CN105568407A - Polymer solution-based magnetofluid self-assembly needle-free electro-spinning device and nanofiber electro-spinning method thereof - Google Patents

Abstract

The invention discloses a polymer solution-based magnetic fluid self-assembled needle-free electrospinning device, which includes a groove, a controllable magnetic field generating module, a high-voltage electric field generating module, and a conductive fiber receiving module for collecting fiber filaments And at least one conical tower with electrical conductivity and magnetic permeability, the surface of the conical tower is provided with threaded grooves spirally rising along the conical tower. The object of the present invention is to provide a high molecular polymer solution-based ferrofluid self-assembled needle-free electrospinning device with simple structure, controllable and easy-to-control operation, and high processing efficiency. A method for electrospinning nanofibers in a spinning device. This method achieves the purpose of controlling the high molecular polymer solution-based magnetic fluid jet by controlling the electric and magnetic fields. The method is controllable and easy to control, and the control accuracy is good.

Description

A polymer solution-based magnetic fluid self-assembled needle-free electrospinning device and method for electrospinning nanofibers thereof

technical field

The invention relates to the technical field of electrospinning, in particular to a polymer solution-based magnetic fluid self-assembled needle-free electrospinning device. At the same time, the invention also discloses an electrospinning machine using the needle-free electrospinning device for spinning. nanofiber approach.

Background technique

At present, in the technical field of electrospinning, the output of various materials is in short supply, especially nano-materials. Nano-fiber materials can be widely used in the purification and filtration of chemical, pharmaceutical and other products, and can also be used to make advanced protective clothing and other fields. .

Electrospinning equipment is a kind of equipment that can prepare nanofiber materials, and the electrospinning technology has been developed relatively maturely. However, there are still some problems, the most obvious problems are the clogging of the injection needle and the need for injection pump injection during the electrospinning process.

CN201110154158.0 discloses an electrospinning device, comprising a spinneret die, a spinneret die cover, a spinneret, a high-voltage power supply device and a receiving plate, and the electrospinning device also includes a raw material delivery device, a mechanical A vibration generating device and a magnetic field generating device, the raw material delivery device is connected to one side of the spinning die, the mechanical vibration generating device is installed on one end of the spinning die, and the magnetic field generating device is installed on the side of the spinning die The other end is located between the spinneret and the receiving plate. It uses a magnetic field to change the trajectory of the polymer filaments ejected from the spinneret die, preventing Taylor cones from appearing and reducing the difficulty of fiber filament collection. However, it adopts a nozzle-type structure, which is prone to the failure of polymers to block the nozzle.

The diameter of the needle of the syringe pump of the traditional electrospinning device is generally relatively small, which leads to the situation: not only the clogging of the needle described above, but also strict requirements on the properties of the polymer solution base. These problems constitute a lot of inconvenience and resistance to the spinning process.

Then, needle-free electrospinning technology appeared. Currently as the world's mainstream needle-free electrospinning technology, it is the Nano spider (NanospiderTM) needle-free electrospinning technology of Czech Elmarco Company, which adopts smooth surface or rollers with different surface features such as threads and patterns on the surface (see WO2005 /024101A1) as an electrospinning head. In the patent WO2005/024101, rollers are used as the launch carrier of the spinning polymer, which is prone to uneven spinning and most of the fibers are relatively thick.

For the improvement of the above technology, the following Chinese patent application can be seen: CN201310186515.0, which discloses a cutting-edge needle-free electrospinning equipment. The chain of the plate drives the needle plate to continuously immerse in the polymer solution through the chain, and then achieves the purpose of spinning through the electric field. However, it has a complex structure and is difficult to precisely control the production process.

CN201510390839.5 discloses an electrospinning device for mass production of nanofibers, which includes a receiving plate, a high-voltage direct current power supply, a solution tank, a motor, and a spinneret. The spinneret uses multiple-point metal discs Or with a needle point helical piece or with a needle point spring, the multiple-pointed metal disc or with a needle point helical piece or with a needle point spring is placed on the solution tank and ensures that the needle point contacts the polymer solution. Although the structure of this device has been simplified compared to CN201310186515.0, the structure is still relatively complicated, and the production process and its parameters such as the shape of the polymer at the needle point are difficult to control.

