CN102409462B - Method for printing disordered micro nanofibers into ordered fiber array - Google Patents

Abstract

Translated fromChinese

本发明属于静电纺丝技术领域，涉及一种采用滑移打印技术将静电纺丝制备的无序微纳米纤维打印成有序排列纤维阵列的方法，选用常规的静电纺丝装置，在先制得无序排列微纳米纤维的基础上，将载有无序纤维的收集衬底旋转180°后，反压在目标衬底上，使无序排列的微纳米纤维恰好夹在收集衬底和目标衬底之间；再对带有无序排列微纳米纤维的收集衬底施加一个竖直压力使上面的收集衬底和下面的目标衬底之间形成挤压力，并按压住上面的收集衬底且保持目标衬底不动，然而平行滑移收集衬底，使两衬底逐渐分离；最后在目标衬底上得到有序排列的微纳米纤维；其总体操作工艺简便，适用条件宽松，目标衬底范围广，节省能源，打印效果好。

The invention belongs to the technical field of electrospinning, and relates to a method for printing disordered micro-nano fibers prepared by electrospinning into an orderly array of fibers by using slip printing technology. On the basis of ordering micro-nanofibers, rotate the collection substrate loaded with disordered fibers by 180°, and press it against the target substrate, so that the disordered micro-nanofibers are sandwiched between the collection substrate and the target substrate. Between; then apply a vertical pressure to the collection substrate with disorderly arranged micro-nano fibers to form a pressing force between the upper collection substrate and the lower target substrate, and press the upper collection substrate And keep the target substrate still, but slide the collecting substrate in parallel, so that the two substrates are gradually separated; finally, orderly arranged micro-nano fibers are obtained on the target substrate; the overall operation process is simple, the applicable conditions are loose, and the target substrate Wide bottom range, energy saving, good printing effect.

Description

A kind of method that unordered micro nanometer fiber is printed as to ordered arrangement fiber array

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 ℃ ofmagnetic 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 alignmentmicro nanometer fiber 1 using collection as collection substrate 2, then get on the horizontal plane that a sheet glass is fixed on experiment porch astarget substrate 5; After being loaded with 180 ° of collection substrate 2 upsets of lack of alignmentmicro nanometer fiber 1, tip upside down intarget substrate 5, lack of alignmentmicro nanometer fiber 1 is clipped between the collection substrate 2 and followingtarget substrate 5 of top just, and the collection substrate 2 of top and followingtarget 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 alignmentmicro nanometer fiber 1; Meanwhile, to collecting on substrate 2, applyhorizontal thrust 3 slowly, make two substrates by vertically over against being progressively separated into separation; Intarget substrate 5 after separation, obtain ordered arrangementmicro 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 technique₂on/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)

Translated fromChinese

1.一种将无序微纳米纤维打印成有序排列纤维阵列的方法，其特征在于制备和打印有序排列微纳米纤维时选用常规的静电纺丝装置，在先制得无序排列微纳米纤维的基础上，再用机械压力代替滚筒和框架收集方式对微纳米纤维进行有序化排列，实现微纳米纤维从收集衬底到目标衬底的转移；先将收集有无序排列微纳米纤维的硅片作为的收集衬底，再取一块玻璃片固定在实验平台的水平面上作为目标衬底；将载有无序排列微纳米纤维的收集衬底翻转180°后倒扣在目标衬底上，无序排列微纳米纤维夹在上边的收集衬底和下边的目标衬底之间，上边的收集衬底和下边的目标衬底竖直方向对正；对载有无序排列微纳米纤维的收集衬底施加竖直压力，使两衬底间有效挤压但又不会压断无序排列微纳米纤维；同时，对收集衬底上施加缓慢的水平推力，使得两衬底由竖直正对逐步分开至分离；在分离后的目标衬底上得到有序排列微纳米纤维；所述的无序排列微纳米纤维原料是聚偏氟乙烯、聚苯乙烯或聚甲基丙烯酸甲酯。 1. A method for printing disordered micro-nano fibers into an ordered array of fibers, characterized in that a conventional electrospinning device is used when preparing and printing ordered micro-nano fibers, and the disordered micro-nano fibers are first prepared On the basis of this method, the mechanical pressure is used instead of the roller and frame collection method to arrange the micro-nanofibers in an orderly manner, so as to realize the transfer of the micro-nanofibers from the collection substrate to the target substrate; The silicon wafer is used as the collection substrate, and a piece of glass is fixed on the horizontal surface of the experimental platform as the target substrate; the collection substrate loaded with disorderly arranged micro-nano fibers is turned over 180° and then buckled upside down on the target substrate. The disorderly arranged micro-nanofibers are sandwiched between the upper collection substrate and the lower target substrate, and the upper collection substrate and the lower target substrate are vertically aligned; The substrate exerts a vertical pressure, so that the two substrates can be effectively squeezed without crushing the disordered micro-nanofibers; at the same time, a slow horizontal thrust is applied to the collecting substrate, so that the two substrates are vertically facing each other. stepwise separation to separation; orderly arranged micronanofibers are obtained on the separated target substrate; the raw material of the disorderly arranged micronanofibers is polyvinylidene fluoride, polystyrene or polymethyl methacrylate. the2.根据权利要求1所述的将无序微纳米纤维打印成有序排列纤维阵列的方法，其特征在于制备无序排列微纳米纤维的纺丝溶液为质量分数为20%的聚偏氟乙烯溶液，先将3.1克聚偏氟乙烯颗粒在磁力搅拌下缓慢加入12.4克二甲基亚砜和丙酮的混合溶液中，二甲基亚砜和丙酮的质量比为1:1；将混合溶液加热到40-60℃磁力搅拌1小时，静置半小时，即得质量分数20%的聚偏氟乙烯静电纺丝前驱体溶液；再将质量分数20%的聚偏氟乙烯静电纺丝前驱体溶液注入到针尖接有高压电源正极的注射器中，选取水平放置的硅片作为收集衬底，高压电源提供的纺丝电压为10千伏，注射器针尖与收集极平板之间的工作距离为7-8厘米，接通电源在室温下进行常规静电纺丝，静电纺丝得到的无序排列微纳米纤维承接在收集衬底上。 2. The method of printing disordered micro-nano fibers into an ordered array of fibers according to claim 1, wherein the spinning solution for preparing disordered micro-nano fibers is polyvinylidene fluoride with a mass fraction of 20% Solution, first slowly add 3.1 grams of polyvinylidene fluoride particles into a mixed solution of 12.4 grams of dimethyl sulfoxide and acetone under magnetic stirring, the mass ratio of dimethyl sulfoxide and acetone is 1:1; the mixed solution is heated Stir magnetically at 40-60°C for 1 hour, and let it stand for half an hour to obtain a 20% mass fraction of polyvinylidene fluoride electrospinning precursor solution; then 20% mass fraction of polyvinylidene fluoride electrospinning precursor solution Inject into a syringe with a needle tip connected to the positive electrode of a high-voltage power supply, select a horizontally placed silicon wafer as the collecting substrate, the spinning voltage provided by the high-voltage power supply is 10 kV, and the working distance between the needle tip of the syringe and the flat plate of the collector is 7-8 cm, turn on the power supply and perform conventional electrospinning at room temperature, and the disordered micro-nano fibers obtained by electrospinning are carried on the collection substrate. the

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