Storage tank pipe penetrating type double-fluid combined control nozzle, spinning device and spinning method

Abstract

The invention provides a storage tank through-pipe type double-fluid parallel combined control nozzle which comprises a capillary tube gathering inlet pipe, at least two capillary tubes and a fluid storage tank, the upper end of any capillary tube extends into the capillary tube gathering inlet pipe, and the lower end of any capillary tube extends into the fluid storage tank. The lower end of any capillary tube downwards penetrates through the upper side wall, the inner cavity and the lower side wall of the fluid storage tank in sequence and protrudes out of the lower side wall of the fluid storage tank, a through hole is formed in the position, adjacent to any capillary tube, of the lower side wall of the fluid storage tank, and the capillary tubes and the through hole form parallel fluid guide-out openings. The two ends of the fluid storage tank are provided with a fluid inlet and a fluid outlet respectively. The invention further provides a multi-jet-flow high-voltage electrostatic spinning device comprising the nozzle and a spinning method. The electrostatic spinning device and the spinning method are easy to apply, simple and convenient in process, convenient to operate and easy to control, and the parallel-structure nanofibers can be effectively prepared in a single step under a high-voltage electric field.

Description

Technical Field

[0001] The present invention belongs to the field of nanomaterial preparation, and in particular relates to a tank-through-tube type dual-fluid parallel combined control nozzle, a multi-jet high-voltage electrospinning device with a tank-through-tube type dual-fluid nozzle, and a method for using the device to perform single-step electrospinning batch preparation of nanofibers with parallel structural characteristics. Background Art

[0002] High-voltage electrospinning (electrospinning) is a top-down nanofabrication technique that uses an external electric field to overcome the surface tension and viscoelastic forces of a droplet at the nozzle tip, forming a jet. Under the combined effects of electrostatic repulsion, Coulomb force, and surface tension, the atomized liquid jet is bent, stretched, and split at high frequencies, stretching tens of millions of times within tens of milliseconds. After solvent evaporation or melt cooling, nanofibers are formed at the receiving end. This technology offers a simple process, easy control, a wide range of materials, strong controllability, and the ability to produce nanofibers with unique microstructures through nozzle design. It is considered the most promising method for the industrial production of continuous nanofibers, and its application in the preparation of functional nanofibers holds great promise.

[0003] The greatest advantage of electrospinning is that, by designing and modifying the spinneret structure, polymer microfibers with specific structural characteristics can be efficiently prepared in a single step. This is difficult to achieve using other "bottom-up" chemical synthesis methods. The most common methods are the use of a coaxial capillary metal sleeve as the spinneret to produce core-sheath nanofibers (Polym. Rev. 2008, 48, 353-377) and the use of a left-right spinneret to produce parallel nanofibers (Chem. Rev. 2013, 113, 5194-5261).

[0004] With the development of nanotechnology today, the concept of simply reducing a product's micro- or nanoscale dimensions to achieve corresponding nano-functionality has gradually faded from the mainstream. Currently, more attention is focused on nanodevices, complex micro- or nanostructures, and the structure-activity relationships at the nanoscale. How to effectively prepare micro- and nanofibers with complete and complex structural features, and how to tailor their functions based on their structural characteristics, is a research hotspot in nanotechnology and a key challenge in the field of micromanufacturing and the production of new micro- and nano-products.

[0005] Functional micro- and nanomaterials can provide high-tech support for the national economic restructuring and the reform of traditional industries. Their industrialized manufacturing is a strategic emerging industry receiving national support and development. In today's nanotechnology era, functional micro- and nanomaterials are rapidly penetrating every application area. A wealth of research results on functional nanomaterials are being produced worldwide, both in developed and developing countries. Against this backdrop, improvements in the industrialized manufacturing of various functional micro- and nanomaterials will lead to preferential access to relevant research findings, potentially yielding greater economic and social benefits.

