CN106948014B - A kind of three-dimensional melting electrostatic Method of printing of big height micro-nano structure - Google Patents

A kind of three-dimensional melting electrostatic Method of printing of big height micro-nano structure Download PDF

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Publication number
CN106948014B
CN106948014B CN201710280584.6A CN201710280584A CN106948014B CN 106948014 B CN106948014 B CN 106948014B CN 201710280584 A CN201710280584 A CN 201710280584A CN 106948014 B CN106948014 B CN 106948014B
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nano structure
printing
micro
height
melting electrostatic
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CN106948014A (en
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贺健康
夏正勋
李涤尘
刘亚雄
王玲
连芩
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Xian Jiaotong University
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Xian Jiaotong University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0015Electro-spinning characterised by the initial state of the material
    • D01D5/003Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0046Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by coagulation, i.e. wet electro-spinning
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y50/00Data acquisition or data processing for additive manufacturing
    • B33Y50/02Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)

Abstract

A kind of three-dimensional melting electrostatic Method of printing of big height micro-nano structure, the mobile program of control platform is first compiled on computers, selection contains conducting medium solution and melting electrostatic printed material for filling, and it is respectively charged into the syringe of the melting electrostatic printing equipment containing multiple spray heads, then melting electrostatic print parameters are selected, it prints to obtain the three-dimensional micro-nano structure of setting thickness by melting electrostatic, conducting medium solution will be contained and be filled into three-dimensional micro-nano structure, make its plastic using the method for temperature crosslink and chemical crosslinking, so that melting electrostatic printing receiving platform increases, the thickness of the distance between printing head and receiving platform one colloid of height-regulating will be melted, repeatedly, until the height of three-dimensional micro-nano structure reaches desired height, realize the three-dimensional micro-nano structure of melting electrostatic printing big height, the present invention overcomes tradition molten Melt the shortcomings that electric field increases with height and decayed in static dump technique, can be widely applied to the fields such as micro-nano device, organizational project.

