CN117358948A - Metal nano-structure 3D printing device and method integrated with annular electrode spray head - Google Patents

Metal nano-structure 3D printing device and method integrated with annular electrode spray head Download PDF

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Publication number
CN117358948A
CN117358948A CN202311348193.5A CN202311348193A CN117358948A CN 117358948 A CN117358948 A CN 117358948A CN 202311348193 A CN202311348193 A CN 202311348193A CN 117358948 A CN117358948 A CN 117358948A
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CN
China
Prior art keywords
printing
spray head
electrode
annular
annular electrode
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Pending
Application number
CN202311348193.5A
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Chinese (zh)
Inventor
王瑞
周君仪
段培开
朱晓阳
杨建军
兰红波
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Qingdao University of Technology
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Qingdao University of Technology
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Priority to CN202311348193.5A priority Critical patent/CN117358948A/en
Publication of CN117358948A publication Critical patent/CN117358948A/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
    • B22F12/50—Means for feeding of material, e.g. heads
    • B22F12/53—Nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling

Abstract

The invention discloses a 3D printing device and a method for a metal nano structure of an integrated annular electrode nozzle, which belong to the field of additive manufacturing, and comprise a printing platform, wherein an injection system for material injection is arranged above the printing platform; the spraying system comprises a printing spray head which is connected with the storage cylinder; the printing spray head comprises an electrospray printing spray head and an electric field focusing module, wherein the electric field focusing module comprises an annular electrode assembly arranged above a printing platform; the annular electrode assembly comprises a plurality of annular electrodes which are sequentially arranged at intervals from top to bottom, through holes are arranged in the annular electrodes, and the inner diameters of the through holes of the plurality of annular electrodes are sequentially reduced from top to bottom.

Description

Metal nano-structure 3D printing device and method integrated with annular electrode spray head
Technical Field
The invention belongs to the field of additive manufacturing, and particularly relates to a metal nano-structure 3D printing device and method integrating an annular electrode nozzle.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The metal nano structure plays an important role in the fields of advanced electronics/optoelectronics, aerospace, micro-nano electromechanical systems, soft robots, new energy sources, metamaterials and the like. However, in the prior art, the manufacturing cost, the complexity of the process, and the limitation of materials greatly limit the manufacturing and application of the nanostructure. Currently, the main fabrication methods of nanoscale metal structures include photolithography, etching, nanoimprinting, aerosol jetting, electrohydrodynamic jetting techniques, and the like. The optical lithography technology has the advantages of high yield, good repeatability, convenient industrialized application and the like, but has the problems of complex mask manufacturing, high manufacturing cost, small area, incapability of realizing complex nanoscale three-dimensional structures and the like; the nano imprinting has the advantages of high production efficiency, high resolution and suitability for mass production, but the template manufacturing requires electron beam lithography and other technologies, and has high manufacturing cost and difficult large-area manufacturing; the etching technology also has the problems of complex and difficult template manufacture, and serious environmental pollution in the manufacturing process. Compared with the traditional material reduction and equal material manufacturing technology, the micro-nano 3D printing technology has wide application in the aspect of nano structure printing, and has the advantages of low cost, simple structure, printing of three-dimensional complex micro-nano structure, no need of mask/mould and direct forming. The aerosol jet printing technology is used as a typical micro-nano 3D printing technology, printing with a characteristic structure of 1 mu m can be achieved, and the Faraday 3D printing technology formed by the composite electric field driving jet can achieve printing of nano-scale metal structures. However, aerosol jet technology has a limited range of printing material viscosities, limiting the range of printing materials.
The electric spray printing is a printing technology based on electrohydrodynamic effect, adopts an external electric field to drive functional liquid to generate fine jet at the outlet of a spray needle, and the jet or the liquid drop which is pulled out to spray liquid drop by means of the action of the strong electric field force on the meniscus of the spray needle has ultrahigh resolution, the diameter of the jet is smaller than 100nm and is far smaller than the inner diameter of the spray needle, but the manufacturing of a sub-micro scale metal structure can only be realized at present due to the limitation of the fineness of conductive paste, and the printing efficiency is lower. Although the electrospray technology can realize the manufacture of nano-scale particles, the ejected nano-particles are disordered and cannot realize the precise formation of a nano-scale three-dimensional structure; meanwhile, the particles generated by electrospray have the problems of uneven size distribution and the like, so that the manufacture of ordered nano-scale structures is limited.
