CN113547739B

CN113547739B - 3D printer for preparing multi-material micro-nano composite film and working method thereof

Info

Publication number: CN113547739B
Application number: CN202110638064.4A
Authority: CN
Inventors: 兰红波; 李鹏飞; 许权; 赵佳伟; 于志浩; 朱晓阳
Original assignee: Qingdao Wuwei Zhizao Technology Co ltd; Qingdao University of Technology
Current assignee: Qingdao Wuwei Zhizao Technology Co ltd; Qingdao University of Technology
Priority date: 2021-06-08
Filing date: 2021-06-08
Publication date: 2023-06-16
Anticipated expiration: 2041-06-08
Also published as: CN113547739A

Abstract

The disclosure provides a 3D printer for preparing a multi-material micro-nano composite film and a working method thereof, and the 3D printer can realize integrated manufacturing of a plurality of multi-scale composite films with different materials and macro/micro/nano dimensions; realizing the integrated manufacture of various different materials and films with complex patterns and macro/micro/nano multi-scale composite films; and has the characteristics of low production cost, good universality, high efficiency, simple process and suitability for batch manufacturing.

Description

3D printer for preparing multi-material micro-nano composite film and working method thereof

Technical Field

The disclosure belongs to the technical field of 3D printing and micro-nano composite film manufacturing, and particularly relates to a 3D printer for preparing a multi-material micro-nano composite film and a working method thereof.

Background

The statements in this section merely provide background information related to the present disclosure and may not necessarily constitute prior art.

The multi-material micro-nano composite film refers to a multi-layer composite film (functional film) composed of micro-scale thickness films and nano-scale thickness films or micro-nano pattern/structure films of a plurality of different materials. Generally, the following three categories are classified: (1) Multilayer composite films (multi-material and multi-scale composite films) of a variety of different materials, macro/micro/nano multi-scale thickness; (2) Multilayer composite films (multi-scale composite films) composed of films of the same material and macro/micro/nano/multiple scale thickness; (3) Multi-layer composite films (multi-material, multi-scale, micro-nano pattern composite films) composed of a plurality of different materials, macro/micro/nano multi-scale thickness and micro/nano pattern films. The micro-nano composite film has very wide application prospects in various fields such as sensors, trace gas detection, wearable equipment, embedded electronics, flexible electronics, solar cells, supercapacitors, flexible display screens, intelligent materials and structures, soft robots and the like. With technological advancement, more and more fields and products need multi-layer composite films (or multi-layer composite films with micro-nano scale thickness) with different materials and different thicknesses to meet different functional requirements and practical application requirements. Meanwhile, more and more severe requirements are also put forward for manufacturing the multi-material micro-nano composite film. The basic requirements for manufacturing the multi-material micro-nano composite film include: the production cost is low; suitable materials are widely varied (e.g., conductive materials, dielectric materials, semiconductor materials, organic materials, inorganic materials, nanomaterials, etc., with viscosities ranging from 1-40000 cp); the efficiency is high, and the universality and the process flexibility are good; can realize the integrated manufacture of large-area thick films with various dimensions and micro-nano composite structures.

The existing composite structure film manufacturing technology comprises casting, spin coating, a pulling method, a knife coating method, a roll coating method, a vapor deposition method, a self-assembly method and the like. Among them, casting is the most conventional film manufacturing method, which does not require a special device, is simple to operate, has high yield, and is only suitable for films with large thickness. The spin coating, lifting and knife coating processes for preparing the film have the advantages of simple and quick process and accurate and controllable film thickness, but the manufacturing of the patterned film/structure is difficult to realize, and particularly, the material is limited to the material with low viscosity, so that the material waste is serious. The vapor deposition has the advantages of wide applicable materials and capability of manufacturing films with different microstructures, but has high production cost, needs special targets, has harsh production conditions and environments (such as high temperature, high pressure and the like), has low efficiency, can not realize continuous production of films, is only suitable for nano-scale films, and is not suitable for manufacturing micro-scale equal-thickness films. The self-assembly method has simple process and no special device, can utilize continuous deposition of different components to prepare a film interlayer two-dimensional even three-dimensional ordered structure, realizes the functions of light, electricity, magnetism and the like of the film, but cannot realize the manufacture of patterns with complex structures, and particularly cannot meet the requirement of mass production.

In summary, the existing technologies cannot meet the manufacturing requirements of the multi-material micro-nano composite film: (1) Manufacturing of micro-nano multi-scale thickness composite films of various different materials is difficult to realize, and particularly manufacturing of micro-nano composite films of materials (1-40000 cp), composite materials, ceramic materials and the like with wider viscosity ranges cannot be realized; (2) The integrated manufacturing of the micro-nano composite film (the integrated manufacturing of micro-scale and nano-scale films of different materials) cannot be realized; (3) It is difficult to realize the integrated manufacture of organic polymer material, inorganic ceramic material and metal material film; (4) Particularly, it is difficult to realize efficient and low-cost manufacture of micro-nano composite films (containing complex micro-nano geometric patterns or structures) of different materials.

Disclosure of Invention

In order to solve the problems, the disclosure provides a 3D printer for preparing a multi-material micro-nano composite film and a working method thereof, and the disclosure can realize integrated manufacturing of a plurality of multi-scale composite films with different materials and macro/micro/nano; realizing the integrated manufacture of various different materials and films with complex patterns and macro/micro/nano multi-scale composite films; and has the characteristics of low production cost, good universality, high efficiency, simple process and suitability for batch manufacturing.

