Cup type double-fluid parallel combined control nozzle, spinning device and spinning method

Abstract

The invention provides a cup-shaped multi-fluid parallel combined control nozzle which comprises a gathering inlet pipe, at least two capillary tubes and a cup body, a sealing cover is arranged in the cup body, a fluid inlet is formed in the sealing cover, penetrating holes with the same number as the capillary tubes are formed in the bottom of the cup body at intervals in the circumferential direction, and the gathering inlet pipe is located in the cup body. The upper end of the capillary tube extends into the gathering inlet pipe, the lower end of the capillary tube penetrates through one penetrating hole and protrudes out of the bottom face of the cup body, and a fluid outlet is formed in the position, adjacent to any penetrating hole, of the bottom face of the cup body. The invention further provides a multi-jet-flow electrostatic spinning device and a method for preparing the parallel-structure nanofibers through the multi-jet-flow electrostatic spinning device. The application is simple, the process is simple and convenient, the scale of preparing the parallel-structure nanofibers can be effectively expanded under a high-voltage electric field, and powerful support is provided for development and production of parallel-structure-based nanoproducts.

Description

Technical Field

[0001] The present invention relates to the field of nano material preparation, in particular to spinning technology, and more particularly to a cup-shaped double-fluid parallel combination control nozzle, a spinning device and a spinning method. Background Art

[0002] High-voltage electrospinning (electrospinning) is a top-down nanofabrication technology that uses an external electric field to overcome the surface tension and viscoelastic forces of the 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 obtained at the receiving end. This technology has a simple process, easy operation, a wide range of materials, and strong controllability. Furthermore, it can produce nanofibers with microstructural characteristics 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 has excellent prospects.

[0003] The greatest advantage of electrospinning is that, through the design and modification of the spinneret structure, polymer micro- and nanofibers 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). With the development of nanotechnology today, the concept of simply reducing the micro- and nanoscale dimensions of products to achieve corresponding nano-functionality has gradually become less mainstream. Currently, more attention is focused on nanodevices, complex micro- and nanostructures, and the structure-activity relationship at the nanoscale. How to efficiently prepare micro- and nanofibers with complete structural integrity and complex features, and how to tailor their functions based on their structural characteristics, is a research hotspot in nanotechnology and a key challenge in micromanufacturing and the production of novel micro- and nano-products.

[0004] Functional micro- and nanomaterials can provide high-tech support for the national economy's industrial 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. Globally, research on functional nanomaterials has yielded remarkable results in both developed and developing countries.

[0005] A 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, the scale is visible to the human eye (approximately 0.1 mm), and below that lies the micro- and nanoscale. 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, many countries and regions have actively formulated relevant strategies or plans, incorporating nanotechnology into the research and development priorities of their basic science and technology plans. Using the keyword "nano" in Web of Science yields over 1.5 million references and over 300,000 patents.

[0006] However, the manufacturing process of the parallel structured nanofibers in the prior art is relatively complicated, and it is impossible to prepare the parallel structured nanofibers with complete structures in a single step effectively and on a large scale. Summary of the Invention

[0007] The purpose of the present invention is to provide a cup-shaped dual-fluid parallel combination control nozzle, a spinning device and a spinning method, which are used to solve the technical problem in the prior art that it is impossible to effectively prepare structurally complete parallel structure nanofibers in a single step and on a large scale in batches.

[0008] The present invention provides a cup-type multi-fluid parallel combination control nozzle, comprising a summary inlet pipe, at least two capillaries and a cup body, a cover is provided in the cup body, a fluid inlet is provided on the cover, and the bottom of the cup body is provided with perforations equal to the number of the capillaries at intervals in the circumferential direction. The summary inlet pipe is located in the cup body and is passed through the cover, the upper end of any capillary extends to the lower end of the summary inlet pipe, the lower end of any capillary passes through one of the perforations and protrudes from the bottom surface of the cup body, and a fluid outlet is provided at an adjacent position of any perforation in the bottom surface of the cup body, and the lower end outlet of the capillary and the fluid outlet constitute a parallel guide outlet structure.

[0009] Furthermore, the number of the capillaries is eight.

[0010] Furthermore, the capillary tube, the cup body and the collecting inlet pipe are all bonded, fixed and sealed with epoxy resin glue.

[0011] Furthermore, the lower end of the capillary tube protrudes 1 mm from the bottom of the cup body.

