CN102409462B - Method for printing disordered micro nanofibers into ordered fiber array - Google Patents
Method for printing disordered micro nanofibers into ordered fiber array Download PDFInfo
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- CN102409462B CN102409462B CN201110255577.3A CN201110255577A CN102409462B CN 102409462 B CN102409462 B CN 102409462B CN 201110255577 A CN201110255577 A CN 201110255577A CN 102409462 B CN102409462 B CN 102409462B
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Abstract
The invention belongs to the technical field of electrostatic spinning and relates to a method for printing disordered micro nanofibers prepared by electrostatic spinning into an ordered fiber array through the slide printing technology, which comprises the following steps of: firstly, selecting and using a conventional electrostatic spinning device, preparing disordered micro nanofibers, rotating a collection substrate loaded with the disordered fibers at an angle of 180 degrees, reversely pressing on a target substrate, and just clamping the disordered micro nanofibers between the collection substrate and the target substrate; next, applying the collection substrate with the disordered micro nanofibers with a vertical pressure to form an extruding force between the collection substrate at the upper end and the target substrate at the lower end, and pressing the collection substrate at the upper end and keeping the target substrate still, then parallelly sliding the collection substrate to gradually separate the two substrates; finally, obtaining the ordered micro nanofibers on the target substrate. The method has the advantages of simple and convenient process, flexible application condition, wide target substrate range, energy saving and good printing effect.
Description
Technical field:
The invention belongs to electrostatic spinning and micro-nano technical field of electronic devices, relate to a kind of ordered arrangement micro nanometer fiber preparation method for nano electron device and photoelectric device, particularly a kind of method that adopts unordered micro nanometer fiber that slippage printing technique is prepared electrostatic spinning to be printed as ordered arrangement fiber array.
Background technology:
Nano wire/the fiber of preparation and assembling ordered arrangement is one of important research direction of current nanometer technology and nano-device.Because the micro nanometer fiber array favorable orientation of ordered arrangement, compares with single nano-wire/fiber device, more easily realize the extensive assembling, integrated and practical of nano-device; Compare with the fiber membrane of lack of alignment, ordered nano line/fiber array shows more excellent performance at aspects such as mechanics, electricity, optics, at radio-frequency field effect transistor (ACS Nano2010; 4:5855), gas sensor (Sensors and Actuators B2010; 145:232), artificial skin (Nature Materials2010; 9:821), nano generator (Nano Letters2010; 10:3151), solar cell (Applied Physics Letters2008; 200810018826.5) etc. 92:183107), optical polarization device (Chinese Patent Application No.: aspect all has broad application prospects.Nano wire/fiber assemble method of report mainly contains microfluid assembling (Science2001 at present; 291:630), the auxiliary assembling of electric field/magnetic field (Applied Physics Letters2000; 77:1399.Chemistry of Materials2005; 17:1320), LB membrane technology (Nano Letters2003; 3:1255), air bubble expansion technology (Nature Nanotechnology2007; (Applied Physics Letters2007 is printed in 2:372), roll/contact; 91:203104.Nano Letters2008; 8:20) etc.In addition Chinese patent (application number: 200910025626.7) also disclose a kind of electrospun fibers that utilizes and assemble the method for one-dimensional nano line array as template from solvent.