According to some embodiments, the present disclosure employs the following technical solutions:

A3D printer for preparing multi-material micro-nano composite film, includes bottom plate, print platform, movable module, accurate slit coating module, adjusts support and a plurality of printing module, wherein:

the printing device comprises a base plate, a movable module and an adjusting bracket, wherein the base plate is provided with a printing platform, the movable module and the adjusting bracket, the movable module is provided with a printing module, and the movable module can drive a printing spray head in each printing module to be variable in three-dimensional position relative to the printing platform;

at least two groups of printing modules are respectively used for manufacturing a patterned film by utilizing an electric field driven jet deposition 3D printing technology and manufacturing a micro-scale/nano-scale film by utilizing an electrospray technology;

the printing module comprises printing spray heads, a feeding unit and a high-voltage power supply, wherein the feeding unit is used for providing printing raw materials for the corresponding printing spray heads, and the high-voltage power supply is used for providing power supplies matched with the corresponding printing spray heads;

the at least one printing module further comprises a back pressure unit for providing a printing pressure matched with the corresponding printing nozzle;

the precise slit coating module is arranged on the adjusting bracket and connected with the third feeding unit and the second back pressure unit, and the third feeding unit and the second back pressure unit are respectively used for providing certain pressure and electric field for the precise slit coating module and are used for manufacturing micro-scale and sub-micro-scale films.

According to the scheme, through ingenious design, electric field driven jet deposition micro-nano 3D printing, electrospray and precise slit coating technology are combined together, and the manufacture of macro-scale/micro-scale/nano-scale structures, micro-scale/nano-scale films and micro-scale and sub-micro-scale films can be realized through one device.

As an alternative implementation manner, the movable module comprises a X, Y and a Z-axis movement module, wherein the Y-axis movement module is arranged on the bottom plate, and a printing platform is arranged on the Y-axis movement module and can drive the printing platform to move in the Y direction; the X-axis movement module and the Z-axis movement module are arranged on the frame, the bottom of the frame is arranged on the bottom plate, the X-axis movement module and the Z-axis movement module are vertically arranged, and the Z-axis movement module is provided with a printing nozzle of the printing module.

As a further limitation, the Z-axis motion module is provided with a print head bracket for fixing each print head.

As a further limitation, the print head support is connected with an observation support, and an observation positioning module is arranged on the observation support and used for observing the printing condition of the print head.

As a further limitation, the print head holder is further provided with a curing module.

As an alternative implementation mode, the printing platform comprises a vacuum adsorption platform, a heating plate, a leveling device and a heat insulation block, wherein the upper part of the heating plate is connected with the vacuum adsorption platform, the leveling device is arranged below the heating plate, and the heat insulation block is arranged at the lower end of the leveling device.

As a further limitation, the vacuum adsorption platform is used for fixing a substrate, and the temperature of the heating plate ranges from 0 ℃ to 300 ℃; the leveling device is used for adjusting the height of the vacuum adsorption platform and keeping the vacuum adsorption platform horizontal, and the heat insulation block is made of insulating heat insulation materials. Can be glass fiber, asbestos, rock wool, silicate, aerogel felt, vacuum plate, etc.

As an alternative implementation mode, the adjusting bracket comprises a coating bracket, a compressible spring and two differential scales, wherein the bottom end of the coating bracket is arranged on the bottom plate, a precise slit coating module is arranged on the coating bracket, a telescopic spring is wound on a stand column of the coating bracket, the top end of the telescopic spring is abutted with the precise slit coating module, and the bottom end of the telescopic spring is abutted with the bottom plate;

and two differential rules are respectively arranged on two sides of the precise slit coating module on the coating support, and the differential rules are contacted with the precise slit coating module.

As a further limitation, the coating bracket comprises two upright posts arranged side by side and a cross rod sleeved at the upper ends of the two upright posts, the differential rule is vertically arranged on the cross rod of the coating bracket, the telescopic spring is wound on the upright posts, and the contact position between the upright post close to one side and the cross rod is adjusted through the differential rule so as to ensure that the precise slit coating module is perpendicular to the printing platform.

As an alternative embodiment, the center line of the precision slit coating module and each printing nozzle is horizontal.

As an alternative embodiment, the back pressure units all include inert gas bottle, connecting trachea and air-vent valve, inert gas bottle is connected with the air-vent valve, and is connected with connecting trachea one end, connecting tracheal other end is connected with printing shower nozzle or accurate slit coating module.

Alternatively, the feeding unit is a cartridge or a syringe pump with an extrusion device.

As an alternative implementation mode, the high-voltage power supply can output direct-current high voltage, alternating-current high voltage and pulse high voltage, bias voltage can be set, the set bias voltage range is 0-2kV continuously adjustable, the direct-current high voltage is 0-5kV, the output pulse direct-current voltage is 0- +/-4 kV continuously adjustable, the output pulse frequency is 0-3000 Hz continuously adjustable, and the alternating-current high voltage is 0- +/-4 kV.

As an alternative embodiment, the nozzles of the printing spray head are all conductive nozzles, and the inner diameter size of the nozzles is 0.5-1000 mu m.

The coating thickness of the precise slit coating module ranges from 100nm to 200 mu m.

The working method based on the 3D printer comprises the following steps of:

step 1: initializing printing, namely moving a printing platform and a printing spray head to a set printing position, adjusting the precision slit coating module to a set height, leveling the printing platform, heating to a set temperature, placing a printing substrate on the printing platform, and fixing the printing substrate through vacuum adsorption;

step 2: according to the composite film structure, selecting a film forming mode, and determining a printing program, corresponding printing process steps and parameters;

step 3: performing the manufacture of a first layer of film or film structure and curing;

step 4: executing a second layer of film or film structure and solidifying; repeating the operation of the step 3 and the step 4 to finish the manufacture of all the layer film structures;

step 5: the printed film is fully cured.

As an alternative embodiment, the specific process of performing the corresponding layer film or film structure in step 3 and step 4 includes:

(1) A printing nozzle is used, and the electric field is combined to drive jet deposition 3D printing, so that the manufacture of the macro-scale/micro-scale film is completed;

(2) Using another printing nozzle, and combining electric field driving jet deposition 3D printing to finish manufacturing of macro-scale/micro-scale/nano-scale structures; and the printing nozzle is used for completing the manufacture of the micro-scale/nano-scale film by utilizing an electrospray technology;

(3) And a precise slit coating module is adopted, and the printing height adjusted by the adjusting bracket is combined to finish the manufacture of the microscale and submicroscale films.