[0012] The present invention also provides a multi-jet electrospinning device, including a high-voltage generator, a first injection pump, a second injection pump, the cup-shaped multi-fluid parallel combination control nozzle, a fiber receiving plate, a first syringe, a second syringe, a first elastic silicone hose and a second elastic silicone hose; the first syringe is installed in the first injection pump, and the second syringe is installed in the second injection pump. The first syringe is connected to the fluid inlet of the cup body through the first elastic silicone hose, and the second syringe is connected to the upper end of the capillary through the second elastic silicone hose. One end of the high-voltage generator is electrically connected to the capillary, and the other end of the high-voltage generator is grounded. The fiber receiving plate is located below the cup-shaped multi-fluid parallel combination control nozzle, and the fiber receiving plate is grounded.

[0013] Furthermore, the cup-shaped multi-fluid parallel combination control nozzle is connected to a fixing clamp, which facilitates hanging and fixing.

[0014] Furthermore, the fiber receiving board is a cardboard wrapped with aluminum foil.

[0015] The present invention also provides a method for preparing parallel structure nanofibers using the multi-jet 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, and the syringe transporting the first spinning solution into the cup body through the first elastic silicone tube and the fluid inlet and then flowing out from the fluid outlet, the second spinning solution is introduced into the capillary through the elastic silicone hose and flows out from the lower end of the capillary, and through the action of the high-voltage electrostatic field, parallel structure nanofibers are prepared and received by the fiber receiving plate.

[0016] Furthermore, the first spinning solution is an ethanol acetic acid aqueous solution containing 8% polyvinyl pyrrolidone and 1% tranexamic acid by mass, the second spinning solution is an ethanol solution containing 25% ethyl cellulose and 5% curcumin by mass, the sheath liquid flow rate of the first syringe is controlled by the first injection pump to be 12 mL / h, the flow rate of the second syringe is controlled by the second injection pump to be 12 mL / h, the receiving distance of the fiber receiving plate is 18 cm, and the voltage of the high-voltage generator is 27 kV.

[0017] The principle behind this invention is that multiple parallel flow outlet structures can be simultaneously installed within a cup-shaped dual-fluid parallel combination control nozzle, synchronously directing two different fluid streams into a high-voltage electrostatic field. Using these multiple parallel flow outlet structures 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 distinct parallel structures within milliseconds. Furthermore, the nozzles are composed of needle-like metal tips (capillaries) coupled with a small polymer (polypropylene) hole structure (fluid outlet) within the cup. 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.

[0018] The present invention has simple application, simple process, convenient operation and easy control. It can effectively expand the scale of preparing parallel structure nanofibers under high voltage electric field, and provide strong support for the development and production of nano products based on parallel structure.

[0019] 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 cup-shaped multi-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. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a schematic diagram of a cup-shaped, multi-fluid parallel combination control nozzle according to the present invention. Reference numerals: 1 - aggregate inlet pipe, 2 - capillary tube, 3 - cup, 4 - cover, 5 - parallel flow guide outlet structure, 18 - fluid inlet, 19 - fluid outlet.

[0021] Figure 2 A schematic diagram of a multi-jet electrospinning device according to the present invention. Reference numerals: 7 - high-voltage generator, 8 - first syringe pump, 9 - second syringe pump, 10 - cup-shaped multi-fluid parallel combination control nozzle, 11 - fiber receiving plate, 12 - first syringe, 13 - second syringe, 14 - first elastic silicone hose, 15 - second elastic silicone hose, 16 - fixing clamp.

[0022] Figure 3 This is a representative picture of the fluid stretching process for the single-step batch preparation of parallel-structured nanofibers of the present invention.

[0023] Figure 4 This is a representative composite Taylor cone image of the single-step batch preparation of parallel structured nanofibers of the present invention.

[0024] Figure 5This is a scanning electron microscope observation image of the parallel structured nanofibers prepared in a single step batch according to the present invention.

[0025] Figure 6 This is a transmission electron microscope observation image of the parallel structured nanofibers prepared in a single step batch according to the present invention. DETAILED DESCRIPTION

[0026] 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.