[0006] The molecule is an interface. Below the molecule lies pure chemical synthesis based on covalent and ionic bonds (corresponding to the chemical industry). Above the molecule, below the visible to the human eye (approximately 0.1 mm), lies the micro- and nanoscale realm. This is a rich source of information for humanity's current understanding of the world and a focal point for its transformation of the material world (corresponding to micro- and nano-fabrication of functional materials, and the new chemical molecular synthesis mentioned above also serves this purpose). In July 1990, the first International Conference on Nanoscience and Nanotechnology was held in Baltimore, USA, marking the official birth of nanoscience and technology. By 1999, nanotechnology had begun to gradually enter the market. Over the past 20 years, numerous countries and regions have formulated relevant strategies and plans, invested heavily in seizing strategic nanotechnology positions, established nanomaterials research centers, and included nanotechnology as a research and development priority in their basic science and technology plans. A search using the keyword "nano" in Web of Science yields over 1.5 million references and over 300,000 patents. However, the application of existing technologies in civilian nano-products remains very limited. Globally, the proportion of nanoscience research output is very low, and the industrialization of nanotechnology is underdeveloped. Therefore, the industrialization of various functional micro- and nanomaterials is extremely important and urgent.

[0007] In the existing technology, parallel structured nanofibers have broad application prospects, but their manufacturing process is relatively complicated and not suitable for industrial production.

[0008] Based on repeated experiments, the present invention follows the behavioral characteristics of fluids under high-voltage electric fields and basic natural laws to develop a tank-through-tube dual-fluid combination control nozzle. By using this nozzle to assemble an electrospinning device and implement the electrospinning process, it is possible to effectively and batch-scale prepare structurally complete parallel-structured nanofibers in a single step, providing possibilities for the design and preparation of new nano-functional materials based on parallel structures. Summary of the Invention

[0009] The present invention provides a tank-through-tube type dual-fluid combined control nozzle, a spinning device and a spinning method, which are used to solve the technical problem of complex process for preparing parallel structure nanofibers in the prior art.

[0010] The present invention provides a tank-through-tube type dual-fluid parallel combination control nozzle, which includes a capillary summary inlet pipe, at least two capillaries, and a fluid storage tank. The upper end of any capillary extends into the capillary summary inlet pipe, the length direction of the fluid storage tank is perpendicular to the length direction of the capillary summary inlet pipe, the lower end of any capillary passes downward through the upper side wall, the inner cavity, and the lower side wall of the fluid storage tank in sequence and protrudes from the lower side wall of the fluid storage tank. The capillaries in the fluid storage tank are arranged at intervals along the length direction of the fluid storage tank, and a through hole is provided in the lower side wall of the fluid storage tank at an adjacent position to any capillary. The capillary and the through hole constitute a parallel fluid lead-out port, and the two ends of the fluid storage tank are respectively provided with a fluid inlet and an outlet.

[0011] Furthermore, the number of the capillaries is six.

[0012] Furthermore, the length of the lower end of the capillary protruding from the lower side wall of the fluid storage tank is 1 mm.

[0013] Furthermore, the interval between any two adjacent capillaries is 3 cm.

[0014] Furthermore, the capillary tube, the capillary tube collecting inlet pipe, and the fluid storage tank are all bonded and sealed with epoxy resin adhesive.

[0015] The present invention also provides a multi-jet high-voltage electrospinning device, comprising a high-voltage generator, a first injection pump, a second injection pump, the tank-through-tube type dual-fluid parallel combination control nozzle, a fiber receiving plate, a first syringe, a second syringe, a first silicone hose and a second silicone hose; the first syringe is installed in the first injection pump, and the outlet of the first syringe is connected to the fluid inlet of the fluid storage tank through the first silicone hose; the second syringe is installed in the second injection pump, and the outlet of the second syringe is connected to the capillary through a pipeline; one end of the current output end of the high-voltage generator is connected to one of the capillaries, and the other end of the current output end of the high-voltage generator is grounded; a fiber receiving plate is provided below the tank-through-tube type dual-fluid parallel combination control nozzle, and the fiber receiving plate is grounded.

[0016] Furthermore, it also includes a hanging rod, which is used to hang the tank through-tube type dual-fluid parallel combination control nozzle, and the capillary tube is hung on the hanging rod.

[0017] Furthermore, the fiber receiving board is a cardboard wrapped with aluminum foil.

[0018] The present invention also provides a method for preparing parallel structure nanofibers using the multi-jet high-voltage electrospinning device, comprising the following steps: adding a first spinning solution into a first syringe, adding a second spinning solution into a second syringe, turning on the first injection pump, the second injection pump, and the high-voltage generator, the first syringe transporting the first spinning solution into a fluid storage tank through a silicone tube, and the second spinning solution being introduced into a capillary through a silicone hose, and preparing parallel structure nanofibers through the action of a high-voltage electrostatic field.

