CN102453965A - Method and device for preparing nanofibers - Google Patents
Method and device for preparing nanofibers Download PDFInfo
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- CN102453965A CN102453965A CN2011100232448A CN201110023244A CN102453965A CN 102453965 A CN102453965 A CN 102453965A CN 2011100232448 A CN2011100232448 A CN 2011100232448A CN 201110023244 A CN201110023244 A CN 201110023244A CN 102453965 A CN102453965 A CN 102453965A
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Abstract
The invention provides a method for preparing nanofibers, which comprises the following steps that: a spinning solution is sprayed to form charged liquid drops by electrostatic spraying; and the charged liquid drops enter a low-temperature environment and quickly exchange energy with an ambient environment, so that the liquid drops are in an unbalanced state, the deformation of the charged liquid drops is promoted, and fluid is induced from the deformed liquid drops under the action of electrostatic repulsive force of charges and is condensed and solidified to form the nanofibers. The invention also provides a device for preparing the nanofibers by the method. In the method, the fluid is induced from the charged liquid drops and then condensed and solidified, so the method is also suitable for low-viscosity liquid, and the types of the nanofibers are expanded.
Description
Technical field
The present invention relates to the nanofiber field, particularly the device of a kind of preparation method of nanofiber and preparation nanofiber.
Background technology
Nanofiber typically refers to diameter or caliber thickness less than the superfine fibre of 100nm, mainly comprises nano silk, nano wire, nanometer rods, nanotube, nano belt and nano-cable.With respect to common fiber; The diameter of nanofiber is minimum; Be nanometer scale, also show many physics and chemical characteristic thus, the maximum characteristics of nanofiber are that specific area is big; Make its surface energy increase thus, thereby produce small-size effect, surface or interfacial effect, quantum size effect and macro quanta tunnel effect etc. with active.The physics of nanofiber and chemical characteristic make it have broad application prospects at numerous areas.
Prior art provides the multiple method for preparing nanofiber, like method of electrostatic spinning, the method for reeling off raw silk from cocoons, template synthetic method, split-phase method and self-assembly method etc.The defective of the method for electrostatic spinning and the method for reeling off raw silk from cocoons is the viscosity of spinning solution is required harshness, narrow application range; The shortcoming of template synthetic method is to prepare the continuous nano-fibre that the root root separates; The production efficiency of split-phase method and self-assembly method is all lower.Above-mentioned several method all is difficult to low-viscosity (mobile) liquid or low viscosity molten mass directly are prepared into nanofiber.
Therefore, provide a kind of and can the method that low-viscosity (mobile) liquid or low viscosity molten mass directly are prepared into nanofiber be had great realistic meaning.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method of nanofiber, and this method is lower to the viscosity limitation of spinning solution, and the scope of application is wider.
In view of this, the present invention provides a kind of preparation method of nanofiber, comprising:
Utilize electrostatic spraying that spinning solution is injected into charged drop;
Said charged drop deforms before solidifying under cryogenic conditions and induces fluid;
Said fluid condensation cured obtains nanofiber.
Preferably, said spinning solution is low-viscosity (mobile) liquid or low viscosity molten mass.
Preferably, said low-viscosity (mobile) liquid is water, inorganic salt solution, small organic molecule liquid.
Accordingly, the present invention also provides a kind of nanofiber by method for preparing.
Accordingly, the present invention also provides a kind of nano-fiber manufacturing apparatus, comprising:
High voltage source;
The static nozzle that links to each other with high voltage source;
The receiver corresponding with the static nozzle position is used for the fluid that the condensation cured charged drop induces, and forms nanofiber.
Preferably, said receiver comprises: cavity and the cryogenic substance that is arranged at cavity cavity place.
Preferably, said cryogenic substance is liquid nitrogen, dry ice or LPG.
Preferably, also comprise:, be used for spinning material is heated into the spinning molten mass with the heater that said static nozzle links to each other.