Alternatively, the curing means may include thermal curing, UV curing, and the like.

Alternatively, the step 1 further includes pre-treating the printing substrate, and if the film needs to be separated from the substrate, the substrate is pre-coated with a layer of hydrophobic material or water-soluble material; if the film is not separated from the substrate, a layer of coupling agent is coated or corona or ozone treatment is performed to improve the surface energy and adhesion strength of the substrate.

Compared with the prior art, the beneficial effects of the present disclosure are:

(1) The 3D printer for preparing the multi-material micro-nano composite film and the working method thereof can realize the integrated manufacture of various multi-scale composite films with different materials and macro/micro/nano.

(2) The 3D printer for preparing the multi-material micro-nano composite film and the working method thereof realize the integrated manufacture of various different materials, complex patterned films and macro/micro/nano multi-scale composite films.

(3) The 3D printer for preparing the multi-material micro-nano composite film and the working method thereof realize the integrated manufacture of a plurality of different materials, a complex 2D/3D micro-nano structure and a macro/micro/nano multi-scale composite film.

(4) The 3D printer for preparing the multi-material micro-nano composite film and the working method thereof can realize the integrated manufacture of organic polymer materials, inorganic ceramic materials and metal material films.

(5) The 3D printer for preparing the multi-material micro-nano composite film and the working method thereof have the outstanding advantages of simple structure, low production cost, good integration level, universality and high-efficiency manufacturing.

(6) The 3D printer for preparing the multi-material micro-nano composite film and the working method thereof have the advantages of high material utilization rate (almost 100 percent), high precision and environment friendliness.

(7) The 3D printer for preparing the multi-material micro-nano composite film and the working method thereof do not need a severe production environment of vacuum, high temperature and high pressure.

(8) The 3D printer for preparing the multi-material micro-nano composite film and the working method thereof can be used for printing a wide range of materials, including composite structure film printing from insulating materials (such as ceramics, resin and the like) to conducting materials (such as graphene and PLA composites, silver paste and the like), from low-viscosity materials to high-viscosity materials, and various materials such as biological materials, metal nano particles and the like.

The foregoing objects, features and advantages of the disclosure will be more readily apparent from the following detailed description of the preferred embodiments taken in conjunction with the accompanying drawings.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate and explain the exemplary embodiments of the disclosure and together with the description serve to explain the disclosure, and do not constitute an undue limitation on the disclosure.

Fig. 1 is a schematic structural diagram of a 3D printer for preparing a multi-material micro-nano composite film according to the first embodiment.

Fig. 2 is a schematic structural diagram of a printing platform of a 3D printer for preparing a multi-material micro-nano composite film according to the first embodiment;

fig. 3 is a schematic diagram of an adjusting bracket structure of a 3D printer prepared by a multi-material micro-nano composite film according to the first embodiment;

FIG. 4 is a schematic diagram of a multi-material micro-nano composite film structure according to the second embodiment;

FIG. 5 is a schematic diagram of a multi-material micro-nano composite film structure according to the third embodiment;

FIG. 6 is a schematic diagram of a multi-material micro-nano composite film structure according to the fourth embodiment;

FIG. 7 is a schematic diagram of a multi-material micro-nano composite film structure according to the fifth embodiment.

FIG. 8 is a schematic diagram of a printing flow of the present disclosure;

the device comprises a printing platform, a base plate, a printing platform, a Y-axis movement module, a regulating support, a light curing module, a vacuum adsorption platform, a high-voltage power supply II, a printing spray head II, a vacuum pump 10, an observing and positioning module 11, a precise slit coating module 12, a feeding unit I I,13, a back pressure unit I I, 14, an observing and positioning module support 15, a printing spray head support 16, a Z-axis movement module 17, an X-axis movement module 18, a frame 19, a back pressure unit I,20, a feeding unit III,21, a feeding unit I,22, a printing spray head I,23 and a high-voltage power supply I, wherein the printing platform is arranged on the printing platform;

201. a heat insulating block 202, a leveling device 203, and a heating plate;

401. coating column, 402, compressible spring, 403, coating bracket, 404, high precision differential rule I,405 high precision differential rule II.

The specific embodiment is as follows:

the disclosure is further described below with reference to the drawings and examples.

It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present disclosure. 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 disclosure belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments in accordance with the present disclosure. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.

In the present disclosure, terms such as "upper", "lower", "left", "right", "front", "rear", "vertical", "horizontal", "side", "bottom", and the like indicate an azimuth or a positional relationship based on the azimuth or the positional relationship shown in the drawings, are merely relational terms determined for convenience in describing structural relationships of the various components or elements of the present disclosure, and do not denote any one of the components or elements of the present disclosure, and are not to be construed as limiting the present disclosure.

In the present disclosure, terms such as "fixedly coupled," "connected," and the like are to be construed broadly and refer to either a fixed connection or an integral or removable connection; can be directly connected or indirectly connected through an intermediate medium. The specific meaning of the terms in the disclosure may be determined according to circumstances, and should not be interpreted as limiting the disclosure, for relevant scientific research or a person skilled in the art.

Based on the problems in the prior art mentioned in the background art, development of new manufacturing technology and device are urgently needed to meet the manufacturing requirements for multi-material micro-nano composite films, so as to realize macro/micro/nano cross-scale manufacturing, efficient and low-cost batch manufacturing of multi-material multi-pattern composite structure film manufacturing, and break through the technical bottleneck of wide engineering application of complex-pattern composite structure composite films.