[0019] Furthermore, the first spinning solution is an ethyl cellulose ethanol solution with a mass percentage concentration of 25%; the second spinning solution is an ethyl pyrrolidone ethanol solution with a mass percentage concentration of 8%; the sheath liquid flow rate of the first syringe is controlled by the first injection pump to be 10 mL / h, and the flow rate of the second syringe is controlled by the second injection pump to be 10 mL / h, the fiberboard receiving distance is 20 cm, and the voltage of the high-voltage generator is 23 kV.

[0020] The principle of the present invention is that multiple parallel fluid outlets can be simultaneously installed within a tank-through-tube dual-fluid parallel combination control nozzle. These outlets synchronously guide two different fluids into a high-voltage electrostatic field. Using the multiple parallel nozzle outlets as a macroscopic template, the interaction between the high-voltage electrostatic field and the fluids stretches the multiple parallel spinning fluids into solid nanofibers with a clear parallel structure within milliseconds. Furthermore, the numerous nozzles of the tank-through-tube dual-fluid parallel combination control nozzle feature a needle-like metal tip and a polymer (polypropylene) hole structure within a basket. This facilitates the guiding effect of the "needle" and the "wall-attaching" effect of the liquid flowing out of the polymer hole, ensuring accurate "replication" of the macroscopic parallel outlet template to the microscopic two-chamber parallel structure of nanofibers under the high-voltage electrostatic field.

[0021] The electrospinning device and spinning method of the present invention are simple to use, simple in process, easy to operate and easy to control. They can effectively prepare parallel structured nanofibers in a single step under a high-voltage electric field, and can be mass-produced by increasing the number of spinning heads, providing strong support for the development and production of nano-products based on parallel structures. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a schematic diagram of a dual-fluid parallel combination control nozzle with a tank-through-tube design according to the present invention. 1 - capillary tube inlet pipe, 2 - capillary tube, 3 - fluid storage tank, 4 - fluid inlet, 5 - parallel fluid outlet.

[0023] Figure 2 This is a photograph of the diversion outlet 5 composed of the capillary tube of the tank-through-tube type dual-fluid parallel combination control nozzle and the small hole at the bottom of the tank (as indicated by the arrow) of the present invention.

[0024] Figure 3 This is a schematic diagram of the structure of a multi-jet high-voltage electrospinning device incorporating a dual-fluid parallel combination control nozzle with a tank-through-tube structure according to the present invention. 6 - Suspension rod, 7 - High-voltage generator, 8 - First syringe pump, 9 - Second syringe pump, 10 - Dual-fluid parallel combination control nozzle with a tank-through-tube structure, 11 - Fiber receiving plate, 12 - First syringe, 13 - Second syringe, 14 - First silicone hose, 15 - Second silicone hose.

[0025] Figure 4 A series of Taylor cone images appear after voltage is applied to the nozzle.

[0026] Figure 5 A representative image of the fluid stretching process for the single-step batch preparation of side-by-side structured nanofibers.

[0027] Figure 6 Representative side-by-side composite Taylor cone images of single-step batch preparation of side-by-side structured nanofibers.

[0028] Figure 7 Scanning electron microscope observation of parallel-structured nanofibers prepared in a single step batch.

[0029] Figure 8 Transmission electron microscope observation of parallel-structured nanofibers prepared in a single step batch. DETAILED DESCRIPTION

[0030] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0031] Example 1

[0032] like Figure 1-Figure 2 As shown, the present invention provides a tank-through-tube type dual-fluid parallel combination control nozzle 10, comprising a capillary summary inlet pipe 1, at least two capillaries 2, and a fluid storage tank 3. The upper end of any capillary tube 2 extends into the capillary summary inlet pipe 1 (all capillaries 2 are upwardly summarized along the capillary summary inlet pipe 1), the length direction of the fluid storage tank 3 is perpendicular to the length direction of the capillary summary inlet pipe 1, and the lower end of any capillary tube 2 passes downward through the upper side wall, the inner cavity, and the lower side wall of the fluid storage tank 3 in sequence and protrudes from the lower side wall of the fluid storage tank 3. The capillaries 2 in the fluid storage tank 3 are arranged at intervals along the length direction of the fluid storage tank 3, and a through hole is provided in the lower side wall of the fluid storage tank 3 at a position adjacent to any capillary tube 2, such as Figure 3As shown, the capillary 2 and the through hole constitute a parallel fluid outlet 5 (forming a parallel flow diversion mode in which two fluids are introduced into the high-voltage electrostatic field in parallel), and the two ends of the fluid storage tank 3 are respectively provided with a fluid inlet 4 and an outlet.

