CN102517800B - Electrostatic spinning method for controlling assembly of nanofibers with two-dimensional and three-dimensional structures - Google Patents
Electrostatic spinning method for controlling assembly of nanofibers with two-dimensional and three-dimensional structures Download PDFInfo
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- CN102517800B CN102517800B CN2011103976801A CN201110397680A CN102517800B CN 102517800 B CN102517800 B CN 102517800B CN 2011103976801 A CN2011103976801 A CN 2011103976801A CN 201110397680 A CN201110397680 A CN 201110397680A CN 102517800 B CN102517800 B CN 102517800B
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Abstract
The invention belongs to the field of micro/nanofibers prepared by an electrostatic spinning technology, and relates to a process for freely controlling self-assembled fibers with a three-dimensional stacking structure by the electrostatic spinning technology, in particular to an electrostatic spinning method for controlling the assembly of nanofibers with two-dimensional and three-dimensional structures. The method comprises the following three steps of: self-assembling the nanofibers with the three-dimensional structure, wherein a positive electrode of a high-voltage direct-current power supply is connected to a spinning needle by the conventional electrostatic spinning device, a filter collection device is a grounded aluminum foil, and a spinning solution with positive charges is sprayed from the spinning needle under the action of an electrostatic field and is stretched, split and refined to form the micro/nanofibers which fall on the grounded aluminum foil; converting the three-dimensional stacking structure into a two-dimensional film; and converting a two-dimensional stacking structure into a three-dimensional film, so that free control is realized. The whole process is simple and easy to operate and control, used equipment is technically mature, an electrostatic spinning effect is good, efficiency is high, and environment friendliness is achieved.
Description
Technical field:
The invention belongs to electrostatic spinning technique and prepare the micro nanometer fiber field, the technical matters that relates to a kind of electrostatic spinning self assembled three-dimensional stacking provisions fiber and macrostructure (for example two-dimensional film and the three-dimensional stacking) realization of electrospun fibers is freely controlled, particularly a kind of electrospinning process of controlling the assembling of 2 and 3 dimensional organization nanofiber.
Background technology:
Electrostatic spinning technique is a kind of method that efficient low-consume prepares micro nanometer fiber.Than other method, the electrostatic spinning subtraction unit is simple, flexible operation, is applicable to the continuous electro-spinning of most of polymer.Traditional electrostatic spinning apparatus comprises three parts: high voltage source, fiber emitter and the fiber collecting device of spinning solution are housed; Generally, high-voltage power cathode is connected on the fiber emitter, negative pole is connected on the upper also ground connection of fiber collecting device (for example aluminium foil), form a high voltage electric field between fiber emitter and gathering-device, operating voltage is greatly between the 5-30 kilovolt, and the distance between spinning nozzle and gathering-device is generally 8-20 centimetre; During experiment, spinning solution is added in the fiber emitter, add high voltage, spinning solution forms taylor cone at the tip of emitter, under the electric field force effect, the jet ejected from taylor cone occurs to stretch or the splitting refinement, is accompanied by the volatilization of solvent in spinning process, fiber further solidifies, and deposits on gathering-device.Generally, due to gathering-device ground connection, the positive charge on fiber is led away, and fiber can be laid in the unordered two-dimensional film structure of formation on gathering-device.Along with development in science and technology, the technology that existing electrostatic spinning prepares the two-dimensional fiber film is comparative maturity, but it is not yet common that electrostatic spinning prepares the report of three-dimensional stacking provisions nanofiber, electrospinning three-dimensional structure nanofiber all has wide practical use in fields such as biological support, organizational project, battery electrode and solar cells.According to literature survey, adopting at present method of electrostatic spinning to prepare the three-dimensional structure nanofiber process mainly is present in following several: the one, increase the electrospinning time, thereby increase the thickness of spinning film, obtain the three-dimensional structure tunica fibrosa, for example, but this method operating time is very long (tens of hours) often, and tunica fibrosa thickness can only reach several millimeters; The 2nd, the two-dimensional fiber film prepared is taken off from collector, by the mode such as artificial folding obtain the three-dimensional structure fiber (Energy Environmental Science 2011,4:2807); The 3rd, three-dimensional gathering-device is replaced to two-dimentional gathering-device (Journal of Power Sources 2007,164:874; Nano Letters 2008,8:3283; International Journal of Biological Macromolecules 2009,45:504); In addition, by add blowing agent in solution, (Biomaterials 2006,27:3782; Journal of Biomedical Materials Research Part B:Applied Biomaterials 2007,104) etc. 81B (1): mode also has report, but, more complicated, the more high deficiency of cost of said method ubiquity operation, for electrostatic spinning self assembled three-dimensional structure nano fiber and form mechanism and can freely control problems such as generating two dimension or three-dimensional structure electrospinning fibre, all rarely has report both at home and abroad.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, on the basis of electrostatic spinning ratio juris and prior art, seek a kind of method of freely changing of utilizing the electrostatic spinning technique self assembly to prepare three-dimensional structure nanofiber, also realization two dimension and three-dimensional structure micro nanometer fiber.Utilize low-cost, the extensive self assembled three-dimensional stacking provisions nanofiber of electrostatic spinning technique and macrostructure (for example two-dimensional film and the three-dimensional stacking) realization of electrospun fibers is freely controlled.