Although the above-mentioned needle-free spinning technology effectively solves the problems existing in traditional electrospinning equipment, the structure of these needle-free electrospinning equipment is too complicated, and the production process is difficult to control stably, which brings inconvenience to the mass production of nanofiber materials.

Contents of the invention

The purpose of the present invention is to provide a polymer solution-based ferrofluid self-assembled needle-free electrospinning device with simple structure, controllable and easy-to-control operation and high processing efficiency. At the same time, the present invention also provides a needle-free electrospinning device using the The needle-free electrospinning method achieves the purpose of controlling the polymer jet by controlling the electromagnetic field, the operation is controllable and easy to control, and the control precision is high.

The specific technical scheme of the present invention is: a polymer solution-based ferrofluid self-assembled needle-free electrospinning device, including a polymer solution-based magnetic fluid self-assembled needle-free electrospinning device, including grooves, controllable A magnetic field generating module, a high-voltage electric field generating module, a conductive fiber receiving module for collecting fiber filaments, and at least one conductive and magnetically conductive conical tower. thread groove;

The conical tower is arranged in the groove, the fiber receiving module is arranged above the conical tower, and the controllable magnetic field generating module is arranged below the groove and is used to apply a controllable magnetic field to the conical tower. One end of the high-voltage electric field generating module is electrically connected to the fiber receiving module and the other end is electrically connected to the conical tower;

When the polymer solution-based ferrofluid is added to the groove, the controllable magnetic field generation module makes the polymer solution-based ferrofluid rise along the thread groove of the conical tower and arrange it in a peak shape on the edge of the thread groove; the high-voltage electric field generates The module makes the polymer solution-based magnetic fluid form a jet under the action of an electric field, and forms magnetic nanofiber filaments on the fiber receiving module.

In the present invention, the number of conical towers is preferably 1, and of course it does not exclude the number of conical towers being 2 or 3.

As a further preference of the present invention, the controllable magnetic field generating module comprises an iron core and an excitation coil wound on the surface of the iron core, and the excitation coil is electrically connected to a regulated DC power supply and a first rheostat.

Further, the high-voltage electric field generating module includes a high-voltage direct current power supply and a second rheostat.

Further, the voltage of the high-voltage electric field generating module can be adjusted as low as 0V, and as high as 40KV; the adjustable magnetic field strength of the controllable magnetic field generating module ranges from 0 to 400mT.

Further, the taper range of the conical tower is 0.18-0.3; the height range of the conical tower is 5cm-8cm; the depth range of the thread groove is 0.20cm-0.5cm; the pitch range of the thread groove is 0.5cm- 1cm.

Further, the material of the groove is plexiglass or engineering plastics, such as polycarbonate (PC), polyamide (PA) and other materials.

Further, the fiber receiving module is a good conductor of electricity, such as aluminum foil; the conical tower is a good conductor of electricity and magnetism, such as electrical pure iron, steel, etc.

Further, the fiber receiving module is a structure with a concave curved surface, the fiber receiving module corresponds to the conical tower, and the distance between the groove and the fiber receiving module is 17cm to 20cm.

Another object of the present invention is to provide a method of electrospinning nanofibers spun using the above-mentioned needleless electrospinning device, specifically, first adding a high molecular polymer solution-based magnetic fluid into the groove, Start the controllable magnetic field generating module, and periodically increase the current value in the excitation coil, so that the polymer solution-based ferrofluid rises along the threaded groove of the conical tower and is arranged in a peak shape on the edge of the threaded groove; then start the high-voltage electric field The generating module generates a constant electric field strength after stabilization, so that the polymer solution-based magnetic fluid forms a jet under the action of the electric field, and forms magnetic nanofiber filaments on the fiber receiving module.

In the present invention, the step of periodically increasing the current value in the exciting coil may specifically be: increasing the current value in the exciting coil by 0.5A every minute.

As a further preference of the present invention, the adjustable range of the magnetic field strength is 0-0.4T, and the working voltage of the high-voltage electric field generating module is 20KV-40KV.