The present disclosure employs the following solutions:

(1) Combines the advantages of three technologies of electric field driven jet deposition micro-nano 3D printing, electrospray and precise slit coating, and is integrated into the same printing platform. The device specifically comprises two forming functional modules, wherein the first forming functional module adopts slit coating to efficiently manufacture a precise micro-nano film, and is mainly used for manufacturing films with different viscosity, large area and micro-nano scale (thickness);

The second forming functional module adopts electric field driven jet deposition micro-nano 3D printing and electrospray technology, and prints micro-nano structure or complex geometric pattern film and macro/micro/nano film with various thickness in a designated (set) area with high precision, which is mainly used for high-precision manufacturing of films with different materials, micro-nano structures (2D or 3D) and complex geometric patterns, and realizes multi-material, macro/micro/nano cross-scale and multi-layer composite film integrated manufacturing containing micro-nano structures or geometric patterns.

(2) The micro-nano film and the micro-nano pattern film are manufactured by adopting an electric field driven jet deposition micro-nano 3D printing technology, a high voltage power supply is applied to the conductive nozzle, a strong electric field is formed between the nozzle and the receiving substrate, the printing material is jetted by the electric field force, a special pattern film can be formed in a specific area of the substrate, the high-precision and high-efficiency manufacturing of the composite film with the set area and the complex geometric pattern is realized, the composite film is suitable for manufacturing films from materials with high viscosity, and the molding materials are wide.

(3) The electrospray technology is adopted, the electrospray nozzle is connected with a high-voltage power supply, the forming material is atomized into tiny liquid drops under the action of high voltage (the material is pulled out from the nozzle to form jet flow to be atomized under the action of an electric field), and the tiny liquid drops are deposited on a printing substrate or a base material.

The above solution is illustrated in detail by the following examples. It should be apparent to those skilled in the art that the aspects of the present disclosure are not limited to the following examples.

Embodiment one:

as shown in fig. 1, there is provided a 3D printer for preparing a multi-material micro-nano composite film, comprising: the device comprises a bottom plate 1, a Y-axis motion module 3, a printing platform 2, a printing spray head I22, a printing spray head II8, a feeding unit I21, a feeding unit II12, a back pressure unit I19, a back pressure unit II13, a high-voltage power supply I23, a high-voltage power supply II7, a printing spray head support 15, an observation positioning module 10, an observation positioning module support 14, a photocuring module 5, an X-axis motion module 17, a Z-axis motion module 16, a frame 18, a precise slit coating module 11, a feeding unit III20 and an adjusting support 4. Wherein the Y-axis movement module 3 is arranged on the bottom plate 1 and is perpendicular to the central line of the frame 18; y is placed on top of the Y-axis motion module 3.

The printing spray head I22 and the printing spray head II8 are arranged above the printing platform and perpendicular to the printing platform; the printing spray head I22 and the printing spray head II8 are fixed on the printing spray head support 15, and the printing spray head support 15 is connected with a Z-axis module of the XZ-axis movement module 16; the upper end of the printing spray head I22 is connected with the feeding unit I21; the upper end of the printing nozzle I22 is connected with the back pressure unit I19; the lower end of the printing nozzle I22 is connected with a high-voltage power supply I23; the upper end of the printing spray head II8 is connected with the feeding unit II 12; the lower end of the printing spray head II8 is connected with a high-voltage power supply II 7; the XZ axis movement module 16 is fixed on a beam of the frame 18; the lower part of the frame 18 is fixed to the base plate 1.

The precise slit coating module 11 is connected with the feeding unit III 20; the precise slit coating module 11 is connected with the back pressure unit II 13; the precise slit coating module 11 is connected with the adjusting bracket 4, and the precise slit coating module 11 is arranged at the rear parts of the printing nozzle I22 and the printing nozzle II8 and is vertical to the printing platform; the lower part of the adjusting bracket 4 is fixed on the bottom plate 1; the observation positioning module 10 is fixed on the observation positioning module bracket 14 and is arranged on the other side of the printing nozzle I22 and the printing nozzle II 8; the observation positioning module bracket 14 is connected with the printing nozzle bracket 15; the photo-curing module 5 is fixed on the printing head holder 15 and is placed in the middle between the printing head I22 and the printing head II 8.

The printing platform 2 comprises a vacuum adsorption platform 6, a heating plate 203, a leveling device 202 and a heat insulation block 201. The upper part of the heating plate 203 is connected with the vacuum adsorption platform 6, the upper and lower ends of the heating plate 203 are connected with the leveling device 202, and the heating plate 203 is fixed on the Y-axis motion module 3 through the heat insulation block 201. The vacuum adsorption stage 6 is connected to a vacuum pump 9 for fixing a base material (substrate). The temperature of the heating plate 203 ranges from 0 to 300 ℃. The leveling device 202 is used for adjusting the height of the printing platform 2 and keeping the height horizontal. The heat insulation block 201 is made of asbestos insulating heat insulation materials.

In this embodiment, the printing nozzle I22, the feeding unit I21, the back pressure unit I19, and the high voltage power supply I23 form a printing nozzle module I, and the printing nozzle module I uses an electric field driven jet deposition 3D printing technology. The method is used for manufacturing macro-scale/micro-scale films and manufacturing macro-scale/micro-scale/nano-scale structures (patterned films).

In this embodiment, print shower nozzle II8, feed unit II12, high voltage power supply II7 constitute and print shower nozzle module II, print shower nozzle module II adopts the electrospray technique. Is used for manufacturing micro-scale/nano-scale films.

In this embodiment, the precise slit coating module 11, the feeding unit III20, and the back pressure unit II13 constitute a precise slit coating unit. Is used for manufacturing micro-scale and sub-micro-scale films.

In this embodiment, the adjusting bracket 4 comprises a coating bracket 403, a coating column 401, a compressible spring 402, a high-precision differential rule I404, and a high-precision differential rule I405. The precise slit coating module 11 is fixed on the beam of the coating bracket 403, is installed on the bottom plate 1 through the coating upright post 401, the telescopic spring is wound on the coating upright post 401, the upper end is connected with the precise slit coating module 11, the bottom end is connected with the bottom plate 1, the high-precision differential ruler I404 and the high-precision differential ruler I405 are installed on the coating bracket 403 and are contacted with the precise slit coating module 11, the printing spray head I22 and the printing spray head II8 jointly use one printing platform 2, and the center lines of the printing platform 2 module, the precise slit coating module 11, the printing spray head I22 and the printing spray head II8 are parallel (coincide or are collinear).