To achieve these goals, the present invention includes self assembled three-dimensional structure nano fiber, three-dimensional stacking three processing steps of transformation to the transformation of two-dimensional film and two-dimentional stacking to three-dimension film:
(1) self assembled three-dimensional structure nano fiber: utilize existing electrostatic spinning apparatus, the positive pole of high-voltage DC power supply is received on the spinning syringe needle, fiber collecting device is the ground connection aluminium foil, under electrostatic field, positively charged spinning solution ejects from the spinning syringe needle, produce and stretch or the splitting refinement, form micro nanometer fiber and fall on the ground connection aluminium foil; Due to aluminium foil ground connection, positive charge on fiber is led away, obtain unordered nano-fiber film on aluminium foil, spin volatility and the relative air humidity of liquid viscosity, solvent by control, on the inherent aluminium foil of electrospinning fibre 20-40 minutes, self assembly forms large-sized three-dimensional stacking provisions, and it is highly 10 centimetres; The fiber band negative electrical charge at its three-dimensional stacking provisions top, reason is formed by the highfield polarization; Formation mechanism and the process of three-dimensional stacking provisions are as follows: after electrostatic spinning starts, a small amount of electrospinning fibre, owing to solidifying rapidly in air, has mechanical strength, then is deposited on the electrospinning fibre kick that the ground connection aluminium foil upwards forms; Joint effect due to electrostatic induction and polarization in strong electrostatic field, make the top fiber of electrospinning fibre kick with negative electrical charge, causes the electric field at the tip that electric field action of formation is stronger between spinning syringe needle and electrospinning fibre kick-tip; Along with the carrying out of electrostatic spinning, positively charged jet fiber constantly deposits in the electrospinning fibre kick, makes in the electrospinning fibre kick and accumulates rapidly, constantly grows tall and grows up, and forms three-dimensional stacking provisions nanofiber;
(2) three-dimensional stacking is to the transformation of two-dimensional film: at the ground connection aluminium foil, as collector success self assembly, obtain on the basis of three-dimensional stacking provisions fiber, need not change the experiment condition of spinning solution, place the plastic board of an insulation on gathering-device ground connection aluminium foil, now on plastic board, can collect the nano-fiber film of two-dimensional structure; The ambroin plate part intercepts electrostatic field, particularly blocking the positive charge that is deposited on nanofiber on plastic board can not lead away from the ground connection aluminium foil, fiber with positive charge mutually repels under the Coulomb repulsion effect, be difficult to form the three-dimensional structure of self assembly, so be laid on the ambroin flat board, form the nanofiber of two-dimensional film structure, realize the controlled transformation from three-dimensional stacking to the two-dimensional film structure;
(3) two-dimensional film is to the transformation of three-dimensional stacking: in the situation that collect the two-dimensional fiber film on the ambroin flat board, the induction machine negative pole is received to the fiber membrane on the ambroin flat board, rotate induction machine, continue electrostatic spinning simultaneously, reappear the three-dimensional stacking provisions of self assembly on the ambroin flat board, the electrizer negative pole can constantly provide negative electrical charge to neutralize on fiber membrane and be with the ground positive charge, the nanofiber of original positively charged on the ambroin flat board is become to electroneutral nanofiber, the jet fiber of unnecessary negative electrical charge meeting suction band positive charge constantly deposits, promptly grow tall and grow up, again self assembly forms three-dimensional stacking provisions nanofiber, the controlled transformation of realization from two-dimensional film to three-dimensional stacking provisions.