Method provided by the invention is to utilize electrostatic spraying earlier; Fluid jet is become charged fine droplet, and quick exchange heat takes place with surrounding environment after getting into low temperature environment in charged drop on the one hand that eject immediately, receives the effect of electric charge electrostatic repulsion forces on the other hand; The original heat of charged drop, electric equilibrium are destroyed; Stretcher strain takes place in it under the out-of-balance force effect, gradually become the fusiform fusiformis charged drop of middle part circle by initial sphere, and is stretched at tip portion and induces fluid; The above-mentioned distortion that charged drop takes place and the process of inducing fluid are very fast, before solidifying, can accomplish; The fluid cross-section radius that induces is less, and surface area is bigger, and heat conduction velocity is very fast, and fluid is in case formation just is frozen into nanofiber rapidly.Because method provided by the invention is to induce fluid condensation cured again from charged drop earlier, therefore low-viscosity (mobile) liquid also is suitable for, and has expanded the kind of nanofiber.
The present invention also provides the device of using the method for preparing nanofiber, and corresponding, the device of preparation nanofiber provided by the invention is applicable to the spinning solution of viscosity wider range, has higher applicability.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the deformation sketch map of charged drop under low temperature environment;
Fig. 2 is the structural representation of the device of preparation nanofiber provided by the invention;
Fig. 3 is the microscope picture of the nanofiber of the embodiment of the invention 1 preparation;
Fig. 4 is the embodiment of the invention 2 receiver cavity inner wall photos;
Fig. 5 is the photo of the nanofiber of the embodiment of the invention 3 preparations.
The specific embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of preparation method of nanofiber, comprise the steps:
A), utilize electrostatic spraying that spinning solution is injected into charged drop;
B), said charged drop deforms before solidifying under cryogenic conditions and induces fluid;
C), said fluid condensation cured, obtain nanofiber.
Method provided by the invention is to utilize electrostatic spraying earlier, and fluid jet is become charged fine droplet, makes spinning solution become droplet-like and is with electric charge.
Quick exchange heat takes place with surrounding environment after getting into low temperature environment in charged drop on the one hand that eject; Charged drop receives the effect of electric charge electrostatic repulsion forces on the other hand; The original heat of charged drop, electric equilibrium are destroyed, and stretcher strain takes place under the out-of-balance force effect for it.Referring to shown in Figure 1 be the deformation sketch map of charged drop, the deforming process of charged drop is following:
Charged drop a gradually becomes the fusiform fusiformis charged drop b of middle part circle by initial sphere under the effect of out-of-balance force;
The tip of fusiformis drop b is the charge concentration position, and under the effect of electric charge electrostatic repulsion forces, the point of drop is stretched, and induces fluid c gradually; The above-mentioned distortion that charged drop takes place and the process of inducing fluid are very fast, before charged drop solidifies, can accomplish;
The fluid c section radius that induces is less, and surface area is bigger, and heat conduction velocity is very fast, and fluid is in case formation just is frozen into nanofiber;
The a large amount of electric charges of the fluid removal that ejects, when electric charge in the drop was not enough to keep the stretching of most advanced and sophisticated fluid, drop gradually became spherical droplets d again under capillary effect, and condensation cured becomes the ice particle.
Method provided by the invention is to utilize electrostatic spraying earlier; Fluid jet is become charged fine droplet; Charged drop gets into the rapid and surrounding environment generation energy exchange of low temperature environment immediately, makes drop be in non-equilibrium state, promotes the charged drop distortion; Drop after the distortion induces fluid under the effect of electric charge electrostatic repulsion forces, the fluid condensation cured forms nanofiber.Because method provided by the invention is to induce fluid condensation cured again from the spinning charged drop earlier, therefore low-viscosity (mobile) liquid also is suitable for, and has expanded the kind of nanofiber.
The present invention is a spinning solution with low-viscosity (mobile) liquid under the normal temperature and the low viscosity molten mass under the high temperature preferably; Low-viscosity (mobile) liquid under the normal temperature is preferably water, inorganic salt solution or small organic molecule solution, and the low viscosity molten mass under the high temperature is preferably and is silicon, titanium dioxide, silica.
For being the situation of spinning solution with water, inorganic salt solution and small organic molecule solution, spinning voltage preferably is made as 3～5kV, and condensation temperature preferably is made as-190～-130 ℃.