In this embodiment, the feeding unit I21 is a barrel including a precise extrusion device, and the feeding unit II12 and the feeding unit III20 are precise syringe pumps or constant-speed syringe pumps.

In this embodiment, the back pressure unit I19 and the back pressure unit II13 include an inert gas bottle (nitrogen is selected in this embodiment), a precise pressure regulating valve and a connecting gas pipe, the inert gas bottle is connected with the connecting gas pipe, and the precise pressure regulating valve is used for regulating the gas supply pressure. The working pressure range of the precise pressure regulating valve is as follows: 0-8bar.

In the embodiment, the Y-axis movement module 3 is a linear motor module, the effective travel range of the linear motor module is 0-1000mm, the repeated positioning precision is greater than or equal to +/-1 mu m, the positioning precision is greater than or equal to +/-3 mu m, the maximum speed is 1000mm/s, and the maximum acceleration is greater than or equal to 1g.

In this embodiment, the X-axis movement module 17 includes a linear motor module having an effective stroke range of 0-1000mm, a repeated positioning accuracy of greater than or equal to + -1 μm, a positioning accuracy of greater than or equal to + -3 μm, a maximum speed of 1000mm/s, and a maximum acceleration of greater than or equal to 1g.

In this embodiment, the Z-axis movement module 16 is a servo motor module, the effective stroke range is 0-200mm, the repeated positioning accuracy is greater than or equal to + -1 μm, and the positioning accuracy is greater than or equal to + -3 μm.

In this embodiment, the observation positioning module 10 is a high-resolution CCD, and employs a lens with a magnification of more than 8.

In the embodiment, the nozzles used by the printing nozzle I22 and the printing nozzle II8 are stainless steel conductive nozzles, and the inner diameter size of the nozzles is 0.5-1000 mu m.

In this embodiment, the coating width of the precision slit coating module 11 is 200mm.

In this embodiment, the high-precision differential rule I404 and the high-precision differential rule I405 are horizontally and vertically mounted on the coating bracket 403, the precision is 1 μm, and the displacement range is 0-125mm. Which matches the vertical height of the compressible spring 402 while ensuring that the precision slot coating module 11 is perpendicular to the printing platform 2.

In the embodiment, the high-voltage power supply I23 and the high-voltage power supply II7 have the following functions and output direct-current high voltage; outputting alternating-current high voltage; the output pulses are high voltage and can be set with a bias voltage. The set bias voltage range is 0-2kV continuously adjustable, the direct current high voltage is 0-5kV, the output pulse direct current voltage is 0- +/-4 kV continuously adjustable, the output pulse frequency is 0-3000 Hz continuously adjustable, and the alternating current high voltage is 0- +/-4 kV.

Example two

In this embodiment, the printing device of this embodiment is mainly applied to the printing of the micro-nano composite film containing complex patterns with the same material, different thicknesses of different materials, and can realize the integrated printing of complex patterns, multi-material, and trans-scale multilayer structure composite films.

The working method of the 3D printer for preparing the multi-material micro-nano composite film is provided, wherein PDMS is selected as the first layer and the fourth layer of substrate film, the thickness of the first layer is 50 mu m, the thickness of the fourth layer of film is 100 mu m, and the shape of the fourth layer of film is square with the size of 100 multiplied by 100 mm; the second layer of film material is made of graphene and TPU composite, and has a transverse serpentine pattern, a thickness of 30 μm and a size of 80X 80mm; the third layer of film material is PEDOT PSS with longitudinal serpentine pattern, thickness of 30 μm and size of 80×80mm; the prepared PEDOT, PSS, graphene and TPU composite conductive pattern composite film (shown in figure 4) comprises the following specific process steps:

step 1: initializing printing, namely moving an X-axis movement module 17, a Y-axis movement module 3 and a Z-axis movement module 16 to a printing station, moving a printing nozzle I22 and a printing nozzle II8 to a set printing height, adjusting the precision slit coating module 11 to the set height, leveling and heating the printing platform 2 to a set temperature, placing a glass substrate on the printing platform 2, and fixing the glass substrate through vacuum adsorption;

step 2: print data file preparation. According to the requirements of a composite film structure (thickness, pattern, structure and material), a first layer of film and a fourth layer of film are in a coating mode, a second layer of pattern film is in an electric field driven spray deposition 3D printing mode, a third layer of film is in an electrospray mode, and a printing program (path and speed) is set according to the film thickness pattern.

Step 3: PDMS is arranged in a feeding unit III20, graphene and TPU compound are arranged in a feeding unit I21, PEDOT PSS is arranged in a feeding unit II12, and required working parameters such as the feeding unit I21, the feeding unit II12, the feeding unit III20, a back pressure unit I19, a back pressure unit II13, a high-voltage power supply I23, a high-voltage power supply II7 and the like are set according to the thickness of a required film.

Step 4: the feeding unit III20 and the back pressure unit II13 are started. And combining the Y-axis movement module 3 to directionally move at a set speed, printing a layer of PDMS film on the glass substrate under the action of back pressure, starting the heating plate 203, setting the required temperature, and quickly curing the PDMS film.