Accordingly, the existing printing technology has various disadvantages and limitations in terms of printing materials, printing stability, printing resolution, and the like. In particular, the prior art has a great challenge in printing nano-scale electrodes. Therefore, development of a technology capable of realizing nano-scale electrode printing is urgently needed, and stability, consistency and material applicability of a printing structure are improved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a 3D printing device and a method for a metal nano structure of an integrated annular electrode nozzle, which break through the limitations of the printing resolution, printing stability, printing materials and the like of the prior printing technology and realize the manufacture of the metal structure with nano scale.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a metal nano-structure 3D printing device integrated with a ring electrode spray head, which comprises a printing platform, wherein an injection system for material injection is arranged above the printing platform; the spraying system comprises a printing spray head which is connected with the storage cylinder; the printing spray head comprises an electrospray printing spray head and an electric field focusing module, wherein the electric field focusing module comprises an annular electrode assembly arranged above a printing platform; the annular electrode assembly comprises a plurality of annular electrodes which are sequentially arranged at intervals from top to bottom, through holes are arranged in the annular electrodes, and the inner diameters of the through holes of the plurality of annular electrodes are sequentially reduced from top to bottom.
As a further technical scheme, a plurality of annular electrodes are coaxially arranged, annular baffle plates are arranged at the through holes of the annular electrodes and are arranged on the surfaces of the annular electrodes, and the baffle plates have set heights; each annular electrode is externally connected with a positive electrode of a high-voltage pulse power supply.
As a further technical scheme, each annular electrode is connected to the storage cylinder through an electrode fixing frame, and the outer diameters of the annular electrodes are sequentially increased from top to bottom; the electrode fixing frame is made of transparent materials and is of a cylindrical structure.
As a further technical scheme, the ring electrode at the lowest part is provided with a solution discharge port, the solution discharge port is connected with a discharge unit, the discharge unit comprises a discharge pipe and an injector, the discharge pipe is connected with the solution discharge port of the ring electrode, and the discharge pipe is communicated with the injector.
As a further technical scheme, the electrospray printing nozzle comprises a metal nozzle and a quartz glass nozzle, wherein the quartz glass nozzle is sleeved on the outer layer of the metal nozzle; the electrospray printing spray head is connected to the lower end of the storage cylinder and connected with the positive electrode of the high-voltage pulse power supply.
As a further technical scheme, the tip end position of the electrospray printing nozzle is positioned above the annular electrode; the voltage difference range of the electrospray printing nozzle and the annular electrode is 2000-2500V.
As a further technical scheme, the device also comprises an observation unit, wherein the observation unit is aligned with the position of the electrospray printing nozzle.
As a further technical scheme, the injection system further comprises a back pressure control unit and a feeding unit, wherein the back pressure control unit comprises a pneumatic tube connected with the storage cylinder, and the pneumatic tube is provided with a precise pressure regulating valve; the feeding unit comprises a feeding pipe connected with the storage cylinder, and the feeding pipe is connected with the microinjection pump.
As a further technical scheme, the top of the printing platform is fixedly provided with a printing substrate, the storage cylinder is fixed on a Z-axis workbench through a fixing frame, and the Z-axis workbench controls the height difference of the printing spray head from the printing substrate; the printing platform is connected with the negative electrode of the high-voltage pulse power supply.
In a second aspect, the present invention also provides a working method of the metal nano-structure 3D printing device integrated with the ring electrode spray head, which comprises the following steps:
preparing a printing spray head, connecting the electrospray printing spray head to the lower end of a storage cylinder, placing the storage cylinder on a Z-axis workbench, and adjusting the position of an observation unit so as to observe the printing condition of the spray head;
the annular electrode is fixed, so that the distance between the electrospray printing nozzle and the annular electrode is ensured to be set, and the electrospray printing nozzle and the annular electrode are respectively connected with a high-voltage pulse power supply; the discharge hole of the lowest annular electrode is connected with a discharge pipe and an injector;
placing a printing substrate on a printing platform, moving the printing platform and the Z-axis workbench to a printing position, starting a high-voltage pulse power supply, spraying liquid drops from an electrospray printing nozzle by using a printing material under the action of an electric field, and spraying the liquid drops from a through hole of an annular electrode by using the focusing action of the electric field of the annular electrode by using the printing material to form cone jet; in combination with the motion of the printing platform, the material is deposited on the substrate to realize micro-nano structure manufacturing; in the printing process, observing the condition of depositing solution on the annular electrode in real time, and pumping out the solution by using a syringe when the solution is excessively deposited;
and after printing is finished, the high-voltage pulse power supply is turned off, the printing platform and the Z-axis workbench are moved to the original station, and the printing workpiece is taken down from the printing platform.