Compared with prior art, its whole technological process is simple in the present invention, and easy controlled operation is used the equipment and technology maturation, and electrospinning is effective, and efficiency is high, environmental friendliness.
The accompanying drawing explanation:
The electrostatic spinning principle schematic that Fig. 1 is the control nanofiber assembling that the present invention relates to, comprise syringe 1, spinning solution 2, spinning syringe needle 3, wire 4, high-voltage DC power supply 5, ground connection aluminium foil 6, electrospinning fibre kick 7, ambroin flat board 8, electrizer negative pole 9 and induction machine 10.
Fig. 2 is the three-dimensional stacking provisions nanofiber of polystyrene for preparing of the electrostatic spinning technique that the present invention relates to and the photo of two-dimensional fiber film, the optical photograph that wherein (a) is three-dimensional stacking provisions nanofiber; (b) be the optical photograph of two-dimensional nano fiber membrane; (c) be scanning electronic microscope (SEM) photo of the three-dimensional stacking provisions nanofiber of polystyrene.
The specific embodiment:
Below by embodiment, also be described further by reference to the accompanying drawings.
The present embodiment comprises self assembled three-dimensional structure nano fiber, three-dimensional stacking three processing steps of transformation to the transformation of two-dimensional film and two-dimentional stacking to three-dimension film:
(1) self assembled three-dimensional structure nano fiber: utilize existing electrostatic spinning apparatus, the positive pole of high-voltage DC power supply 5 is received on spinning syringe needle 3, fiber collecting device is ground connection aluminium foil 6, under electrostatic field, positively charged spinning solution 2 ejects from spinning syringe needle 3, produce and stretch or the splitting refinement, form micro nanometer fiber and fall on ground connection aluminium foil 6; Due to aluminium foil ground connection, positive charge on fiber is led away, obtain unordered nano-fiber film on aluminium foil, spin volatility and the relative air humidity of liquid viscosity, solvent by control, on the inherent aluminium foil of electrospinning fibre 20-40 minutes, self assembly forms large-sized three-dimensional stacking provisions, and it is highly 10 centimetres; The fiber band negative electrical charge at its three-dimensional stacking provisions top, reason is formed by the highfield polarization; Formation mechanism and the process of three-dimensional stacking provisions are as follows: after electrostatic spinning starts, a small amount of electrospinning fibre, owing to solidifying rapidly in air, has mechanical strength, then is deposited on the electrospinning fibre kick 7 that ground connection aluminium foil 6 upwards forms; Joint effect due to electrostatic induction and polarization in strong electrostatic field, make the top fiber of electrospinning fibre kick 7 with negative electrical charge, causes the electric field at the tip that electric field action of formation is stronger between spinning syringe needle 3 and electrospinning fibre kick 7-tip; Along with the carrying out of electrostatic spinning, positively charged jet fiber constantly deposits in electrospinning fibre kick 7, makes in electrospinning fibre kick 7 and accumulates rapidly, constantly grows tall and grows up, and forms three-dimensional stacking provisions nanofiber;
(2) three-dimensional stacking is to the transformation of two-dimensional film: at ground connection aluminium foil 6, as collector success self assembly, obtain on the basis of three-dimensional stacking provisions fiber, need not change the experiment condition of spinning solution, place the plastic board 8 of an insulation on gathering-device ground connection aluminium foil 6, now on plastic board 8, can collect the nano-fiber film of two-dimensional structure; Dull and stereotyped 8 parts of ambroin intercept electrostatic field, particularly blocking the positive charge that is deposited on nanofiber on plastic board 8 can not lead away from ground connection aluminium foil 6, fiber with positive charge mutually repels under the Coulomb repulsion effect, be difficult to form the three-dimensional structure of self assembly, so be laid on ambroin flat board 8, form the nanofiber of two-dimensional film structure, realize the controlled transformation from three-dimensional stacking to the two-dimensional film structure;
(3) two-dimensional film is to the transformation of three-dimensional stacking: in the situation that collect the two-dimensional fiber film on ambroin flat board 8, induction machine negative pole 9 is received to the fiber membrane on ambroin flat board 8, rotate induction machine 10, continue electrostatic spinning simultaneously, reappear the three-dimensional stacking provisions of self assembly on ambroin flat board 8, electrizer negative pole 9 can constantly provide negative electrical charge to neutralize on fiber membrane and be with the ground positive charge, the nanofiber of original positively charged on ambroin flat board 8 is become to electroneutral nanofiber, the jet fiber of unnecessary negative electrical charge meeting suction band positive charge constantly deposits, promptly grow tall and grow up, again self assembly forms three-dimensional stacking provisions nanofiber, the controlled transformation of realization from two-dimensional film to three-dimensional stacking provisions.