It should be noted that the high-molecular polymer solution-based magnetic fluid of the present invention can be selected as ferroferrofluid polymer, wherein the high-molecular polymer is polyvinyl alcohol (PVA) or polyvinylpyrrolidone (PVP), and the high-molecular polymer The preparation method of the polymer solution-based magnetic fluid can be as follows: first configure a 7% aqueous solution of PVA, after mixing evenly, add the surface-modified Fe ₃ O ₄ nanoparticles to the above solution at a concentration of 0.2g/ml and mix Uniformly; or first configure the dehydrated ethanol solution of polyvinylpyrrolidone (PVP) with a mass volume ratio of ₇ %, after mixing uniformly, the coated _Fe3O4 powder 0.2g/ml is added to the solution and mixed uniformly. The present invention is not overly limited.

Compared with prior art, the beneficial effect of the present invention is:

Compared with the prior art, the present invention realizes the self-helical rise of the polymer solution-based magnetic fluid under the action of the magnetic field by adopting the controllable magnetic field and the high-voltage electric field, and expands laterally into a peak, which forms a jet under the action of the electric field , stretched by an electric field, and during this process, the solvent is volatilized and the polymer is solidified to obtain a polymer fiber filament. The invention overcomes the shortcomings of traditional needleless electrospinning that needs to be constantly driven by a driving mechanism and has a complicated structure, and realizes the goals of simplifying the structure, simplifying the operation process, and improving production efficiency, and the polymer fiber filaments produced by the device of the invention are continuous and The specifications are consistent.

The present invention adopts the optimal parameters of the conical tower and the threaded groove, the controllable magnetic field generating module and the selection of its parameters, so as to realize the stable rise of the polymer along the threaded groove, and further stretch the edge of the threaded groove to form a peak under the action of the magnetic field. Contribute to the formation of stable polymer jets and uniform specifications.

The present invention further preferably can achieve following purpose to groove, conical tower, fiber receiving module, on the one hand the material of groove preferably can reduce the influence to magnetic field, improves the stability of magnetic field acting on high molecular polymer solution base magnetic fluid, reduces The impact on the magnetic field, on the one hand, the good electrical conductivity and magnetic permeability of the conical tower realize that both the electric field and the magnetic field can effectively act on the polymer solution-based magnetic fluid, improving the stability of the preparation process, and on the other hand, the fiber receives The material selection of the module also increases the strength of the electric field, which helps to improve the stability of the polymer fiber preparation.

Description of drawings

Fig. 1 is the overall structure schematic diagram of embodiment 1 of the present invention and embodiment 2 of the present invention;

Fig. 2 is a working principle diagram of Embodiment 1 of the present invention and Embodiment 2 of the present invention.

detailed description

The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments, but this does not constitute any limitation to the present invention.

Example 1

As shown in Figures 1 and 2, this embodiment provides a polymer solution-based ferrofluid self-assembled needle-free electrospinning device, including a groove 1 made of plexiglass, a controllable magnetic field generating module 2, and a high-voltage electric field generating module 3 1. A conductive fiber receiving module 4 for collecting fiber filaments and a conductive and magnetically conductive conical tower 5, the surface of the conical tower 5 is provided with a threaded groove 51 spirally rising along the conical tower 5;

The conical tower 5 is evenly distributed in the groove 1, the fiber receiving module 4 is arranged above the conical tower 5, and the controllable magnetic field generating module 2 is arranged below the groove 1 and is used to apply a controllable The magnetic field is on the conical tower 5 , one end of the high-voltage electric field generating module 3 is electrically connected to the fiber receiving module 4 and the other end is electrically connected to the conical tower 5 .

In this embodiment, through the use of a controllable magnetic field and a high-voltage electric field, the polymer solution-based magnetic fluid spirals upward under the action of a magnetic field and expands laterally into a peak A. Under the action of an electric field, the peak A forms a jet. After electric field stretching, and during this process, the solvent is volatilized and the polymer is solidified to obtain polymer fiber filaments. The invention overcomes the disadvantages of traditional needleless electrospinning that need to be constantly driven by a driving mechanism and has a complicated structure, realizes the goals of simplified structure and simplified operation process, and the polymer fiber filaments produced by the device of the invention are continuous and consistent in specification.

Further preferably, the controllable magnetic field generating module 2 includes an iron core 21 and an excitation coil 22 wound on the surface of the iron core 21, and the excitation coil 22 is electrically connected to a regulated DC power supply 23 and a first rheostat 24, The high-voltage electric field generating module 3 includes a high-voltage DC power supply 31 and a second rheostat 32 .