The beneficial effects of the invention are as follows:
according to the metal nano-structure 3D printing device, the electrospray printing spray head is arranged to be matched with the electric field focusing module, the spray of nano-scale liquid drops can be realized by utilizing the electrospray principle, and only liquid drops with specific size range can be sprayed out of the spray head due to the limitation of the focusing effect of the annular electrode.
According to the metal nano-structure 3D printing device, the plurality of annular electrodes are arranged, the annular electrodes are sequentially arranged at intervals from top to bottom, the inner diameter of the through hole of each annular electrode is sequentially reduced from top to bottom, an electric field can be effectively focused, liquid drops sprayed from an electrospray nozzle are gathered in a smaller inner diameter range, and printing resolution is improved.
The 3D printing device with the metal nano structure can effectively utilize the electric field between electrospray, the annular electrode and the printing substrate, and can control the direction of the electric field force and the direction of the ion movement among the electrospray, the annular electrode and the printing substrate by changing different pressure differences, so that the printing size can be accurately controlled.
The 3D printing device of the metal nano structure has wider viscosity range of printing materials, can realize printing of conductive materials of 0-10000 mPa.s, has simple steps for manufacturing the micro-nano structure, can form a two-dimensional/three-dimensional structure by a printing process, and greatly reduces the production cost.
According to the metal nano-structure 3D printing device, the material utilization rate is improved in the additive manufacturing process, the deposition solution of the annular electrode is pumped out through the discharging unit, so that the material can be recycled, no waste liquid or waste gas is generated, and the environment is friendly.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a schematic illustration of the printing principle of a nano-scale metal structure 3D printing device integrated with a ring electrode spray head in the invention;
FIG. 2 is a schematic illustration of a nano-scale metal structure 3D printing device structure incorporating a ring electrode showerhead of the present invention;
FIG. 3 is a cross-sectional view of a print head of a nano-scale metal structure 3D printing device of the integrated ring electrode head of the present invention;
FIG. 4 is an enlarged view of a print head of a nano-scale metal structured 3D printing device of the present invention incorporating a ring electrode head;
in the figure: the mutual spacing or size is exaggerated for showing the positions of all parts, and the schematic drawings are used only for illustration;
the device comprises a printing platform 1, a printing substrate 2, a ring electrode 3, an electrode fixing frame 4, a discharging unit 5, an electrospray printing nozzle 6, a fixing frame 7, a material storage cylinder 8, a Z-axis workbench 9, a microscope 10, a precise pressure regulating valve 11, a pneumatic tube 12, a material supply tube 13, a microinjection pump 14 and a high-voltage pulse power supply 15.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As described in the background art, aiming at the defects and limitations existing in the existing micro-nano 3D printing technology, the invention provides a metal structure 3D printing device and method integrating a ring electrode spray head in order to solve the technical problems.
Example 1
In an exemplary embodiment of the present invention, as shown in fig. 2, a metal nano-structure 3D printing device integrated with a ring electrode showerhead is proposed, which includes a printing platform 1, an injection system for material injection, an observation unit; the spraying system comprises a printing spray head, a back pressure control unit, a feeding unit, a storage cylinder 8 and a high-voltage pulse power supply 15, wherein the printing spray head comprises an electrospray printing spray head 6 and an electric field focusing module, and the electric field focusing module comprises an annular electrode assembly, an electrode fixing frame 4 and a discharging unit 5.