Step 5: after the first layer of film is printed, the feeding unit III20 and the back pressure unit II13 are closed, the PDMS film is taken as a receiving substrate, and the feeding unit I21, the back pressure unit I19 and the high-voltage power supply I23 are opened. In combination with the movement of the X-Y workbench according to a set path, under the action of back pressure, the graphene and TPU compound are extruded from the feeding unit I21 to the printing nozzle I22, a high-voltage power supply is applied to the conductive nozzle, a strong electric field is formed between the nozzle and the receiving substrate, charges are induced to gather at the nozzle and repel each other, the printing material at the nozzle is formed into a Taylor cone by the strong electric field force, when the sum of the electric field force and the back pressure of gas is greater than the sum of the surface tension and the viscosity force of the Taylor cone formed by the printing material, the printing material jet is ejected from the Taylor cone tip, the graphene and TPU compound ejected by the nozzle are deposited on a first layer of film, a transverse multi-snake-shaped curve pattern film is printed on a specific area of the PDMS film, the printing of a second layer of graphene and TPU compound pattern film is completed, and the heating plate 203 is set to be at a required temperature, and the solvent in the TPU compound is enabled to volatilize rapidly.

Step 6: after the second layer of transverse multi-serpentine pattern film is printed, the feeding unit I21, the back pressure unit I19 and the high-voltage power supply I23 are closed, and the feeding unit II12 and the high-voltage power supply II7 are opened. When high pressure is applied to the PEDOT-PSS solution, droplets of the PEDOT-PSS solution are ejected in the form of a spray. The droplets under the action of high pressure are continuously diffused in space due to the concentration of an electric field generated at the spray tip, when the electric charge reaches the Rayleigh limit, the droplets are continuously decomposed into smaller droplets to be deposited on the PDMS film due to the coulomb repulsion action among the droplets, a longitudinal multi-serpentine curve pattern film is printed on the PDMS film, the longitudinal multi-serpentine curve pattern film is vertically and crosswise distributed with a second layer of transverse multi-serpentine curve pattern film, the third layer PEDOT-PSS pattern film printing is completed by combining with the movement of an X-Y workbench according to a set path, and the heating plate 203 is set to be at a required temperature, so that the PEDOT-PSS is rapidly solidified.

Step 7: and (3) closing the feeding unit II12 and the high-voltage power supply II7, repeating the step (4), reprinting and solidifying a layer of PDMS film, closing the feeding unit III20 and the back pressure unit II13, enabling the X-axis movement module 17, the Y-axis movement module 3 and the Z-axis movement module 16 to move to an initial station, adjusting the precise slit coating module 11 to the initial station, and taking down the substrate and the printed film from the printing platform 2.

Step 8: and (3) carrying out post-treatment, namely fully and completely curing the printing film, and stripping the printing film from the substrate.

Example III

In this embodiment, the printing device of this embodiment is mainly applied to the printing of the micro-nano composite film of different materials, different thickness, can realize complex pattern, multi-material, multi-scale multilayer structure composite film integration printing.

In a typical embodiment of the present application, a working method of a 3D printer for preparing a multi-material micro-nano composite film is provided, wherein a first film layer is made of a mixture of ceramic material zirconia and nickel oxide, has a thickness of 150 μm, and is shaped as a square of 150×150 mm; the second film is made of ceramic zirconia, and has a thickness of 10 μm and a square shape of 150×150mm; the prepared multilayer ceramic film (shown in fig. 5) comprises the following specific process steps:

step 1: initializing printing, namely moving an X-axis movement module 17, a Y-axis movement module 3 and a Z-axis movement module 16 to a printing station, moving a printing nozzle I22 and a printing nozzle II8 to a set printing height, adjusting the precision slit coating module 11 to the set height, leveling and heating the printing platform 2 to a set temperature, placing a silicon wafer on the printing platform 2, and fixing the silicon wafer through vacuum adsorption;

Step 2: print data file preparation. According to the requirements of a composite film structure (thickness, pattern, structure and material), a first layer of film adopts a coating mode, a second layer adopts an electric field driving jet deposition 3D printing mode, and a printing program (path and speed) is set according to the film thickness pattern.

Step 3: the mixture of zirconium oxide and nickel oxide is placed in a feeding unit III20, zirconium oxide is placed in a feeding unit I21, and the required working parameters of the feeding unit I21, the feeding unit III20, a back pressure unit I19, a back pressure unit II13, a high-voltage power supply I23 and the like are set according to the thickness of the required film.

Step 4: the feeding unit III20 and the back pressure unit II13 are started. And combining the Y-axis movement module 3 to directionally move at a set speed, and printing a layer of zirconia and nickel oxide mixture film on the ceramic plate under the action of back pressure.

Step 5: after the first layer of film is printed, the feeding unit III20 and the back pressure unit II13 are closed, the zirconium oxide and nickel oxide mixture film is used as a receiving substrate, and the feeding unit I21, the back pressure unit I19 and the high-voltage power supply I23 are opened. In combination with the movement of the X-Y workbench according to a set path, zirconia is extruded from a feeding unit I21 to a printing spray head I22 under the action of back pressure, a high-voltage power supply is applied to a conductive nozzle, a strong electric field is formed between the nozzle and a receiving substrate, charges are induced to gather at the nozzle and repel each other, the strong electric field force enables printing materials at the nozzle to form a Taylor cone, when the sum of the electric field force and the back pressure of gas is greater than the sum of the surface tension and the viscosity force of the Taylor cone formed by the printing materials, jet flow of the printing materials is sprayed from the tip of the Taylor cone, and an oxidation pick sprayed by the nozzle is arranged on a first layer of film and a film on a specific area of a zirconium oxide and nickel oxide mixture film.

Step 6: the feeding unit I21, the back pressure unit I19 and the high-voltage power supply I23 are closed, the X-axis movement module 17, the Y-axis movement module 3 and the Z-axis movement module 16 are moved to an initial station, the precise slit coating module 11 is adjusted to the initial station, and the silicon wafer is taken down from the printing platform 2.

Step 7: placing the ceramic film in a high-temperature sintering furnace, setting the temperature to 1500 ℃, taking out the silicon wafer after 14 hours, and taking down the ceramic film.

Example IV

In this embodiment, the printing device of this embodiment is mainly applied to the printing of the composite film of the same material, different thickness, different material containing micro-nano structure, can realize the integrated printing of complex pattern, multi-material, trans-scale multilayer structure composite film.