[0033] Furthermore, the number of the capillaries 2 is six.

[0034] Furthermore, the length of the bottom of the capillary tube 2 protruding from the lower side wall of the fluid storage tank 3 is 1 mm.

[0035] Furthermore, the interval between any two adjacent capillaries 2 is 3 cm.

[0036] Furthermore, the capillary tube 2, the capillary tube collecting inlet pipe 1 and the fluid storage tank 3 are all bonded and sealed with epoxy resin adhesive.

[0037] The capillary inlet 1 is a polypropylene plastic tube. The capillaries 2 are all made of conductive metal. The fluid inlet 4 can also be used as a cleaning port.

[0038] Example 2

[0039] The present invention also provides a multi-jet high-voltage electrospinning device, the composition diagram of which is shown in FIG. Figure 3 As shown, its basic structure includes a high-pressure generator 7, a first injection pump 8, a second injection pump 9, a tank-through-tube type dual-fluid parallel combination control nozzle 10, a fiber receiving plate 11, a first syringe 12, a second syringe 13, a first silicone hose 14 and a second silicone hose 15; The first syringe 12 is installed in the first injection pump 8, and the outlet of the first syringe 12 is connected to the fluid inlet 4 of the fluid storage tank 3 through the first silicone hose 14. The second syringe 13 is installed in the second injection pump 9, and the outlet of the second syringe 13 is connected to the capillary 2 through a pipeline. One end of the current output end of the high-voltage generator 7 is connected to one of the capillaries 2, and the other end of the current output end of the high-voltage generator 7 is grounded. A fiber receiving plate 11 is provided below the tank-through-tube type dual-fluid parallel combination control nozzle 10, and the fiber receiving plate 11 is grounded.

[0040] Furthermore, it also includes a hanging rod 6, which is used to hang the tank through-tube type dual-fluid parallel combination control nozzle 10, and the capillary tube 2 is hung on the hanging rod 6.

[0041] Furthermore, the fiber receiving board 11 is a cardboard wrapped with aluminum foil.

[0042] The present invention also provides a method for preparing parallel structure nanofibers using a multi-jet high-voltage electrospinning device, comprising the following steps: adding a first spinning solution into a first syringe 12, adding a second spinning solution into a second syringe 13, turning on the first injection pump 8, the second injection pump 9, and the high-voltage generator 7, the first syringe 12 transports the first spinning solution into the fluid storage tank 3 through the silicone tube 14, and the second spinning solution is introduced into the capillary 2 through the silicone hose 15, and the parallel structure nanofibers are prepared through the action of a high-voltage electrostatic field.

[0043] Application Example 1 Electrospinning was performed using the multi-jet high-pressure electrospinning apparatus described in Example 2, which included a tank-through-tube type dual-fluid parallel combination control nozzle, to directly prepare parallel structured nanofibers in batches in a single step. The steps were as follows: (1) Preparation of spinning solution The first spinning solution is an ethyl cellulose ethanol solution with a mass percentage concentration of 25%, and the preparation method is as follows: 25 g of ethyl cellulose is added to 75 g of ethanol, and stirred to obtain an ethyl cellulose ethanol solution with a mass percentage concentration of 25%; The second spinning solution is an 8% by weight polyvinyl pyrrolidone ethanol solution, which is prepared as follows: 8 g of polyvinyl pyrrolidone is added to 92 g of ethanol and stirred to obtain an 8% by weight polyvinyl pyrrolidone ethanol solution; (2) adding the first spinning solution and the second spinning solution obtained in step (1) into the first syringe and the second syringe respectively, and then starting the first injection pump and the second injection pump; (3) The sheath liquid flow rate of the first syringe 12 is controlled to 10 ml / h by the first syringe pump, and the flow rate of the second syringe 13 is controlled to 10 ml / h by the second syringe pump. The receiving distance of the fiberboard is adjusted to 20 cm, and the voltage of the high-voltage generator 7 is increased to 23 kV. Parallel structure nanofibers can be prepared in a single step. The series of Taylor cones after the actual voltage is applied are as follows Figure 4 As shown, the representative fluid stretching process of single-step batch preparation of parallel structure nanofibers is shown in Figure 5 As shown, the representative composite Taylor cone images of the single-step batch preparation of parallel structured nanofibers are shown in Figure 6 shown.