The printing platform 1 is positioned at the bottom, and the printing substrate 2 is arranged on the printing platform 1 and is fixed on the printing platform 1 in a vacuum adsorption mode. An annular electrode assembly is arranged above the printing substrate 2, a discharge unit 5 is connected to a solution discharge hole at the bottom of the annular electrode assembly, and the annular electrode assembly is fixed at the bottom of a storage cylinder 8 through an electrode fixing frame 4. The electrospray printing nozzle 6 is connected to the lower end of a storage cylinder 8, and the storage cylinder 8 and a microscope 10 are fixed on a Z-axis workbench 9 through a fixing frame 7. The precise pressure regulating valve 11 and the air pressure pipe 12 form a back pressure control unit, the feed pipe 13 and the microinjection pump 14 form a feed unit, the feed unit and the back pressure control unit are both connected with a storage cylinder, and the upper end of the storage cylinder 8 is specifically connected with the air pressure pipe 12 and the feed pipe 13. The electrospray printing nozzle 6 and the annular electrode 3 are connected with a high-voltage pulse power supply 15 to provide a required printing electric field. The printing platform 1 is connected with the cathode of the high-voltage pulse power supply.
In the embodiment, the printing platform 1 is a two-dimensional working platform, the maximum motion displacement of the working platform is 400mm multiplied by 400mm, and the motion in the X-Y direction is controlled.
In this embodiment, the print substrate 2 is a conductive or nonconductive substrate such as silica gel, glass, silicon wafer, or resin.
Specifically, the annular electrode assembly is composed of three annular electrodes 3, through holes are arranged in the annular electrodes 3, the three annular electrodes 3 are coaxially arranged, the three annular electrodes 3 are sequentially arranged at intervals from top to bottom, and the inner diameters of the through holes of the three annular electrodes are sequentially reduced from top to bottom.
The annular electrode assembly can effectively focus an electric field, so that high-strength electric field drives liquid drops to be ejected from the annular electrode through holes, and meanwhile, the annular electrode assembly can gradually block the liquid drops with larger sizes and only allow the liquid drops with specific sizes to be ejected from the through holes. The through hole of the annular electrode is provided with the annular baffle plate, and the baffle plate is arranged on the surface of the annular electrode and has a certain height, so that the solution can be effectively prevented from flowing out of the through hole to influence the printing resolution.
Each annular electrode 3 is connected to a storage cylinder 8 through an electrode fixing frame 4, and the outer diameters of the three annular electrodes are sequentially increased from top to bottom, so that the annular electrodes are conveniently and sequentially installed. Each annular electrode is externally connected with the positive electrode of a high-voltage pulse power supply 15, and the applied voltage is regulated and controlled according to the applied range of the electrospray glass printing nozzle.
The annular electrodes with different inner diameters and different outer diameters are prepared by utilizing a metal 3D printing process, then the annular electrodes are fixed on an annular electrode fixing frame, and an electric field focusing effect is realized by respectively externally applying power to the three annular electrodes.
The ring electrode 3 is prepared by metal 3D printing, and the optional materials are copper, aluminum, silver, and the like. The three ring electrodes have an inner diameter of 30-400 μm, an outer diameter of 1-50mm, and a thickness of 1-500 μm. In this example, the three annular electrode through holes have an inner diameter of 200 μm, 150 μm and 100 μm in this order from top to bottom.
The solution discharge hole is reserved at the position of the lowest layer annular electrode 3, the solution discharge hole is connected with the discharge unit 5, the discharge unit 5 comprises a discharge pipe and an injector, the discharge pipe is connected with the solution discharge hole of the annular electrode, and the discharge pipe is communicated with the injector, so that materials can be recovered conveniently. When the annular electrode solution is excessively deposited, the solution is timely pumped out of the discharge pipe by a syringe.
The electrode fixing frame 4 is fixed at the bottom of the storage cylinder, is made of visual transparent materials, and is made of PP, PC, silica gel and the like, so that the electrospray morphology can be observed conveniently. The size of the electrode fixing frame is set according to the size of the annular electrode, and the electrode fixing frame is cylindrical, detachable and in a sealing state, so that the solution is prevented from being sprayed out. The electrode fixing frame is provided with a discharge hole at the connection part of the annular electrode and the discharge unit, and the discharge hole corresponds to the solution discharge hole of the annular electrode, so that the solution can flow out from the discharge hole conveniently; the electrode fixing frame is provided with a through hole at the connection part of the annular electrode and the power supply, so that the connection of the high-voltage pulse power supply is facilitated.
