space surrounded by the plurality of threads, the air outlet directions of a plurality of air holes of the plurality of hollow tubes are respectively towards a single thread of the plurality of threads, and the air outlet direction of the air knives is towards the plurality of threads;

optionally, the spinning solution conveying device is a mesh, the air jet device is an air knife, the air knife is positioned inside a space surrounded by the mesh, and the air outlet direction of the air knife is perpendicular to the mesh;

optionally, the diameter of the single wire and the plurality of wires is 0.1-0.5 mm;

optionally, the mesh number of the mesh cloth is 10-800 meshes.

6. The pinless solution spinning apparatus of claim 1, wherein the continuous liquid supply unit further comprises a driven roller cooperating with the powered roller to squeeze the dope delivery means.

7. A method for spinning by using the pinhead-free solution air spinning device of any one of claims 1 to 6, which is characterized by comprising the following steps:

(1) opening the compressed gas supply device and the pressure reducing valve so as to enable the gas spraying device to spray gas flow;

(2) the spinning solution conveying device conveys the spinning solution contained in the solution tank to the air jet device under the driving of the power roller and the supporting shaft, and the air flow carries out blowing and drafting on the solution carried by the spinning solution conveying device and is collected by the collecting unit to obtain the micro-nano fibers.

8. The method according to claim 7, wherein in the step (2), the spinning solution comprises a polymer solution or a mixed solution containing a polymer and an inorganic precursor;

optionally, the polymer material in the polymer solution or the mixed solution containing polymer and inorganic precursor includes at least one of polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyvinyl butyral, polyethylene glycol, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyvinylidene fluoride, polystyrene, polyurethane, polymethyl methacrylate, polylactic acid, polycaprolactone, polyethersulfone, polyimide, polyamide, cellulose acetate, methyl cellulose, carboxymethyl cellulose, polyaniline, and polycarbonate;

optionally, the solvent of the spinning dope includes at least one of water, methanol, ethanol, N-butanol, N-propanol, isopropanol, hexafluoroisopropanol, t-butanol, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetone, acetylacetone, butanone, N-hexane, cyclohexane, N-heptane, acetonitrile, dichloromethane, chloroform, carbon tetrachloride, toluene, xylene, formic acid, and tetrahydrofuran;

optionally, the inorganic precursor comprises ethyl orthosilicate, methyl orthosilicate, aluminum chloride, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum isopropoxide, aluminum acetylacetonate, tetrabutyl titanate, isobutyl titanate, titanium isopropoxide, zirconium oxychloride, zirconium acetate, zirconium n-propoxide, zirconium n-butoxide, zirconium hydroxide, zirconium acetylacetonate, yttrium nitrate, yttrium acetate, copper chloride, copper acetate, hafnium tetrachloride, hafnium sulfate, hafnium n-butoxide, hafnium ethoxide, hafnium hydroxide, hafnium oxychloride, at least one of hafnium oxide nitrate, barium acetate, tin chloride, tantalum pentachloride, cobalt acetate, zinc acetate, nickel acetate, titanium isopropoxide, cerium nitrate, magnesium acetate, zinc nitrate, silver nitrate, tantalum isopropoxide, niobium acetate, ferric chloride, ferric citrate, germanium isopropoxide, manganese acetate, indium nitrate, polycarbosilane, chromium nitrate, chromium chloride, tungsten isopropoxide, magnesium nitrate, ferric nitrate, manganese chloride, and cobalt nitrate;

optionally, the polymer solution has particulate matter dispersed therein;

optionally, the particulate matter comprises at least one of silica, alumina, titania, zirconia, ceria, vanadia, chromia, manganese dioxide, triiron tetroxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, and yttrium oxide;

optionally, the gauge pressure of the gas flow is 0.01-0.5 MPa.

9. The method according to claim 7, wherein in the step (2), the speed of the spinning solution conveying device is 0.5 to 10 cm/s;

optionally, the distance between the spinning solution conveying device and the air injection device is 2-10 mm.

10. A micro-nanofiber, which is characterized by being prepared by using the device of any one of claims 1-6 or the method of any one of claims 7-9.

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