[0044] Application Example 2 The surface of the parallel structure nanofibers prepared in Example 1 was sprayed with gold using a field scanning electron microscope and the results were as follows: Figure 7 The prepared parallel structure nanofibers were collected evenly and showed a good linear state, with a diameter of 780 ± 210 nm. The prepared parallel structure nanofibers were observed using high-resolution transmission electron microscopy, and the results were shown in Figure 2. Figure 8 As shown, the upper and lower parts of the nanofiber are composed of two grayscale parts, reflecting the parallel structural characteristics.

[0045] The above description is merely an example of the implementation of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements can be made without departing from the technical principles of the present invention. These improvements should also be regarded as within the scope of protection of the present invention.

Claims

1. A tank-through-tube dual-fluid parallel combination control nozzle, characterized by: The invention comprises a capillary summary inlet pipe, at least two capillaries, and a fluid storage tank. The upper end of any capillary extends into the capillary summary inlet pipe. The length direction of the fluid storage tank is perpendicular to the length direction of the capillary summary inlet pipe. The lower end of any capillary passes downward through the upper side wall, the inner cavity, and the lower side wall of the fluid storage tank in sequence and protrudes from the lower side wall of the fluid storage tank. The capillaries in the fluid storage tank are arranged at intervals along the length direction of the fluid storage tank. A through hole is provided in the lower side wall of the fluid storage tank at an adjacent position to any capillary. The capillary and the through hole constitute a parallel fluid outlet. The two ends of the fluid storage tank are respectively provided with a fluid inlet and an outlet.

2. According to claim 1, a tank-through-tube type dual-fluid parallel combination control nozzle, characterized in that: The number of the capillaries is six.

3. According to claim 1, a tank-through-tube type dual-fluid parallel combination control nozzle, characterized in that: The length of the lower end of the capillary tube protruding from the lower side wall of the fluid storage tank is 1 mm.

4. The tank-through-pipe dual-fluid parallel combination control nozzle according to claim 1, characterized in that: The distance between any two adjacent capillaries is 3 cm.

5. The tank-through-tube type dual-fluid parallel combination control nozzle according to claim 1, characterized in that: The capillary tube, the capillary tube collecting inlet pipe and the fluid storage tank are all bonded and sealed with epoxy resin adhesive.

6. A multi-jet high-voltage electrospinning device, characterized by: It includes a high-voltage generator, a first injection pump, a second injection pump, the tank-through-tube type dual-fluid parallel combination control nozzle according to claim 1, a fiber receiving plate, a first syringe, a second syringe, a first silicone hose and a second silicone hose; the first syringe is installed in the first injection pump, the outlet of the first syringe is connected to the fluid inlet of the fluid storage tank through the first silicone hose, the second syringe is installed in the second injection pump, the outlet of the second syringe is connected to the capillary through a pipeline, one end of the current output end of the high-voltage generator is connected to one of the capillaries, the other end of the current output end of the high-voltage generator is grounded, and a fiber receiving plate is provided below the tank-through-tube type dual-fluid parallel combination control nozzle, and the fiber receiving plate is grounded.

7. The tank-through-pipe type dual-fluid parallel combination control nozzle according to claim 6, characterized in that: It also includes a hanging rod, which is used for hanging a tank through-tube type double-fluid parallel combination control nozzle, and the capillary tube is hung on the hanging rod.

8. According to claim 6, a tank-through-tube type dual-fluid parallel combination control nozzle, characterized in that: The fiber receiving plate is a cardboard wrapped with aluminum foil.

9. A method for preparing parallel structured nanofibers using the multi-jet high-voltage electrospinning device according to claim 6, characterized in that: The method includes the following steps: adding a first spinning solution into a first syringe, adding a second spinning solution into a second syringe, turning on the first injection pump, the second injection pump, and the high-voltage generator, the first syringe transporting the first spinning solution into a fluid storage tank through a silicone tube, and the second spinning solution being introduced into a capillary through a silicone hose, and preparing parallel structured nanofibers through the action of a high-voltage electrostatic field.

10. The method for preparing parallel structure nanofibers according to claim 9, wherein: The first spinning solution was an ethyl cellulose ethanol solution with a mass percentage concentration of 25%; the second spinning solution was an ethanol solution of polyvinyl pyrrolidone with a mass percentage concentration of 8%; the sheath liquid flow rate of the first syringe was controlled by a first injection pump at 10 mL / h, and the flow rate of the second syringe was controlled by a second injection pump at 10 mL / h. The fiberboard receiving distance was 20 cm, and the voltage of the high-voltage generator was 23 kV.

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