[0027] Example 1

[0028] like Figure 1 As shown, the present invention provides a cup-type multi-fluid parallel combination control nozzle, including a summary inlet pipe 1, at least two capillaries 2 and a cup body 3, a cover 4 is provided in the cup body 3, a fluid inlet 18 is provided on the cover 4, and the bottom of the cup body 3 is provided with perforations equal to the capillaries 2 at intervals in the circumferential direction. The summary inlet pipe 1 is located in the cup body 3 and is passed through the cover 4. The upper end of any capillary 2 extends to the lower end of the summary inlet pipe 1, and the lower end of any capillary 2 passes through one of the perforations and protrudes from the bottom surface of the cup body 3. A fluid outlet 19 is provided at an adjacent position of any perforation in the bottom surface of the cup body 3, and the lower end outlet of the capillary 2 and the fluid outlet 19 constitute a parallel guide outlet structure 5.

[0029] Furthermore, the number of the capillaries 2 is eight.

[0030] Furthermore, the capillary tube 2, the cup body 3 and the collecting inlet pipe 1 are all bonded, fixed and sealed with epoxy resin glue.

[0031] Furthermore, the lower end of the capillary tube 2 protrudes 1 mm from the bottom of the cup body 3 .

[0032] Specifically, the summary inlet pipe 1 is a polypropylene plastic tube, the cup body 3 is made of polypropylene, and the capillary tube 2 is made of metal.

[0033] Example 2

[0034] like Figure 2As shown, the present invention also provides a multi-jet electrospinning device, including a high-voltage generator 7, a first injection pump 8, a second injection pump 9, a cup-type multi-fluid parallel combination control nozzle 10, a fiber receiving plate 11, a first syringe 12, a second syringe 13, a first elastic silicone hose 14 and a second elastic silicone hose 15; the first syringe 12 is installed in the first injection pump 8, and the second syringe 13 is installed in the second injection pump 9. The first syringe 12 is connected to the fluid inlet 18 of the cup body 3 through the first elastic silicone hose 14, and the second syringe 13 is connected to the upper end of the capillary 2 through the second elastic silicone hose 15. One end of the high-voltage generator 7 is electrically connected to the capillary 2, and the other end of the high-voltage generator 7 is grounded. The fiber receiving plate 11 is located below the cup-type multi-fluid parallel combination control nozzle 10, and the fiber receiving plate 11 is grounded.

[0035] Furthermore, the cup-shaped multi-fluid parallel combination control nozzle 10 is connected to a fixing clamp 16 , which facilitates hanging and fixing.

[0036] Furthermore, the fiber receiving board 11 is a cardboard wrapped with aluminum foil.

[0037] The present invention also provides a method for preparing parallel structure nanofibers using the multi-jet 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 syringe 12 transports the first spinning solution into the cup body 3 through the first elastic silicone tube 14 and the fluid inlet 18 and then flows out from the fluid outlet 19, the second spinning solution is introduced into the capillary 2 through the elastic silicone hose 15 and flows out from the lower end of the capillary 2, and through the action of the high-voltage electrostatic field, parallel structure nanofibers are prepared and received by the fiber receiving plate 11.

[0038] Application Example 1 Electrospinning was performed using a multi-jet electrospinning device comprising a cup-shaped multi-fluid parallel combination control nozzle as described in Example 2 to directly prepare parallel structured nanofibers in batches in a single step. The steps are as follows: (1) Preparation of spinning solution The first spinning solution is an ethanol acetic acid aqueous solution containing 8% polyvinyl pyrrolidone and 1% tranexamic acid by mass, and the preparation method is as follows: 80 g polyvinyl pyrrolidone and 10 g tranexamic acid are added to 910 g of a mixed solvent, wherein the mixed solvent comprises ethanol and glacial acetic acid in a volume ratio of 80:20, and stirred to obtain an ethanol acetic acid aqueous solution containing 8% polyvinyl pyrrolidone and 1% tranexamic acid by mass; The second spinning solution is an ethanol solution containing 25% by mass ethyl cellulose and 5% by mass curcumin; the preparation method is as follows: 250g of ethyl cellulose and 50g of curcumin are added to 700g of ethanol, and stirred to obtain an ethanol solution containing 25% by mass ethyl cellulose and 5% by mass curcumin; (2) adding the first spinning solution and the second spinning solution obtained in step (1) into the first syringe 12 and the second syringe 13 respectively, and then starting the first injection pump 8 and the second injection pump 9; (3) The sheath liquid flow rate of the first syringe 12 is controlled to 12 mL / h by the first syringe pump 9, and the flow rate of the second syringe 13 is controlled to 12 mL / h by the second syringe pump 9. The high-voltage generator 7 is turned on, and the receiving distance of the fiber receiving plate 11 (i.e., the vertical distance from the lower end outlet of the capillary 2 to the fiber receiving plate 11) is adjusted to 18 cm. The voltage is increased to 27 kV for electrospinning, that is, parallel structure nanofibers are mass-produced.