Description

A kind of three-dimensional melting electrostatic Method of printing of big height micro-nano structure
Technical field
The present invention relates to minute manufacturings and increases material manufacturing technology field, and in particular to a kind of three-dimensional of big height micro-nano structure Melting electrostatic Method of printing.
Background technique
Melting electrostatic printing is a kind of high-precision micro nanometer fiber manufacturing technology, and the technology is using polymer melt strong Micro nanometer fiber is formed under electric field and carries out electrostatic direct write, in conjunction with the principle and method of traditional increasing material manufacturing, passes through layer upon layer reality Existing various three-dimensional micro-nano structures.The technology not only has that fibre diameter is small, fiber homogeneity is good, can be realized sub-micron, nanometer Advantages such as scale, and it is many to can be used for melting electrostatic printed material, including from insulating polymer to conducting polymer, from inorganic High molecular material is to biomaterial, therefore the technology has wide practical use in fields such as micro-nano device, organizational projects.
But due to the limitation of printing technology, which is asked in terms of making big height three-dimensional micro-nano structure there are still some Topic: since the technology is to realize the deposition of fiber using high-pressure electrostatic driving, with being continuously increased for three-dimensional micro-nano structure height, Electric field strength also changes correspondingly, and original printing technology changes, so that the three-dimensional micro-nano structure limited height that can be made, maximum high Degree is usually no more than 2mm, it is impossible to be used in constructs the three-dimensional micro-nano structure compared with big height.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide the three of a kind of big height micro-nano structure Melting electrostatic Method of printing is tieed up, can stablize, continuously print the three-dimensional micro-nano structure with big height, can be widely applied to The fields such as micro-nano device, organizational project.
In order to achieve the above object, the technical scheme adopted by the invention is as follows:
A kind of three-dimensional melting electrostatic Method of printing of big height micro-nano structure, comprising the following steps:
1) program of control mobile platform is compiled on computers according to the complex pattern or threedimensional model of wanting printing;
2) solution containing conducting medium is configured, concentration of polymer solution containing conducting medium is between 1~20%;
3) melting electrostatic printed material is chosen, melting electrostatic printed material includes polycaprolactone, polylactic acid, polypropylene, gathers Poly lactic coglycolic acid, ethylene/polyvinyl alcohol copolymer, nylon series polymer the high polymer with polar group, It is different according to the fusing point of material, determine the heating temperature of Electrothermal ring or water oil bath circulation, Electrothermal ring temperature range 40~ Between 500 DEG C, oil bath circulating temperature range is between 40~200 DEG C, and water-bath circulating temperature range is between 40~100 DEG C;
4) the melting electrostatic printed material that solution containing conducting medium and step 3) that step 2) is prepared are chosen is respectively charged into In the syringe of melting electrostatic printing equipment containing multiple spray heads, wherein solution printing head is used to contain what is configured in step 2) Conducting medium solution is printed in a manner of squeezing out, melting printing head be used for the melting electrostatic printed material of choosing step 3) with The mode of melting electrostatic printing prints;
5) according to the line width of required fiber, feature sizes are between 1~100 μm, so that it is determined that the movement of mobile platform Speed: 1~300mm/s, the model for melting printing head: 100~1000 μm, and high-accuracy injection pump discharge: 5~ 1000uL/h, melting electrostatic printing head connect positive voltage, receiving platform on mobile platform ground connection, adjustment melting printing head with The distance between receiving platform: between 0.5~10mm, high voltage power supply is opened, adjustment voltage is to needing amplitude: 0.1~20Kv;
6) program for controlling mobile platform is inputted into host, program controls motion platform and melting electrostatic by control module Printing head realizes that layer upon layer obtains the three-dimensional micro-nano structure of 0.1~2mm;
7) after the three-dimensional micro-nano structure of single printing to be done, melting electrostatic printing head is switched to solution automatically by program Solution containing conducting medium in step 2) is filled into gained in step 6) by printing head, solution printing head in a manner of squeezing out Three-dimensional micro-nano structure in, solution packed height is slightly lower than the height of three-dimensional micro-nano structure, utilizes temperature crosslink or chemistry The method of crosslinking makes the plastic of solution containing conducting medium, and the salting liquid containing conductive ion does not have to then carry out crosslinking Treatment, is formed new Receiving platform, program automatically will melt the distance between printing head and receiving platform height-regulating one colloid thickness: 0.1~ 2mm;
8) automatic to repeat step 6) and step 7) according to the program of control mobile platform, until the height of three-dimensional micro-nano structure Degree reaches desired height, obtains the composite construction of three-dimensional micro-nano structure and dielectric solution and hydrogel;
9) dielectric inside the composite construction that step 8 obtains is removed by way of cleaning, changing temperature or chemical reaction Solution or hydrogel obtain big height micro-nano structure.
Solution containing conducting medium includes the various salting liquids containing conductive ion in the step 2), and salting liquid includes chlorine Change sodium solution, calcium chloride solution, or the gel with certain electric conductivity-particle mixed solution.
The gel includes that the gelatin and agarose, the chitosan of chemical crosslinking and sodium alginate, light of temperature crosslink are handed over The polyethylene glycol and gelatin of connection or the mixed solution of these materials.
The invention has the benefit that
Compared with existing melting electrostatic Method of printing, the advantage of this patent is can by the filling into three-dimensional micro-nano structure The conducting medium solution of flowing overcomes conventional melt electrostatic to beat so that receiving platform dynamic conductive in print procedure increases The shortcomings that electric field increases with height and is decayed in print technique, to realize being integrated for big height three-dimensional micro-nano structure.
Detailed description of the invention
Fig. 1 is embodiment step 6) obtained three-dimensional micro-nano structure.
Fig. 2 is embodiment step 7) obtained three-dimensional micro-nano structure.
Fig. 3 is embodiment step 8) obtained three-dimensional micro-nano structure and dielectric is molten and the composite construction of hydrogel.
Fig. 4 is embodiment step 9) obtained three-dimensional micro-nano structure.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is described in further detail.
A kind of three-dimensional melting electrostatic Method of printing of big height micro-nano structure, comprising the following steps:
1) program of control mobile platform is compiled on computers according to the complex pattern or threedimensional model of wanting printing;
2) solution containing conducting medium is configured, after selected solution containing conducting medium is mutually mixed for gelatin and agarose Solution, mass concentration are 5% and 1.5%;
3) choosing polycaprolactone is melting electrostatic printed material, determines the heating temperature of Electrothermal ring are as follows: 70 DEG C;
4) polycaprolactone that gelatin and agarose mixed solution and step 3) that step 2) is prepared are chosen is respectively charged into and is contained In the syringe of the melting electrostatic printing equipment of multiple spray heads, wherein solution printing head is used to lead containing for configuration in step 2) Dielectric solution is printed in a manner of squeezing out, what the material that melting printing head is used to choose step 3) was printed with melting electrostatic Mode prints;
5) 8 μm of line widths as fiber are selected, so that it is determined that the movement speed of mobile platform: 30mm/s, melting printing spray The model of head: 400 μm and high-accuracy injection pump discharge: 100uL/h, melting electrostatic printing head connect positive voltage, mobile platform On receiving platform ground connection, adjustment melting the distance between printing head and receiving platform: 3mm opens high voltage power supply, and adjustment is electric It is depressed into and needs amplitude: 3Kv;
6) program for controlling mobile platform is inputted into host, program controls mobile platform and melting electrostatic by control module Printing head realizes that layer upon layer obtains three-dimensional micro-nano structure, and the printing number of plies is 100 layers, i.e. single printing micro-nano structure height is 1mm, as shown in Figure 1;
7) after the three-dimensional micro-nano structure of single printing to be done, melting electrostatic printing head is switched to solution automatically by program Printing head, solution printing head by step 2) gelatin and agarose mixed solution be filled into three-dimensional obtained in step 6) Micro-nano structure, as shown in Figure 2;Solution packed height is slightly lower than the height of three-dimensional micro-nano structure, to guarantee the three of subsequent printing Tie up micro-nano structure and the partial 3-D micro-nano structure can abundant adhesion, temperature, which is reduced to 18 DEG C or less, makes its plastic, formation New receiving platform will melt the thickness of the distance between printing head and receiving platform one colloid of height-regulating: 1mm;
8) automatic to repeat step 6) and step 7) according to the program of control mobile platform, until the height of three-dimensional micro-nano structure Degree reaches desired height, and: 5mm obtains the composite construction of three-dimensional micro-nano structure and dielectric solution and hydrogel, such as Fig. 3 institute Show;
9) composite construction obtained in step 8) is put into 50 DEG C of warm water and is impregnated 2 hours, it can be by gelatin and agar Sugar removal, obtains big height three-dimensional micro-nano structure, the height of three-dimensional micro-nano structure is about 5mm, as shown in Figure 4.