The preparation method of existing nano wire and nanofiber has a lot, such as chemical vapour deposition (CVD), template, Chemical self-assembly method, electrostatic spinning etc.; Electrostatic spinning technique is a kind of simple method of preparing micro nanometer fiber, its main feature is that equipment is simple, easy to operate, experimental cost is low and is applicable to many different types of materials, micro nanometer fiber diameter range prepared by electrostatic spinning is in several nanometers between several microns, and fiber yield is higher; But micro nanometer fiber prepared by conventional electrostatic spinning apparatus is the form with nonwoven fabric to be existed, and fiber alignment is unordered, this has limited electrospinning fibre application aspect some at nano electron device and optics etc.In recent years, researcher, by improving conventional electrostatic device for spinning, has successfully improved the ordered arrangement degree of electrospinning micro nanometer fiber, and published method has cylinder collection, parallel pole or slit collection, framework to collect, assist external electric field or magnetic field collection etc.For example, patent applicant seminar has reported method (the Chinese Physics Letters2008 that a kind of slit and step are collected; 201010184068.1) and use compound frame collection technique (Chinese Patent Application No.: the micro nanometer fiber of 201110137420.0) preparing ordered arrangement 25:3067), the centrifugal electrospinning process of a kind of low pressure (Chinese Patent Application No.: has also been proposed.These methods be all by experimental provision, particularly electrospinning fibre gathering-device is improved to improve the order of fiber, but also there is some problems or restriction.For example, these methods need to be carried out preliminary treatment or processing to collecting screen, the Area comparison of the ordered fiber of collecting is little, restricted to collecting the material shielding, can not be optionally on a large scale at non-conductive flexibility or the upper ordered fiber of collecting of elastic substrate (sheet glass, plastic sheet, rubber pattern, the scraps of paper etc.).
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, do not changing on the basis of routine intravenous electric spinning device, design and a kind ofly the micro nanometer fiber of lack of alignment can be transformed into the Method of printing of ordered arrangement fiber, and the scope of application of expansion target substrate; The slippage Method of printing adopting, the unordered micro nanometer fiber that can on a large scale be prepared by routine intravenous Electrospun is printed by contact, transfer to selectively in target substrate and be transformed into the fiber of ordered arrangement, target substrate adopts hard silicon chip and sheet glass, or employing flexible plastic sheet and the scraps of paper, the print position of ordered fiber in target substrate, and the area operation of target substrate is controlled, be beneficial to and promote electrospun fibers at nano electron device, the particularly application of flexible nano device aspect.
To achieve these goals, the method of preparing ordered arrangement micro nanometer fiber is printed in the slippage that the present invention proposes, when preparation and printing ordered arrangement micro nanometer fiber, select conventional electrostatic spinning apparatus, formerly make on the basis of lack of alignment micro nanometer fiber, by mechanical pressure, replace cylinder and framework collection mode to carry out ordering arrangement to micro nanometer fiber again, realize micro nanometer fiber from collecting substrate to the transfer of target substrate; First will be loaded with after the collection substrate Rotate 180 ° of unordered fiber, back-pressure, in another piece target substrate, is just clipped in the micro nanometer fiber of lack of alignment and collects between substrate and target substrate; Again the collection substrate with lack of alignment micro nanometer fiber being applied to a vertical pressure makes to form extruding force between collection substrate above and target substrate below, and press collection substrate above and keep target substrate motionless, then parallel slip is collected substrate, makes to collect substrate and staggers gradually to separated with target substrate; The last micro nanometer fiber that obtains ordered arrangement in target substrate.
The present invention compared with prior art, the one, fiber is transferred in various hard, soft, conduction or dielectric substrate in order, expanded the scope of target substrate; The 2nd, do not change routine intravenous electric spinning device structure, do not need auxiliary electric field or magnetic field; The 3rd, experimental provision is simple, easy operating; The 4th, applied widely, the lack of alignment micro nanometer fiber of multiple material all can be printed and be obtained ordered fiber by slippage; The 5th, to spinning voltage, spin the not directly restriction of the conditions such as liquid concentration; Its overall operation simple process, applicable elements is loose, and target substrate scope is wide, saves the energy, and printing effect is good.
Accompanying drawing explanation:
Fig. 1 is operation principle structural representation of the present invention.
Fig. 2 is ESEM (SEM) photo of Kynoar (PVDF) micro nanometer fiber prepared of the present invention: wherein Fig. 2 (a) is for collecting the SEM photo of unordered PVDF micro nanometer fiber on substrate; Fig. 2 (b) is the SEM photo of ordered arrangement PVDF fiber in target substrate.
The specific embodiment:
Below by embodiment, be also described further by reference to the accompanying drawings.