The present invention also provides a kind of nano-fiber manufacturing apparatus of realizing above-mentioned preparation nanofiber process, referring to shown in Figure 2, is the structural representation of nano-fiber manufacturing apparatus provided by the invention, and nano-fiber manufacturing apparatus provided by the invention comprises:
The static nozzle 2 that links to each other with high voltage source;
With the receiver 3 corresponding with static nozzle 2 positions.
In the above-mentioned receiver 3, the shell 312 preferred containers that adopt insulation shift bottle like liquid nitrogen, and the inner bag 311 preferred material that adopt good heat conductivity are like copper or aluminium.For the cryogenic substance of depositing in the cavity, the present invention preferably adopts liquid nitrogen, dry ice or LPG.Vertical range between shower nozzle 22 and the receiver 3 is preferably 15～70mm.
As preferred version, this device can also comprise the heater that links to each other with static nozzle,, sets up heater and is used for spinning material is heated into the spinning molten mass down for solid-state spinning material for normal temperature.
Advantage based on above-mentioned nanofiber preparation method; Nano-fiber manufacturing apparatus provided by the invention; Applied widely, being particularly suitable for low-viscosity (mobile) liquid or low viscosity molten mass is that spinning solution prepares inorganic nano-fiber or micromolecule organic nanofibers, has enriched the kind of nanofiber thus.
In order further to understand the present invention, below in conjunction with embodiment the device of nanofiber preparation method provided by the invention and preparation nanofiber to be described, protection scope of the present invention is not limited by the following examples.
Following examples all adopt the device of preparation nanofiber as shown in Figure 2, and syringe inner diameter is 20mm in this device, and the internal diameter of spinneret is 0.1mm, and external diameter is 0.5mm, and the cryogenic substance of depositing in the cavity is a liquid nitrogen, and temperature is-190～-130 ℃ in the inner chamber.
The vertical range of regulating between spout and the receiver is 70mm; In liquid storage cylinder, add deionized water, open high voltage source, it is 3.2kV that voltage is set; It is 0.0942mL/min that the interior deionized water injection speed of liquid storage cylinder is set; Collect the nanofiber in the receiver cavity behind the 30min, referring to the microscope picture of the nanofiber for the present embodiment preparation shown in Figure 3, by scheming to know that the fiber of preparing according to the method for present embodiment is a nanoscale.
The vertical range of regulating between spout and the receiver is 30mm, in liquid storage cylinder, adds the LiCl aqueous solution of 4mol/L, opens high voltage source; It is 4.2kV that voltage is set; Be provided with that the injection speed of solution is 0.0628mL/min in the liquid storage cylinder, collect the nanofiber in the receiver cavity behind the 30min, referring to shown in Figure 4 be receiver cavity inner wall photo; Can know by figure, be attached with a large amount of nanofiber c1 in the lower surface of receiver cavity inner wall.
The vertical range of regulating between spout and the receiver is 20mm; The NaCl aqueous solution that in liquid storage cylinder, adds 0.1mol/L; Open high voltage source, it is 3.9kV that voltage is set, and the injection speed that solution in the liquid storage cylinder is set is 0.0471mL/min; Collect the nanofiber in the receiver cavity behind the 30min, referring to the photo of the nanofiber for preparing for present embodiment shown in Figure 5.
The vertical range of regulating between spout and the receiver is 50mm; In liquid storage cylinder, add ethanol water; The volume fraction of ethanol is 1% in the solution, opens high voltage source, and it is 3.15kV that voltage is set; The injection speed that solution in the liquid storage cylinder is set is 0.0942mL/min, collects the nanofiber in the receiver cavity behind the 30min.
Embodiment 5
The vertical range of regulating between spout and the receiver is 30mm; In liquid storage cylinder, add glycol water; The volume fraction of ethylene glycol is 50% in the solution, opens high voltage source, and it is 3.02kV that voltage is set; The injection speed that solution in the liquid storage cylinder is set is 0.0942mL/min, collects the nanofiber in the receiver cavity behind the 30min.
Embodiment 6
The vertical range of regulating between spout and the receiver is 30mm; In liquid storage cylinder, add dimethyl sulphoxide aqueous solution; The volume fraction of dimethyl sulfoxide (DMSO) is 50% in the solution, opens high voltage source, and it is 3.34kV that voltage is set; The injection speed that solution in the liquid storage cylinder is set is 0.0942mL/min, collects the nanofiber in the receiver cavity behind the 30min.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (8)
1. the preparation method of a nanofiber is characterized in that, comprising:
Utilize electrostatic spraying that spinning solution is injected into charged drop;
Said charged drop deforms before solidifying under cryogenic conditions and induces fluid;
Said fluid condensation cured obtains nanofiber.