In an exemplary embodiment of the present application, a working method of a 3D printer for preparing a multi-material micro-nano composite film is provided, where a first layer and a third layer of substrate film are selected from Ecoflex solution, the thickness of the first layer is 10 μm, the thickness of the third layer film is 50 μm, and the shape is a rectangle of 100×150 mm; the second layer of film material is conductive silver paste, the film structure is a grid with a period of 50 μm, the line width is 10 μm, the height is 50 μm, and the size is 80×100mm; the prepared microstructure conductive film (shown in fig. 6) comprises the following specific process steps:

Step 1: initializing printing, namely moving an X-axis movement module 17, a Y-axis movement module 3 and a Z-axis movement module 16 to a printing station, moving a printing nozzle I22 and a printing nozzle II8 to a set printing height, adjusting the precision slit coating module 11 to the set height, leveling and heating the printing platform 2 to a set temperature, placing PET on the printing platform 2, and fixing the PET through vacuum adsorption;

step 2: print data file preparation. According to the requirements of a composite film structure (thickness, pattern, structure and material), a first layer of film and a third layer of film are in a coating mode, a second layer of pattern film is in an electric field driven jet deposition 3D printing mode, and a printing program (path and speed) is set according to the film thickness pattern.

Step 3: the Ecoflex solution is placed in a feeding unit III20, the conductive silver paste is placed in a feeding unit I21, and the required working parameters such as the feeding unit I21, the feeding unit III20, a back pressure unit I19, a back pressure unit II13, a high-voltage power supply I23 and the like are set according to the thickness of the required film.

Step 4: the feeding unit III20 and the back pressure unit II13 are started. The Y-axis movement module 3 is combined to directionally move at a set speed, a layer of Ecoflex film is printed on PET under the action of back pressure, the heating plate 203 is started, and the required temperature is set, so that the Ecoflex film is quickly solidified.

Step 5: after the first layer of film is printed, the feeding unit III20 and the back pressure unit II13 are closed, the Ecoflex film is taken as a receiving substrate, and the feeding unit I21, the back pressure unit I19 and the high-voltage power supply I23 are opened. In combination with the movement of the X-Y workbench according to a set path, under the action of back pressure, conductive silver paste is extruded from a feeding unit I21 to a printing spray head I22, a high-voltage power supply is applied to a conductive nozzle, a strong electric field is formed between the nozzle and a receiving substrate, charges are induced to gather at the nozzle and repel each other, the strong electric field force enables printing materials at the nozzle to form a Taylor cone, when the sum of the electric field force and the back pressure of gas is greater than the sum of the surface tension and the viscosity force of the Taylor cone formed by the printing materials, jet flow of the printing materials is ejected from the tip of the Taylor cone, the conductive silver paste ejected by the nozzle prints a conductive grid with a period of 0.2mm and a line width of 50 mu m on a specific area of the Ecoflex film, the micro-structure printing of a second conductive grid is completed, and the heating plate 203 is set to be at a required temperature, so that the conductive grid is cured rapidly.

Step 6: after the second layer of conductive grid microstructure is printed, the feeding unit I21, the back pressure unit I19 and the high-voltage power supply I23 are closed. Repeating the step 4, printing a layer of Ecoflex film on the conductive mesh, setting the heating plate 203 to the required temperature, and curing the Ecoflex film.

Step 7: and closing the feeding unit III20 and the back pressure unit II13, enabling the X-axis movement module 17, the Y-axis movement module 3 and the Z-axis movement module 16 to move to an initial station, adjusting the precise slit coating module 11 to the initial station, and taking the PET off the printing platform 2.

Step 8: placing in a vacuum drying oven, setting the temperature to 120 ℃, taking out PET after 1 hour, and taking down the film.

Example five

In a typical embodiment of the present application, a working method of a 3D printer for preparing a multi-material micro-nano composite film is provided, wherein a PVA aqueous solution is selected as a first layer and a third layer of substrate film, the thickness of the first layer is 1 μm, the thickness of the third layer of film is 10 μm, and the shape is a square of 150×150 mm; the second layer of film material is light-cured resin, the film is micro-lens array pattern with the size of 100X 100mm, the radius of lens is 5 μm, and the interval is 5mm; the preparation method of the microlens array film (shown in fig. 7) comprises the following specific process steps:

step 2: print data file preparation. According to the requirements of the composite film structure (thickness, pattern, structure and material), the first layer film and the third layer film are in a coating mode, the second layer pattern film is in an electrospray mode, and a printing program (path and speed) is set according to the film thickness pattern.

Step 3: the PVA aqueous solution is placed in a feeding unit III20, the photo-curing resin is placed in a feeding unit II12, and the required working parameters of the feeding unit II12, the feeding unit III20, a back pressure unit II13, a high-voltage power supply II7 and the like are set according to the thickness of the required film.

Step 4: the feeding unit III20 and the back pressure unit II13 are started. And combining the Y-axis movement module 3 to directionally move at a set speed, printing a layer of PVA film on the glass substrate under the action of back pressure, starting the heating plate 203, setting the required temperature, and quickly solidifying the PVA film.

Step 5: after the first layer of film is printed, the feeding unit III20 and the back pressure unit II13 are closed, and the feeding unit II12 and the high-voltage power supply II7 are opened. When high pressure is applied to the photocurable resin solution, droplets of the photocurable resin solution are ejected in the form of a spray. Because the high pressure acts on the electric field concentration generated at the spray tip, the liquid drops under the high pressure are deposited on the PVA water solution film, and the microlens array is printed on the PVA water solution film. And starting the photo-curing module 5, and curing the micro-lens array for 3 minutes.

Step 6: and (3) closing the feeding unit II12, the high-voltage power supply II7 and the light curing module, repeating the step (4), reprinting a layer of PVA aqueous solution film, and setting the heating plate 203 to be at a required temperature to be cured.