Specifically, the electrospray printing nozzle 6 includes a metal nozzle and a quartz glass nozzle, the quartz glass nozzle is sleeved on the outer layer of the metal nozzle, the quartz glass nozzle is prepared by using a needle forging instrument, and then the quartz glass nozzle is fixed on the metal nozzle by using a photoresist to realize electrospray deposition. The metal spray head has an optional inner diameter of 250-220 μm and an outer diameter of 400-450 μm. The quartz glass spray nozzle is prepared by adopting a capillary, the inner diameter of the capillary adopted in the embodiment is selected to be 400-500 mu m, and the inner diameter of the tip end of the quartz glass spray nozzle prepared by a needle forging instrument at high temperature is selected to be 10-50 mu m.
The position of the tip of the electrospray printing nozzle 6 is ensured to be above the annular electrode. The electrospray printing nozzle 6 is connected with the positive electrode of the high-voltage pulse power supply 15, and the pressure difference between the voltage applied by the electrospray printing nozzle and the voltage applied by the annular electrode is 2000-2500V.
The microscope 10 constitutes an observation unit, the microscope 10 is aligned with the electrospray printing nozzle 6, and the printing condition of the nozzle is observed through the microscope.
The Z-axis workbench 9 controls the height difference between the printing nozzle and the printing substrate, and the electric field distribution between the nozzle and the substrate can be controlled by changing the height difference, so that the deposition size of the cone jet is changed.
The feeding unit and the back pressure control unit can realize continuous feeding in the printing process; the air pressure pipe 12 is provided with a precise pressure regulating valve 11 for regulating air pressure; the two ends of the feed pipe 13 are respectively connected with a microinjection pump 14 and a storage cylinder 8, and the flow rate of the microinjection pump is regulated and controlled in real time according to the viscosity of the printing material. When the viscosity of the material is smaller, the back pressure control unit is closed, and the material deposition can be realized only by controlling the flow rate of the injection pump, and the flow rate of the injection pump can be selected from 0-10ml/h. When the viscosity of the material is too high, the material storage cylinder is required to convey air pressure by an air pressure pipe, and the material is easy to extrude by applying the air pressure. The precise pressure regulating valve may be selected in the range of 0 to 100kPa, wherein the printing material having a viscosity of 0 to 1000cp may be applied in the range of 0 to 50kPa.
The working principle of the printing device of the invention is as follows:
as shown in fig. 1, by applying a high pressure to the electrospray printing head, the liquid material is caused to form a taylor cone at the printing head, and when the positive pressure is applied so that the taylor cone reaches the upper rayleigh limit (the surface charge coulomb repulsion and the surface tension of the critical point are equal), charged ions are separated from the tip of the taylor cone. As the solvent evaporates, the charge density of the large droplets increases, causing the large droplets to break down into multiple small droplets, forming an electrospray. By adding a ring electrode, a high-strength electric field is formed around the spray. When the diameter of the liquid drop is smaller than 10nm, the liquid drop is driven to be ejected from the annular electrode through hole by the high-strength electric field. The annular electrode with the gradually decreasing inner diameter of the through hole can collect liquid drops to a smaller inner diameter range. Meanwhile, under the action of the electric field force of the printing platform electrode, the cone jet is driven to be deposited on the printing substrate accurately, so that the nano-scale 3D printing conductive or nonconductive structure is realized.
Example 2
In another exemplary embodiment of the present application, a working method of the 3D printing device is provided, and specific process steps are as follows:
step 1: preparing a printing spray head, placing printing materials in a micro injection pump, connecting a feed pipe and an air pressure pipe connected with the injection pump to the upper end of a storage cylinder, connecting an electrospray printing spray head to the lower end of the storage cylinder, then placing the storage cylinder on a fixing frame of a Z-axis workbench, and adjusting the position of a microscope to facilitate observation of the printing condition of the spray head;
step 2: the annular electrode is fixed, the annular electrode is fixed on the storage cylinder by utilizing an electrode fixing frame, the distance between the electrospray printing nozzle and the annular electrode is ensured to be a certain distance, and then the electrospray printing nozzle and the annular electrode are respectively connected with a high-voltage pulse power supply; the discharge hole of the outermost annular electrode is connected with a discharge pipe and an injector;
step 3: setting a printing program, namely placing a processed printing substrate on a printing platform, moving the printing platform and a Z-axis workbench to a printing position, setting proper printing parameters, starting a high-voltage pulse power supply, starting a pre-designed printing pattern or circuit structure program, spraying liquid drops from an electrospray printing nozzle by a printing material under the action of an electric field, and spraying the liquid drops from a ring electrode through hole by gathering the liquid drops under the action of focusing of an electric field of a ring electrode; in combination with the motion of the printing platform, the material is deposited on the substrate to realize micro-nano structure manufacturing; in the printing process, the condition of depositing solution on the annular electrode is observed in real time, and when the solution is excessively deposited, the solution is timely pumped out by using a syringe;
step 4: and after printing is finished, a high-voltage pulse power supply, a precise pressure regulating valve, a microinjection pump and the like are closed, the printing platform and the Z-axis workbench are moved to an original station, and a printing workpiece is taken down from the printing platform.