[0039] The representative fluid stretching process of the present invention for single-step batch preparation of parallel structure nanofibers is shown in the following figure: Figure 3 As shown, the representative composite Taylor cone photographs of the single-step batch preparation of parallel structure nanofibers of the present invention are shown in FIG. Figure 4 shown.

[0040] 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 5 As shown. The prepared parallel structure nanofibers were collected evenly and showed a good linear state, with a diameter of 710 ± 170 nm. High-resolution transmission electron microscopy was used to observe the prepared parallel structure nanofibers, and the results were shown as follows. Figure 6 As shown, the left and right sides of the nanofiber consist of two grayscale parts, reflecting the parallel structural characteristics.

[0041] 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 cup-shaped multi-fluid parallel combination control nozzle, characterized in that: The invention comprises a summary inlet pipe, at least two capillaries and a cup body, wherein a sealing cover is provided in the cup body, and a fluid inlet is provided on the sealing cover. The bottom of the cup body is provided with perforations equal to the number of the capillaries at intervals in the circumferential direction. The summary inlet pipe is located in the cup body and penetrates the sealing cover. The upper end of any capillary extends into the lower end of the summary inlet pipe, and the lower end of any capillary passes through one of the said perforations and protrudes from the bottom surface of the cup body. A fluid outlet is provided at an adjacent position of any perforation in the bottom surface of the cup body. The lower end outlet of the capillary and the fluid outlet constitute a parallel guide outlet structure.

2. The cup-shaped multi-fluid parallel combination control nozzle according to claim 1, characterized in that: The number of the capillaries is eight.

3. The cup-shaped multi-fluid parallel combination control nozzle according to claim 1, characterized in that: The capillary tube, the cup body and the collecting inlet pipe are all bonded, fixed and sealed by epoxy resin glue.

4. The cup-shaped multi-fluid parallel combination control nozzle according to claim 1, characterized in that: The lower end of the capillary tube protrudes 1 mm from the bottom of the cup body.

5. A multi-jet electrospinning device, characterized in that: It includes a high-voltage generator, a first injection pump, a second injection pump, the cup-type multi-fluid parallel combination control nozzle according to claim 1, a fiber receiving plate, a first syringe, a second syringe, a first elastic silicone hose and a second elastic silicone hose; the first syringe is installed in the first injection pump, the second syringe is installed in the second injection pump, the first syringe is connected to the fluid inlet of the cup body through the first elastic silicone hose, the second syringe is connected to the upper end of the capillary through the second elastic silicone hose, one end of the high-voltage generator is electrically connected to the capillary, the other end of the high-voltage generator is grounded, the fiber receiving plate is located below the cup-type multi-fluid parallel combination control nozzle, and the fiber receiving plate is grounded.

6. The multi-jet electrospinning device according to claim 5, characterized in that: The cup-shaped multi-fluid parallel combination control nozzle is connected with a fixing clip.

7. The multi-jet electrospinning device according to claim 5, characterized in that: The fiber receiving plate is a cardboard wrapped with aluminum foil.

8. A method for preparing parallel structure nanofibers using the multi-jet electrospinning device according to claim 5, characterized in that: The method comprises 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, and the syringe conveying the first spinning solution into the cup body through the first elastic silicone tube and the fluid inlet and then flowing out from the fluid outlet; the second spinning solution is introduced into the capillary through the elastic silicone hose and flows out from the lower end of the capillary; and through the action of a high-voltage electrostatic field, parallel structured nanofibers are prepared and received by a fiber receiving plate.

9. The method for preparing parallel structure nanofibers according to claim 8, characterized in that: The first spinning solution is an ethanol-acetic acid aqueous solution containing 8% polyvinyl pyrrolidone and 1% tranexamic acid by mass, the second spinning solution is an ethanol solution containing 25% ethyl cellulose and 5% curcumin by mass, the sheath liquid flow rate of the first syringe is controlled by a first injection pump to be 12 mL / h, the flow rate of the second syringe is controlled by a second injection pump to be 12 mL / h, the receiving distance of the fiber receiving plate is 18 cm, and the voltage of the high-voltage generator is 27 kV.

Images