Step 7: and closing the feeding unit III20 and the back pressure unit II13, enabling the X-axis movement module 17, the Y-axis movement module 3 and the Z-axis movement module 16 to move to an initial station, adjusting the precise slit coating module 11 to the initial station, and taking the glass off the printing platform 2.

The foregoing description of the preferred embodiments of the present disclosure is merely illustrative of the present disclosure and is not intended to be limiting, since various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.

While the specific embodiments of the present disclosure have been described above with reference to the drawings, it should be understood that the present disclosure is not limited to the embodiments, and that various modifications and changes can be made by one skilled in the art without inventive effort on the basis of the technical solutions of the present disclosure while remaining within the scope of the present disclosure.

Claims

1. A3D printer for preparing a multi-material micro-nano composite film is characterized in that: including bottom plate, print platform, movable module, accurate slit coating module, regulation support and a plurality of printing module, wherein:

at least two groups of printing modules are respectively used for manufacturing a transverse serpentine pattern film by utilizing an electric field driven jet deposition 3D printing technology and manufacturing a micro-scale/nano-scale pattern film by utilizing an electrospray technology;

the precise slit coating module is arranged on the adjusting bracket and connected with the third feeding unit and the second back pressure unit, and the third feeding unit and the second back pressure unit are respectively used for providing certain pressure and electric field of the precise slit coating module and are used for manufacturing micro-scale and sub-micro-scale films; the coating thickness of the precise slit coating module ranges from 100nm to 200 mu m;

the adjusting bracket comprises a coating bracket, a compressible spring and two micro-ruler, wherein the bottom end of the coating bracket is arranged on the bottom plate, a precise slit coating module is arranged on the coating bracket, a telescopic spring is wound on a stand column of the coating bracket, the top end of the telescopic spring is abutted with the precise slit coating module, and the bottom end of the telescopic spring is abutted with the bottom plate; the precise slit coating module and the printing spray head commonly use one printing platform, and the central lines of the printing platform, the dense slit coating module and the printing spray head are parallel;

two differential rules are respectively arranged on two sides of the precise slit coating module on the coating support, and the differential rules are contacted with the precise slit coating module;

The coating bracket comprises two upright posts which are arranged side by side, and a cross rod sleeved at the upper ends of the two upright posts, the differential rule is vertically arranged on the cross rod of the coating bracket, the telescopic spring is wound on the upright posts, and the contact position between the upright post close to one side and the cross rod is adjusted through the differential rule so as to ensure that the precise slit coating module is vertical to the printing platform; the precision of the differential rule is 1 mu m, and the displacement range is 0-125mm;

the high-voltage power supply can output direct-current high voltage, alternating-current high voltage and pulse high voltage, can set bias voltage, is continuously adjustable in a set bias voltage range of 0-2kV, is continuously adjustable in a direct-current high voltage range of 0-5kV, is continuously adjustable in an output pulse direct-current voltage range of 0- +/-4 kV, is continuously adjustable in an output pulse frequency range of 0-3000 Hz, and is continuously adjustable in an alternating-current high voltage range of 0- +/-4 kV.

2. The 3D printer for preparing the multi-material micro-nano composite film according to claim 1, wherein the 3D printer is characterized in that: the movable module comprises X, Y and a Z-axis movement module, wherein the Y-axis movement module is arranged on the bottom plate, and a printing platform is arranged on the Y-axis movement module and can drive the printing platform to move in the Y direction; the X-axis movement module and the Z-axis movement module are arranged on the frame, the bottom of the frame is arranged on the bottom plate, the X-axis movement module and the Z-axis movement module are vertically arranged, and the Z-axis movement module is provided with a printing nozzle of the printing module.

3. The 3D printer for preparing the multi-material micro-nano composite film according to claim 2, wherein the 3D printer is characterized in that: the Z-axis movement module is provided with a printing nozzle support, and the printing nozzle support is used for fixing each printing nozzle.

4. A 3D printer for the preparation of a multi-material micro-nano composite film according to claim 3, wherein: the printing nozzle comprises a printing nozzle support, wherein an observation support is connected to the printing nozzle support, and an observation positioning module is arranged on the observation support and used for observing the printing condition of the printing nozzle.

5. A 3D printer for the preparation of a multi-material micro-nano composite film according to claim 3, wherein: and the printing nozzle bracket is also provided with a curing module.

6. The 3D printer for preparing the multi-material micro-nano composite film according to claim 1, wherein the 3D printer is characterized in that: the printing platform comprises a vacuum adsorption platform, a heating plate, a leveling device and a heat insulation block, wherein the upper part of the heating plate is connected with the vacuum adsorption platform, the leveling device is arranged below the heating plate, and the heat insulation block is arranged at the lower end of the leveling device.

7. The 3D printer for preparing the multi-material micro-nano composite film according to claim 1, wherein the 3D printer is characterized in that: the back pressure unit comprises an inert gas bottle, a connecting air pipe and a pressure regulating valve, wherein the inert gas bottle is connected with the pressure regulating valve and one end of the connecting air pipe, and the other end of the connecting air pipe is connected with the printing spray head or the precise slit coating module.

8. The 3D printer for preparing the multi-material micro-nano composite film according to claim 1, wherein the 3D printer is characterized in that: the nozzles of the printing spray heads are all conductive nozzles, and the inner diameter size of the nozzles is 0.5-1000 mu m.

9. A method of operation based on a 3D printer according to any one of claims 1-8, characterized by: the method comprises the following steps:

step 5: the printed film is fully cured.

10. The method of operation of claim 9, wherein: the specific process of executing the corresponding layer film or film structure in the step 3 and the step 4 comprises the following steps:

11. The method of operation of claim 9, wherein: the step 1 further comprises pre-treating the printing substrate, and if the film needs to be separated from the substrate, coating a layer of hydrophobic material or water-soluble material on the substrate in advance; if the film is not separated from the substrate, a layer of coupling agent is coated or corona or ozone treatment is performed to improve the surface energy and adhesion strength of the substrate.