Wherein, the adjustable range of the magnetic field intensity of the controllable magnetic field generating module 2 is 0-0.4T; the adjustable voltage range of the high-voltage electric field generating module 3 is 0-40KV.

In the present embodiment, specifically, the taper of described conical tower 5 is 0.21; The height of described conical tower 5 is 5.71cm; The depth of thread groove 51 is 0.30cm; The pitch of thread groove 51 is 0.67cm , the distance between the fiber receiving module 4 and the groove 1 is 18cm. The fiber receiving module 4 is a structure with a concave curved surface.

In the production process, the specific method of electrospinning nanofibers is as follows:

S1: Add an appropriate amount of high-molecular polymer solution-based magnetic fluid B to the groove 1; the preparation method of high-molecular polymer solution-based magnetic fluid B is: first configure polyvinylpyrrolidone (PVP) with a mass-to-volume ratio of 7wt% Anhydrous ethanol solution, after mixing evenly, add 0.2g/ml of coated Fe ₃ O ₄ powder into the above solution and mix evenly;

S2: Start the controllable magnetic field generating module 2, periodically increase the current value in the excitation coil 22, that is, increase the current value in the excitation coil 22 by 0.5A every minute, so that the polymer in the groove 1 polymerizes The solution-based ferrofluid B rises longitudinally along the edge of the threaded groove 51 of the conical tower 5, and extends laterally into a peak; specifically, the magnetic field intensity of the controllable magnetic field generating module 2 gradually increases from 0T to 0.4T.

S3: Start the high-voltage electric field generating module 3, and adjust the voltage from 0KV to 40KV, so that the polymer solution-based magnetic fluid forms a jet under the action of the electric field. Magnetic nanofiber filaments are formed on module 4 .

The device in this embodiment has a simple structure, does not need nozzles in the traditional technology, and does not need the rotating drive device in the traditional needleless spinning. The purpose of preparing magnetic nanofibers can be achieved only by changing the strength of the magnetic field and electric field, and the processing efficiency is high.

The method of this embodiment is simple and easy to control, and the purpose of preparing magnetic nanofibers can be achieved by changing the strength of the magnetic field and electric field, and the purpose of accurately adjusting the specifications of the magnetic nanofibers can be achieved.

Example 2

In this embodiment, referring also to Fig. 1 and Fig. 2, the high molecular polymer solution-based ferrofluid self-assembled needle-free electrospinning device is substantially the same as that of Embodiment 1, the difference being specifically: the conical tower 5 The taper is 0.18; the height of the conical tower 5 is 6.67cm; the depth of the thread groove 51 is 0.30cm; the pitch of the thread groove 51 is 0.65cm, and the distance between the fiber receiving module 4 and the groove 1 is 18cm.

In the production process, the specific method of electrospinning nanofibers is as follows:

S1: Add an appropriate amount of high molecular polymer solution-based magnetic fluid B to the groove 1; the preparation method of high molecular polymer solution-based magnetic fluid B is: first configure the polyvinyl alcohol (PVA) with a mass volume ratio of 7wt%. Aqueous solution, after mixing evenly, add 0.2g/ml of coated Fe3O4 powder into the above solution and mix evenly;

S2: Start the controllable magnetic field generating module 2, and increase the current value periodically, that is, the current value in the excitation coil 22 increases by 0.5A every minute, so that the polymer solution-based ferrofluid in the groove 1 B rises longitudinally along the edge of the thread groove 51 of the conical tower 5 and extends laterally to form a peak; specifically, the magnetic field intensity of the controllable magnetic field generating module 2 gradually increases from 0T to 0.4T.

S3: Start the high-voltage electric field generating module 3, and adjust the voltage from 0KV to 40KV, so that the polymer solution-based magnetic fluid forms a jet under the action of the electric field. Magnetic nanofiber filaments are formed on module 4 .

The method of this embodiment is also simple and controllable, and the purpose of preparing magnetic nanofibers can be achieved by adjusting the strength of the magnetic field and electric field, and the purpose of preparing different magnetic nanofibers can be achieved.