Embodiment 1:
The selected spinning solution of the present embodiment is the polystyrene (Polystyrene that mass fraction is 15%, PS) solution, 3 gram Polystyrene powders are dissolved in to 17 gram dimethyl formamide (dimethylformamide, DMF) and oxolane (tetrahydrofuran, THF) in mixed solution, (mass ratio of DMF and THF is 1: 1, each 8.5 grams), with magnetic stirring apparatus, mixed solution is stirred after 4 hours standing 1 hour, obtain the polystyrene electrostatic spinning precursor solution of mass fraction 15%; The polystyrene electrostatic spinning precursor solution that is 15% by mass fraction is injected in the syringe 1 that is connected to high-voltage DC power supply 5 (spinning voltage is the 20kV left and right just very); Distance between spinning syringe needle 3 and ground connection aluminium foil 6 is 14-16 centimetre, under room temperature (10 ℃-20 ℃), switches on power and carries out spinning; Due to the particularly rapid volatilization of oxolane of solvent, electrospinning fibre deposits on aluminium foil, and self assembly forms three-dimensional stacking provisions nanofiber at short notice, after three-dimensional stacking provisions grows into default height, from the ambroin flat board 8 of the most advanced and sophisticated top surfacing of concora crush from top to bottom of three-dimensional stacking provisions fiber as new fiber collecting device, after this spinning is proceeded, and makes the two-dimensional fiber film on ambroin flat board 8; The negative pole of the induction machine 9 of fiber membrane access on plastic board 8 shakes induction machine negative electrical charge is provided in spinning, on ambroin flat board 8, can again obtain three-dimensional stacking provisions; After spinning finishes, powered-down, cleaning laboratory apparatus; Accompanying drawing 2 has provided the photo of the three-dimensional stacking provisions fiber of the polystyrene prepared by the method and two-dimensional fiber film, illustrates that the nanofiber that utilizes the method can freely control generation is two-dimensional film structure or three-dimensional stacking provisions.
The present embodiment is except the polystyrene spinning solution, with the polyvinylpyrrolidone (PVP that contains a small amount of nitrate (such as ferric nitrate, cobalt nitrate, nickel nitrate etc.), 25wt%) ethanolic solution carries out electrospinning, can access equally the three-dimensional stacking provisions nanofiber of large scale self assembly.