Claims (3)

1. a kind of three-dimensional melting electrostatic Method of printing of big height micro-nano structure, which comprises the following steps:
1) program of control mobile platform is compiled on computers according to the complex pattern or threedimensional model of wanting printing;
2) solution containing conducting medium is configured, concentration of polymer solution containing conducting medium is between 1~20%;
3) melting electrostatic printed material is chosen, melting electrostatic printed material includes polycaprolactone, polylactic acid, polypropylene, polylactic acid- Co-glycolic acid, ethylene/polyvinyl alcohol copolymer, nylon series polymer the high polymer with polar group, according to The fusing point of material is different, determines the heating temperature of Electrothermal ring or water oil bath circulation, Electrothermal ring temperature range is at 40~500 DEG C Between, oil bath circulating temperature range is between 40~200 DEG C, and water-bath circulating temperature range is between 40~100 DEG C;
4) the melting electrostatic printed material that solution containing conducting medium and step 3) that step 2) is prepared are chosen is respectively charged into containing more In the syringe of the melting electrostatic printing equipment of a spray head, wherein solution printing head is used to be configured in step 2) containing conduction Medium solution is printed in a manner of squeezing out, and melting printing head is used for melting electrostatic printed material that step 3) is chosen to melt The mode of static dump prints;
5) according to the line width of required fiber, feature sizes are between 1~100 μm, so that it is determined that the movement speed of mobile platform: 1~300mm/s, the model for melting printing head: 100~1000 μm and high-accuracy injection pump discharge: 5~1000uL/h melts Melt static dump spray head and connect positive voltage, receiving platform on mobile platform ground connection, adjustment melting printing head and receiving platform it Between distance: between 0.5~10mm, open high voltage power supply, adjustment voltage is to needing amplitude: 0.1~20Kv;
6) program for controlling mobile platform is inputted into host, program controls motion platform by control module and melting electrostatic prints Spray head realizes that layer upon layer obtains the three-dimensional micro-nano structure of 0.1~2mm;
7) after the three-dimensional micro-nano structure of single printing to be done, melting electrostatic printing head is switched to solution printing automatically by program Solution containing conducting medium in step 2) is filled into three obtained in step 6) by spray head, solution printing head in a manner of squeezing out It ties up in micro-nano structure, solution packed height is slightly lower than the height of three-dimensional micro-nano structure, utilizes temperature crosslink or chemical crosslinking Method make the plastic of solution containing conducting medium, the salting liquid containing conductive ion does not have to then carry out crosslinking Treatment, forms new connect It is closed flat platform, program will melt the thickness of the distance between printing head and receiving platform one colloid of height-regulating: 0.1~2mm automatically;
8) automatic to repeat step 6) and step 7) according to the program of control mobile platform, until the height of three-dimensional micro-nano structure reaches To desired height, the composite construction of three-dimensional micro-nano structure and dielectric solution and hydrogel is obtained;
9) dielectric solution inside the composite construction that step 8 obtains is removed by way of cleaning, changing temperature or chemical reaction Or hydrogel, obtain big height micro-nano structure.
2. a kind of three-dimensional melting electrostatic Method of printing of big height micro-nano structure according to claim 1, it is characterised in that: Solution containing conducting medium includes the various salting liquids containing conductive ion in the step 2), and salting liquid includes that sodium chloride is molten Liquid, calcium chloride solution, or the gel with certain electric conductivity-particle mixed solution.
3. a kind of three-dimensional melting electrostatic Method of printing of big height micro-nano structure according to claim 2, it is characterised in that: The gel includes the poly- second of the gelatin and agarose of temperature crosslink, the chitosan of chemical crosslinking and sodium alginate, photo-crosslinking The mixed solution of two pure and mild gelatin or these materials.
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CN113793965B (en) * 2021-09-01 2024-01-09 西安交通大学 Multi-material printing device and method for flexible ion gel battery
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WO2016050357A1 (en) * 2014-10-02 2016-04-07 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e. V. Methods for preparing and orientating biopolymer nanofibres and a composite material comprising the same
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CN104887346B (en) * 2015-06-19 2017-01-04 西安交通大学 A kind of high-precision biological 3D Method of printing
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WO2022117667A1 (en) * 2020-12-02 2022-06-09 Technische Universität München Electro-spinning/writing system and corresponding method
WO2022132769A3 (en) * 2020-12-15 2022-09-01 Illumina, Inc. Flow cell coating methods

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