The above descriptions are only preferred embodiments of the present invention, and any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. A polymer solution-based ferrofluid self-assembled needle-free electrospinning device, comprising a groove (1), is characterized in that, also includes a controllable magnetic field generating module (2), a high-voltage electric field generating module (3), for A conductive fiber receiving module (4) for collecting fiber filaments and at least one conductive and magnetically permeable conical tower (5), the surface of the conical tower (5) is provided with a spiral rise along the conical tower (5). The thread groove (51); The conical tower (5) is arranged in the groove (1), the fiber receiving module (4) is arranged above the conical tower (5), and the controllable magnetic field generating module (2) is arranged in the concave Below the slot (1) and used to apply a controllable magnetic field on the conical tower (5), one end of the high-voltage electric field generating module (3) is electrically connected to the fiber receiving module (4) and the other end is connected to the conical tower (5) electrical connection; After the high molecular polymer solution-based magnetic fluid is added to the groove (1), the controllable magnetic field generating module (2) makes the high molecular polymer solution-based magnetic fluid rise along the threaded groove (51) of the conical tower (5) and The edges of the thread grooves (51) are arranged in a peak shape; the high-voltage electric field generating module (3) makes the high molecular polymer solution-based magnetic fluid form a jet under the action of an electric field, and forms magnetic nanofiber filaments on the fiber receiving module (4). 2. polymer solution base ferrofluid self-assembly needleless electrospinning device according to claim 1, is characterized in that, described controllable magnetic field generation module (2) comprises iron core (21) and is wound on iron core ( 21) The excitation coil (22) on the surface, the excitation coil (22) is electrically connected to the regulated DC power supply (23) and the first rheostat (24). 3. polymer solution-based ferrofluid self-assembled needle-free electrospinning device according to claim 2, is characterized in that, described high-voltage electric field generation module (3) comprises high-voltage DC power supply (31) and second varistor (32 ). 4. The polymer solution-based ferrofluid self-assembled needle-free electrospinning device according to claim 3, characterized in that the voltage of the high-voltage electric field generating module (3) can be adjusted to 0V at the lowest, and the highest adjustable is greater than or equal to 40KV; the adjustable range of the magnetic field intensity of the controllable magnetic field generating module (2) is 0-400mT. 5. The polymer solution-based ferrofluid self-assembled needle-free electrospinning device according to any one of claims 1 to 4, characterized in that, the conical tower (5) has a taper range of 0.18 to 0.3; The height of the conical tower (5) ranges from 5cm to 8cm; the depth of the thread groove (51) ranges from 0.20cm to 0.5cm; the pitch of the thread groove (51) ranges from 0.5cm to 1cm. 6. The polymer solution-based ferrofluid self-assembled needle-free electrospinning device according to claim 5, characterized in that, the material of the groove (1) is plexiglass or engineering plastics. 7. polymer solution base ferrofluid self-assembly needleless electrospinning device according to claim 6, is characterized in that, described fiber receiving module (4) is the good conductor of electricity; Described conical tower (5) Good conductor of electricity and magnetism. 8. The polymer solution-based ferrofluid self-assembled needle-free electrospinning device according to claim 7, characterized in that, the described fiber receiving module (4) has a structure with a concave curved surface, and the described fiber receiving module (4) Corresponding to the conical tower (5), the distance between the groove (1) and the fiber receiving module (4) is 17cm to 20cm. 9. A method of utilizing the needleless electrospinning device described in any one of claims 1 to 8 to carry out spinning electrospun nanofiber method, it is characterized in that, high molecular polymer solution-based magnetic fluid is added to the groove ( In 1), start the controllable magnetic field generating module (2), periodically increase the current value in the excitation coil, so that the polymer solution-based ferrofluid rises along the threaded groove (51) of the conical tower (5) and The edges of the thread grooves (51) are arranged in a peak shape; then the high-voltage electric field generating module (3) is started, and after stabilization, a constant electric field intensity is generated, so that the high molecular polymer solution-based magnetic fluid forms a jet under the action of the electric field, and flows in the fiber receiving module (4) Magnetic nanofiber filaments are formed on the surface. 10. The method for electrospinning nanofibers according to claim 9, characterized in that the adjustable range of the magnetic field strength is 0-0.4T, and the operating voltage of the high-voltage electric field generating module (3) is 20KV- 40KV.