Claims (1)
1. control the electrospinning process that the 2 and 3 dimensional organization nanofiber is assembled for one kind, it is characterized in that comprising that self assembled three-dimensional structure nano fiber, three-dimensional stacking arrive the transformation of two-dimensional film and three processing steps of transformation that two-dimensional film arrives three-dimensional stacking:
(1) self assembled three-dimensional structure nano fiber: utilize existing electrostatic spinning apparatus, the positive pole of high-voltage DC power supply is received on the spinning syringe needle, fiber collecting device is the ground connection aluminium foil, under electrostatic field, positively charged spinning solution ejects from the spinning syringe needle, produce and stretch or the splitting refinement, form micro nanometer fiber and fall on the ground connection aluminium foil; Due to aluminium foil ground connection, positive charge on fiber is led away, obtain unordered nano-fiber film on aluminium foil, spin volatility and the relative air humidity of liquid viscosity, solvent by control, on the inherent aluminium foil of electrospinning fibre 20-40 minutes, self assembly forms three-dimensional stacking provisions, and it is highly 10 centimetres; The fiber band negative electrical charge at its three-dimensional stacking provisions top, reason is formed by the highfield polarization; Formation mechanism and the process of three-dimensional stacking provisions are as follows: after electrostatic spinning starts, a small amount of electrospinning fibre solidifies and has mechanical strength rapidly in air, then is deposited on the ground connection aluminium foil and forms the electrospinning fibre kick; Joint effect due to electrostatic induction and polarization in strong electrostatic field, make the top fiber of electrospinning fibre kick with negative electrical charge, causes forming an electric field action tip-most advanced and sophisticated electric field between spinning syringe needle and electrospinning fibre kick; Along with the carrying out of electrostatic spinning, positively charged jet fiber constantly deposits in the electrospinning fibre kick, makes in the electrospinning fibre kick and accumulates rapidly, constantly grows tall and grows up, and forms three-dimensional stacking provisions nanofiber;
(2) three-dimensional stacking is to the transformation of two-dimensional film: at the ground connection aluminium foil, as collector success self assembly, obtain on the basis of three-dimensional stacking provisions fiber, do not change the experiment condition of spinning solution, place an ambroin flat board on gathering-device ground connection aluminium foil, now on the ambroin flat board, can collect the nano-fiber film of two-dimensional structure; The ambroin plate part intercepts electrostatic field, blocking-up is deposited on the positive charge of nanofiber on plastic board and can not leads away from the ground connection aluminium foil, fiber with positive charge mutually repels under the Coulomb repulsion effect, do not form the three-dimensional structure of self assembly, so be laid on the ambroin flat board, form the nanofiber of two-dimensional film structure, realize the controlled transformation from three-dimensional stacking to the two-dimensional film structure;
(3) two-dimensional film is to the transformation of three-dimensional stacking: in the situation that collect the two-dimensional fiber film on the ambroin flat board, the induction machine negative pole is received to the fiber membrane on the ambroin flat board, rotate induction machine, continue electrostatic spinning simultaneously, reappear the three-dimensional stacking provisions of self assembly on the ambroin flat board, the induction machine negative pole can constantly provide negative electrical charge to neutralize on fiber membrane and be with the ground positive charge, the nanofiber of original positively charged on the ambroin flat board is become to electroneutral nanofiber, the jet fiber of unnecessary negative electrical charge meeting suction band positive charge constantly deposits, promptly grow tall and grow up, again self assembly forms three-dimensional stacking provisions nanofiber, the controlled transformation of realization from two-dimensional film to three-dimensional stacking provisions.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040052685A (en) * | 2004-04-28 | 2004-06-23 | 정도성 | Electrospinning apparatus equipped with evacuated rotatable spinneret |
| CN101736436A (en) * | 2008-11-11 | 2010-06-16 | 苏州纳米技术与纳米仿生研究所 | Composite electrostatic spinning integrated by initiator and preparation method thereof |
| CN201520821U (en) * | 2009-09-27 | 2010-07-07 | 上海大学 | Device for preparing spatial ordered electrostatic spinning nanofibers |
| CN102206878A (en) * | 2011-05-24 | 2011-10-05 | 厦门大学 | Device for electrospinning three-dimensional controlled structure of nanofibers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040052685A (en) * | 2004-04-28 | 2004-06-23 | 정도성 | Electrospinning apparatus equipped with evacuated rotatable spinneret |
| CN101736436A (en) * | 2008-11-11 | 2010-06-16 | 苏州纳米技术与纳米仿生研究所 | Composite electrostatic spinning integrated by initiator and preparation method thereof |
| CN201520821U (en) * | 2009-09-27 | 2010-07-07 | 上海大学 | Device for preparing spatial ordered electrostatic spinning nanofibers |
| CN102206878A (en) * | 2011-05-24 | 2011-10-05 | 厦门大学 | Device for electrospinning three-dimensional controlled structure of nanofibers |
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