CN105332092B - A kind of flexible micro nanometer fiber twisted wire with electromagnetic performance and preparation method thereof - Google Patents
A kind of flexible micro nanometer fiber twisted wire with electromagnetic performance and preparation method thereof Download PDFInfo
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- CN105332092B CN105332092B CN201510853008.7A CN201510853008A CN105332092B CN 105332092 B CN105332092 B CN 105332092B CN 201510853008 A CN201510853008 A CN 201510853008A CN 105332092 B CN105332092 B CN 105332092B
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Abstract
The invention discloses a kind of flexible micro nanometer fiber twisted wire with electromagnetic performance and preparation method thereof, the micro nanometer fiber for being wound in the flexible micro nanometer fiber twisted wire contains photocuring high polymer material, conductive materials and magnetic nanoparticle, the micro nanometer fiber is made by solvent-free electrospinning spinning precursor liquid, electro-spinning process is carried out under few oxygen ultraviolet lighting environment, the spinning precursor liquid contains liquid prepolymer, light trigger, conductive materials and the magnetic nanoparticle of photo-curing material, without organic solvent.The micro nanometer fiber twisted wire has excellent mechanical property, and has good electromagnetic performance, while organic solvent need not be added in electrostatic spinning preparation process, and preparation process more safety and environmental protection is suitable for mass production.
Description
Technical field
The present invention relates to a kind of flexible micro nanometer fiber twisted wire with electromagnetic performance and preparation method thereof, belong to a nanometer material
Expect preparation field.
Background technology
Electrostatic spinning technique is a kind of easy and effective method for preparing micro/nano-fibre, is prepared using electrostatic spinning technique
Nanofiber, the more abundant structure such as twisted wire can be made into, to extend its application.But traditional electrostatic spinning skill
Art, due to most organic solvent can be played in spinning process, cause the very big wasting of resources and environmental pollution, or even some
Organic solvent is also toxic, can damage the health of people.And solvent-free spining technology does not need solvent in spinning process, thus solve
Tradition of having determined has the drawbacks of environment is polluted in solvent spinning.Current solvent-free spinning has melt spinning, heat cure spinning, and UV light is consolidated
Change spinning etc..Material workable for UV photocurings is a lot, and wherein urethane acrylate (PUA) is a kind of ideal ultraviolet
Light-cured resin, it is usually used in coating and adhesive area, its film or fiber after solidifying has the high-wearing feature of polyurethane, adhesion
Power, pliability and excellent resistance to low temperature, it is a kind of radiation curing material of high comprehensive performance.Spun for UV photocurings
Silk is currently limited to Chinese patent (CN104532367A) and has obtained polyurethane micro nanometer fiber by the method for ultra-violet curing, in
State's patent (CN101021017A) has obtained polyurethanes micro nanometer fiber also by the method for ultra-violet curing, but it needs and lived
Property diluent be used in mixed way according to certain ratio, precursor liquid prepares cumbersome, and the fiber for preparing is universal shorter and not
Rule, solidification are incomplete, and length maximum is 1 centimetre, and toughness is poor, it is impossible to the more complicated structure such as twisted wire is processed to,
And these fibers do not possess electric conductivity, the application of material is limited.Obtained by the solvent-free electrospinning of ultra-violet curing
Have excellent mechanical property concurrently, the micro nanometer fiber of electromagnetic performance has not been reported both at home and abroad.
The content of the invention
The purpose of the present invention overcomes prior art insufficient, a kind of remedy technology blank, there is provided flexibility with electromagnetic performance
Micro nanometer fiber twisted wire and preparation method thereof, the micro nanometer fiber twisted wire has excellent mechanical property, and has good electricity
Magnetic property, while organic solvent need not be added in electrostatic spinning preparation process, preparation process more safety and environmental protection, suitable big rule
Mould produces.
To achieve these goals, technical scheme provided by the invention is as follows：
A kind of flexible micro nanometer fiber twisted wire with electromagnetic performance, is wound in the micro- of the flexible micro nanometer fiber twisted wire
Nanofiber contains photocuring high polymer material, conductive materials and magnetic nanoparticle, and the micro nanometer fiber passes through solvent-free
Electrospinning spinning precursor liquid is made, and electro-spinning process is carried out under few oxygen ultraviolet lighting environment, and the spinning precursor liquid contains photocuring
Liquid prepolymer, light trigger, conductive materials and the magnetic nanoparticle of material, without organic solvent.
The flexible micro nanometer fiber of the present invention is under few oxygen environment, and using electrostatic spinning technique, light is used as using ultraviolet light
Source, trigger the photocuring prepolymer rapid polymerization with chemical reactivity, while occur with the splitting of fiber, generate solid-state
Micro nanometer fiber, whole process organic solvent-free participates in, non-volatility organic compound VOC emission, safety and environmental protection, suitable rule
Modelling produces, and under few oxygen environment, oxygen inhibition phenomenon unobvious, photo-curing material polymerization is complete, gained micro nanometer fiber it is longer and
Rule is homogeneous, and pliability is good, and twisted wire is made by this fiber, makes the flexible micro nanometer fiber twisted wire of gained that there is excellent stretching to return
Renaturation energy, it is wound in the fiber of twisted wire and is uniformly distributed this conductive materials and magnetic nanoparticle so that the twisted wire has good
Electromagnetic performance, available for preparing optics, electronic device etc..
Further, the flexible micro nanometer fiber twisted wire has magnetic, and electrical conductivity is 10 in its natural state-4S/cm
The order of magnitude.