Further, the flow rate of the microinjection pump in the step 1 can be selected to have a capacity of 0-50mL/h.
Further, the printing material in the step 1 is not limited to nano silver ink, nano conductive silver paste, silicon dioxide suspension, PEDOT: PSS, PVP and the like, and the viscosity of the printing material ranges from 0 mPa.s to 10000 mPa.s.
Further, in the step 1, the positive pressure applied by the electrospray printing nozzle ranges from 0 KV to 3KV, and the positive pressure applied by the annular electrode ranges from 300V to 900V. The voltage difference range applied by the electrospray printing nozzle and the annular electrode is 2000-2500V, and at the moment, the jetting system can obtain stable cone jet.
Further, in the step 2, the printing platform corresponds to the grounding electrode, the printing substrate comprises a hard substrate and a flexible substrate, the hard substrate comprises but is not limited to a glass sheet, a silicon sheet and an acrylic plate, and the flexible substrate comprises but is not limited to a PET film and a PI film.
In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
The method takes nano silver ink as a printing material, float glass as a printing substrate, and the 3D printing device is adopted to realize the manufacture of the high-resolution metal electrode, and comprises the following specific steps:
step 1: preparing a printing spray head, placing nano silver ink in a micro injection pump, connecting a feed pipe and a pneumatic pipe connected with the injection pump to the upper end of a storage cylinder, wherein the flow rate of the micro injection pump is 4mL/h; connecting an electrospray printing spray head to the lower end of a storage cylinder, then placing the storage cylinder on a fixing frame of a Z-axis workbench, and adjusting the position of a microscope to facilitate observation of the printing condition of the spray head;
step 2: the annular electrode is fixed, the annular electrode is fixed on a storage cylinder by utilizing an electrode fixing frame, the distance between the electrospray printing nozzle and the annular electrode is ensured to be 2cm, and then the electrospray printing nozzle of the printing nozzle and the annular electrode are respectively connected with a high-voltage pulse power supply; the discharge hole of the outermost annular electrode is connected with a discharge pipe and an injector;
step 3: setting a printing program, respectively placing the float glass in an isopropanol solution and deionized water, performing ultrasonic cleaning treatment for 5min, and finally drying the float glass by using inert gas; then, placing the treated float glass on a printing platform; setting a printing platform and a Z-axis workbench to proper printing positions, and adjusting proper printing parameters (printing air pressure is 50kPa, printing speed is 20 mm/s) to ensure that stable cone jet flow can be obtained; setting the voltage of an electrospray printing nozzle to 2500V, setting the voltage of an annular electrode to 500V, starting a high-voltage pulse power supply, and starting a pre-designed printing pattern or circuit structure program; running a printing program, accurately depositing nano silver ink on the surface of float glass under the action of electric field force, and observing the condition of the nano silver ink deposited on the annular electrode in real time in the printing process, and timely pumping the nano silver ink out by using a syringe when the nano silver ink is excessively deposited;
step 4: and after printing is finished, the high-voltage pulse power supply, the precise pressure regulating valve and the microinjection pump are closed, the printing platform and the Z-axis workbench are moved to an original station, and the printed nano silver electrode is taken down from the printing platform.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The 3D printing device with the metal nano structure is characterized by comprising a printing platform, wherein an injection system for injecting materials is arranged above the printing platform; the spraying system comprises a printing spray head which is connected with the storage cylinder; the printing spray head comprises an electrospray printing spray head and an electric field focusing module, wherein the electric field focusing module comprises an annular electrode assembly arranged above a printing platform; the annular electrode assembly comprises a plurality of annular electrodes which are sequentially arranged at intervals from top to bottom, through holes are arranged in the annular electrodes, and the inner diameters of the through holes of the plurality of annular electrodes are sequentially reduced from top to bottom.