2. preparation method according to claim 1 is characterized in that, said spinning solution is low-viscosity (mobile) liquid or low viscosity molten mass.
3. preparation method according to claim 2 is characterized in that, said low-viscosity (mobile) liquid is water, inorganic salt solution, small organic molecule liquid.
4. the nanofiber for preparing according to any method of claim 1～3.
5. a nano-fiber manufacturing apparatus is characterized in that, comprising:
High voltage source;
The static nozzle that links to each other with high voltage source;
The receiver corresponding with the static nozzle position is used for the fluid that the condensation cured charged drop induces, and forms nanofiber.
6. nano-fiber manufacturing apparatus according to claim 5 is characterized in that, said receiver comprises: cavity and the cryogenic substance that is arranged at cavity cavity place.
7. nano-fiber manufacturing apparatus according to claim 6 is characterized in that, said cryogenic substance is liquid nitrogen, dry ice or LPG.
8. nano-fiber manufacturing apparatus according to claim 7 is characterized in that, also comprises: with the heater that said static nozzle links to each other, be used for spinning material is heated into the spinning molten mass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110023244.8A CN102453965B (en) | 2011-01-20 | 2011-01-20 | Method and device for preparing nanofibers |
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| CN201110023244.8A CN102453965B (en) | 2011-01-20 | 2011-01-20 | Method and device for preparing nanofibers |
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| CN102453965A true CN102453965A (en) | 2012-05-16 |
| CN102453965B CN102453965B (en) | 2015-04-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274734A (en) * | 2015-11-27 | 2016-01-27 | 陕西师范大学 | Method for preparing three-dimensional micro-nano fiber membrane based on ice balls as templates |
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| US7083854B1 (en) * | 2005-05-10 | 2006-08-01 | Cornell Research Foundation, Inc. | Fibers from polymer nanoclay nanocomposites by electrospinning |
| CN1823184A (en) * | 2003-10-01 | 2006-08-23 | 中国科学院化学研究所 | Electro-blowing technology for fabrication of fibrous articles and its applications of hyaluronan |
| US20080122131A1 (en) * | 2004-06-29 | 2008-05-29 | Cornell Research Foundation, Inc. | Apparatus and method for elevated temperature electrospinning |
| US20100093093A1 (en) * | 2006-12-05 | 2010-04-15 | Nanyang Technological University | Manufacturing three-dimensional scaffolds using electrospinning at low temperatures |
| WO2010112564A1 (en) * | 2009-04-01 | 2010-10-07 | Centro De Estudios E Investigaciones Técnicas De Gipuzkoa | Template-supported method of forming patterns of nanofibers in the electrospinning process and uses of said nanofibers |
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Patent Citations (5)
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| CN1823184A (en) * | 2003-10-01 | 2006-08-23 | 中国科学院化学研究所 | Electro-blowing technology for fabrication of fibrous articles and its applications of hyaluronan |
| US20080122131A1 (en) * | 2004-06-29 | 2008-05-29 | Cornell Research Foundation, Inc. | Apparatus and method for elevated temperature electrospinning |
| US7083854B1 (en) * | 2005-05-10 | 2006-08-01 | Cornell Research Foundation, Inc. | Fibers from polymer nanoclay nanocomposites by electrospinning |
| US20100093093A1 (en) * | 2006-12-05 | 2010-04-15 | Nanyang Technological University | Manufacturing three-dimensional scaffolds using electrospinning at low temperatures |
| WO2010112564A1 (en) * | 2009-04-01 | 2010-10-07 | Centro De Estudios E Investigaciones Técnicas De Gipuzkoa | Template-supported method of forming patterns of nanofibers in the electrospinning process and uses of said nanofibers |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274734A (en) * | 2015-11-27 | 2016-01-27 | 陕西师范大学 | Method for preparing three-dimensional micro-nano fiber membrane based on ice balls as templates |
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Granted publication date: 20150408 Termination date: 20210120 |