The present embodiment is used conventional electrostatic spinning apparatus, selected spinning solution is that mass fraction is 20% Kynoar (polyvinylidene fluoride, PVDF) solution, first 3.1 grams of PVDF particles are slowly added under magnetic agitation to 12.4 grams of dimethyl sulfoxide (DMSO) (dimethyl sulfoxide, DMSO) and in the mixed solution of acetone (acetone) (mass ratio of DMSO and acetone is 1:1, each 6.2 grams); Mixed solution is heated to 40-60 ℃ of magnetic agitation 1 hour, standing half an hour, obtains the PVDF electrostatic spinning precursor solution of mass fraction 20%; Again the PVDF electrostatic spinning precursor solution of mass fraction 20% is injected in the syringe that needle point is connected to high-voltage power cathode, choose the silicon chip of horizontal positioned as collecting substrate 2, the spinning voltage that high voltage source provides is 10 kilovolts of left and right, operating distance between syringe needle point and collector flat board is 7-8 centimetre, switch on power and at room temperature carry out routine intravenous Electrospun, the lack of alignment micro nanometer fiber that electrostatic spinning obtains is undertaken on to be collected on substrate 2; Spinning finishes, powered-down.
The silicon chip that the present embodiment has a lack of alignment micro nanometer fiber 1 using collection as collection substrate 2, then get on the horizontal plane that a sheet glass is fixed on experiment porch as target substrate 5; After being loaded with 180 ° of collection substrate 2 upsets of lack of alignment micro nanometer fiber 1, tip upside down in target substrate 5, lack of alignment micro nanometer fiber 1 is clipped between the collection substrate 2 and following target substrate 5 of top just, and the collection substrate 2 of top and following target substrate 5 vertical directions align; To being loaded with the collection substrate 2 of lack of alignment micro nanometer fiber, apply vertical pressure 4, make between two substrates effectively extruding but can not break lack of alignment micro nanometer fiber 1; Meanwhile, to collecting on substrate 2, apply horizontal thrust 3 slowly, make two substrates by vertically over against being progressively separated into separation; In target substrate 5 after separation, obtain ordered arrangement micro nanometer fiber 6; Fig. 2 (a) is for collecting the scanning electron microscope sem photo of the PVDF micro nanometer fiber of lack of alignment on substrate, the SEM photo that Fig. 2 (b) is the ordered arrangement PVDF micro nanometer fiber that obtains by slippage Method of printing in target substrate.
The present embodiment is except hard glass sheet, and unordered PVDF fiber can also be transferred to hard SiO in order by slippage printing technique
2on/Si or Si sheet or flexible plastic sheet and the scraps of paper; Except PVDF fiber, other material (polystyrene (polystyrene for example, PS) and the electrospinning lack of alignment micro nanometer fiber of polymethyl methacrylate (poly (methyl methacrylate), PMMA)) also can on different target substrate, be printed as by slip Method of printing ordered arrangement micro nanometer fiber.
Claims (2)
1. a method that unordered micro nanometer fiber is printed as to ordered arrangement fiber array, when it is characterized in that preparation and printing ordered arrangement micro nanometer fiber, select conventional electrostatic spinning apparatus, formerly make on the basis of lack of alignment micro nanometer fiber, by mechanical pressure, replace cylinder and framework collection mode to carry out ordering arrangement to micro nanometer fiber again, realize micro nanometer fiber from collecting substrate to the transfer of target substrate; The silicon chip that first collection is had to a lack of alignment micro nanometer fiber as collection substrate, then get on the horizontal plane that a sheet glass is fixed on experiment porch as target substrate; After being loaded with 180 ° of the collection substrate upsets of lack of alignment micro nanometer fiber, tip upside down in target substrate, lack of alignment micro nanometer fiber is clipped between the collection substrate and following target substrate of top, and the collection substrate of top and following target substrate vertical direction align; To being loaded with the collection substrate of lack of alignment micro nanometer fiber, apply vertical pressure, make between two substrates effectively extruding but can not break lack of alignment micro nanometer fiber; Meanwhile, to collecting on substrate, apply horizontal thrust slowly, make two substrates by vertically over against being progressively separated into separation; In target substrate after separation, obtain ordered arrangement micro nanometer fiber; Described lack of alignment micro nanometer fiber raw material is Kynoar, polystyrene or polymethyl methacrylate.