2. The metal nano-structure 3D printing device integrated with the annular electrode spray head according to claim 1, wherein a plurality of the annular electrodes are coaxially arranged, annular baffle plates are arranged at the through holes of the annular electrodes, the baffle plates are arranged on the surfaces of the annular electrodes, and the baffle plates have set heights; each annular electrode is externally connected with a positive electrode of a high-voltage pulse power supply.
3. The metal nano-structure 3D printing device of the integrated annular electrode spray head of claim 1, wherein each annular electrode is connected to the storage cylinder through an electrode fixing frame, and the outer diameters of the plurality of annular electrodes are sequentially increased from top to bottom; the electrode fixing frame is made of transparent materials and is of a cylindrical structure.
4. The metal nano-structure 3D printing device of the integrated annular electrode spray head according to claim 1, wherein the solution discharge port is reserved at the annular electrode at the lowest part, the solution discharge port is connected with a discharge unit, the discharge unit comprises a discharge pipe and an injector, the discharge pipe is connected with the solution discharge port of the annular electrode, and the discharge pipe is communicated with the injector.
5. The metal nano-structured 3D printing device integrated with the ring electrode spray head according to claim 1, wherein the electrospray printing spray head comprises a metal spray head and a quartz glass spray head, and the quartz glass spray head is sleeved on the outer layer of the metal spray head; the electrospray printing spray head is connected to the lower end of the storage cylinder and connected with the positive electrode of the high-voltage pulse power supply.
6. The metal nano-structured 3D printing device integrated with a ring electrode spray head of claim 1, wherein the electrospray printing spray head tip position is above the ring electrode; the voltage difference range of the electrospray printing nozzle and the annular electrode is 2000-2500V.
7. The metal nano-structured 3D printing apparatus of an integrated ring electrode spray head of claim 1, further comprising an observation unit, the observation unit being aligned with the electrospray printing spray head position.
8. The metal nano-structure 3D printing device of the integrated ring electrode spray head according to claim 1, wherein the spraying system further comprises a back pressure control unit and a feeding unit, the back pressure control unit comprises a pneumatic tube connected with the storage cylinder, and the pneumatic tube is provided with a precise pressure regulating valve; the feeding unit comprises a feeding pipe connected with the storage cylinder, and the feeding pipe is connected with the microinjection pump.
9. The metal nano-structure 3D printing device integrated with the annular electrode spray head according to claim 1, wherein the printing substrate is fixed at the top of the printing platform, the material storage cylinder is fixed on a Z-axis workbench through a fixing frame, and the Z-axis workbench controls the height difference between the printing spray head and the printing substrate; the printing platform is connected with the negative electrode of the high-voltage pulse power supply.
10. A method of operating a metal nanostructured 3D printing device incorporating a ring electrode head according to any of claims 1 to 9, comprising the steps of:
preparing a printing spray head, connecting the electrospray printing spray head to the lower end of a storage cylinder, placing the storage cylinder on a Z-axis workbench, and adjusting the position of an observation unit so as to observe the printing condition of the spray head;
the annular electrode is fixed, so that the distance between the electrospray printing nozzle and the annular electrode is ensured to be set, and the electrospray printing nozzle and the annular electrode are respectively connected with a high-voltage pulse power supply; the discharge hole of the lowest annular electrode is connected with a discharge pipe and an injector;
placing a printing substrate on a printing platform, moving the printing platform and the Z-axis workbench to a printing position, starting a high-voltage pulse power supply, spraying liquid drops from an electrospray printing nozzle by using a printing material under the action of an electric field, and spraying the liquid drops from a through hole of an annular electrode by using the focusing action of the electric field of the annular electrode by using the printing material to form cone jet; in combination with the motion of the printing platform, the material is deposited on the substrate to realize micro-nano structure manufacturing; in the printing process, observing the condition of depositing solution on the annular electrode in real time, and pumping out the solution by using a syringe when the solution is excessively deposited;
and after printing is finished, the high-voltage pulse power supply is turned off, the printing platform and the Z-axis workbench are moved to the original station, and the printing workpiece is taken down from the printing platform.
CN202311348193.5A 2023-10-17 2023-10-17 Metal nano-structure 3D printing device and method integrated with annular electrode spray head Pending CN117358948A (en)

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