2. the method that unordered micro nanometer fiber is printed as to ordered arrangement fiber array according to claim 1, the spinning solution that it is characterized in that preparing lack of alignment micro nanometer fiber is that mass fraction is 20% Kynoar solution, first 3.1 grams of Kynoar particles are slowly added in the mixed solution of 12.4 grams of dimethyl sulfoxide (DMSO)s and acetone under magnetic agitation, the mass ratio of dimethyl sulfoxide (DMSO) and acetone is 1:1; Mixed solution is heated to 40-60 ℃ of magnetic agitation 1 hour, standing half an hour, obtains the Kynoar electrostatic spinning precursor solution of mass fraction 20%; Again the Kynoar electrostatic spinning precursor solution of mass fraction 20% is injected in the syringe that needle point is connected to high-voltage power cathode, choose the silicon chip of horizontal positioned as collecting substrate, the spinning voltage that high voltage source provides is 10 kilovolts, operating distance between syringe needle point and collector flat board is 7-8 centimetre, switch on power and at room temperature carry out routine intravenous Electrospun, the lack of alignment micro nanometer fiber that electrostatic spinning obtains is undertaken on to be collected on substrate.
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| CN102409462B true CN102409462B (en) | 2014-01-22 |
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| CN103219280B (en) * | 2013-03-20 | 2015-06-17 | 华中科技大学 | Method for manufacturing ductile circuit interconnection structure by utilization of electrostatic spinning technique and product thereof |
| CN104878461B (en) * | 2015-05-26 | 2017-05-03 | 青岛大学 | Large-scale magnetic spinning equipment and method using equipment for manufacturing micro-nano-meter fibers |
| CN105862147B (en) * | 2016-06-14 | 2018-03-23 | 扬州纳佰成纳米科技有限公司 | A kind of continuous method of reseptance of the discrete roll-type nano fibrous membrane of electrostatic spinning and its device |
| CN108963069B (en) * | 2018-06-28 | 2022-01-11 | 上海凸申科技有限公司 | Preparation method of 3D printed polyvinylidene fluoride piezoelectric film |
| CN110212806B (en) * | 2019-05-30 | 2020-09-11 | 天津科技大学 | Full-printing preparation method of friction nano-generator based on 3D cellulose aerogel |
| CN110846810A (en) * | 2019-10-09 | 2020-02-28 | 南方科技大学 | High-thermal-conductivity nano composite fiber film and preparation method thereof |
| CN112649470A (en) * | 2020-12-31 | 2021-04-13 | 长春工业大学 | Preparation method of ordered polymer nanofiber array modified three-dimensional organic gas sensor |
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| CN101010780B (en) * | 2004-04-30 | 2012-07-25 | 纳米***公司 | Systems and methods for nanowire growth and harvesting |
| WO2007145701A2 (en) * | 2006-04-07 | 2007-12-21 | President And Fellows Of Harvard College | Nanoscale wire methods and devices |
| US7828539B1 (en) * | 2007-03-26 | 2010-11-09 | Clemson University | Fabrication of three dimensional aligned nanofiber array |
| CN101143705B (en) * | 2007-11-01 | 2010-08-11 | 南京大学 | Method for preparing micrometer and submicron probe arrays |
| CN101255611A (en) * | 2008-02-22 | 2008-09-03 | 哈尔滨工业大学深圳研究生院 | Electro spinning method for preparing orientation arranged polymer spiral nano-fibre and equipment thereof |
| CN101497428A (en) * | 2009-03-03 | 2009-08-05 | 东南大学 | Method for arranging nano-wire array using electrostatic filature |
| CN101857976B (en) * | 2010-05-19 | 2011-06-08 | 青岛大学 | Device for preparing nano fibers with ordered arrangement and cross structures |
| CN102050422A (en) * | 2010-12-01 | 2011-05-11 | 东南大学 | Method for arranging nano wires by combining fiber aid and contact impression |
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