Further, the maximum tension rate of the flexible micro nanometer fiber twisted wire is more than or equal to 200%.Described extensibility
Calculation formula be：
A kind of preparation method of the flexible micro nanometer fiber twisted wire with electromagnetic performance, comprises the following steps：
(1) spinning precursor liquid is configured：The liquid prepolymer of photo-curing material and light trigger, conductive materials, magnetic are received
Rice grain is well mixed under light protected environment, then standing makes its pre-polymerization under natural light environment, obtains spinning precursor liquid；
(2) twisted wire is prepared：The spinning precursor solution that step (1) is matched somebody with somebody is placed in the electrostatic for preparing orderly micro nanometer fiber
In the liquid storage mechanism of device for spinning connection spinning nozzle, and the spinning nozzle of the electrostatic spinning apparatus and collector are placed in less
Electrospinning, the collection of the jet and electrostatic spinning apparatus that are sprayed in electro-spinning process with ultraviolet source to spinning nozzle are carried out under oxygen environment
Pole is irradiated, and collects the micro nanometer fiber of ordered arrangement on collector, and the twisted wire for being wound in even thickness is produced and had
The flexible micro nanometer fiber twisted wire of electromagnetic performance.
It has been recognised by the inventors that prepared by method of electrostatic spinning, the solidification of UV curing materials micro nanometer fiber is incomplete, fiber is generally shorter
And irregular reason is：Electrostatic spinning is used it for preparing photocuring material as a kind of method for preparing micro nanometer fiber
Expect micro nanometer fiber, its obtained micro nanometer fiber has the characteristics of specific surface area is big, and this fibre morphology increases prepolymer
With the contact area of oxygen, it is contacted with the oxygen in air more abundant, be exaggerated UV curing materials in the curing process
Oxygen inhibition phenomenon effect, the polymerizing curable of prepolymer is hindered, so as to cause the micro-nano fibre of obtained photo-curing material
Dimension solidification is incomplete, poor toughness, fiber are generally shorter and irregular, have impact on large-scale production and the application prospect of fiber.This
The preparation method of invention, the progress electro-spinning process under the low few oxygen environment of oxygen concentration is selected to prepare micro nanometer fiber, in spinning
During, pre-polymer solution sprays to form jet under action of high voltage from spinneret, and the light trigger in jet absorbs ultraviolet
The energy of light and produce living radical, living radical trigger prepolymer occur polymerisation, jet fall during companion
There is the splitting of fiber, polymer micro-nanometer fiber is finally formed on collector, so as to realize solvent-free electrostatic spinning.Few oxygen
Spinning environment, the oxygen inhibition phenomenon in electrostatic spinning is effectively prevent, it is regular and continuous so as to which completion of cure, form largely be made
Micro nanometer fiber, and organic solvent-free participates in spinning process, and environment caused by effectively prevent organic solvent volatilization is dirty
Dye, safety and environmental protection, this method are applied to the scale industrial production of photo-curing material micro nanometer fiber.
The photo-curing material of the step (1) is urethane acrylate, epoxy acrylate, polyether acrylate, poly-
One or more in ester acrylate, acrylic resin；The conductive materials are polyaniline, polypyrrole, poly- (3,4- ethylenes two
Oxygen thiophene), polythiophene, poly- (3- hexyl thiophenes), polyacetylene, poly- to styrene, polyphenylene sulfide, polyphenylacetylene, graphene, carbon
One or more in nanotube, metal nanoparticle etc.；The magnetic nanoparticle is γ-Fe2O3、Fe3O4, cobalt, nickel magnetic
The one or more of nano particle or composite magnetic nano particle, the composite magnetic nano particle contain one in iron, cobalt, nickel
Kind is a variety of.
Further, the photo-curing material of the step (1) is urethane acrylate, the light trigger and polyurethane
The mass ratio of acrylate is 1:10~30, the standing pre-polymerization time of the step (1) is 1~2 day.
In numerous photo-curing materials, urethane acrylate (PUA) is a kind of ideal UV-cured resin,
Be usually used in coating and adhesive area, its film or fiber after solidifying have the high-wearing feature of polyurethane, adhesion, pliability,
The optical property and weatherability of high-peeling strength and excellent resistance to low temperature and polyacrylate brilliance, it is a kind of comprehensive
The excellent radiation curing material of energy.The various acrylates used as coating and adhesive, it is easy to carry out polymerisation in bulk,
Oxygen inhibition phenomenon is easier to overcome.
Further, step (1) prepares spinning precursor liquid：The urethane acrylate of 8 grams of addition in conical flask, 0.4
Gram Liquid photoinitiators, and 2 grams of polyaniline powders, 0.3 gram of ferric oxide powder carry out shading stirring with agitator, uses
40~50 degree of heating water baths, stir 2~3 hours, make it well mixed, stand 1~2 day at room temperature, spinning precursor liquid is made.
Further, few oxygen environment of the step (2) is less than 5% spinning environment, the step (2) for oxygen concentration
The spinning voltage of electro-spinning process be 10~30 kilovolts, spinning distance is 5~50 centimetres, and the power of ultraviolet source is 300~500
Watt.
Further, the electrostatic spinning apparatus in the step (2) include high voltage power supply, liquid storage mechanism, spinning nozzle, every
Oxygen mechanism, ultraviolet source and roller collector, the high-voltage power cathode connect spinning nozzle, spinning nozzle connection storage spinning
The liquid storage mechanism of precursor liquid, the roller collector connect high voltage power supply negative pole or are directly grounded, and the oxygen barrier mechanism includes close
Joint sealing, spinning nozzle and the roller collector are located in seal box, ultraviolet source be located in seal box or its transmitting it is ultraviolet
Light can be injected in seal box, and ultraviolet source can irradiate spinning nozzle and roller collects interelectrode space, be set on the seal box
There are air inlet and gas outlet, the air inlet connects gas source, and the gas source is source nitrogen, carbon dioxide source or inert gas
Source, is additionally provided with the seal box and hinders gas to be directly blown into the baffle plate in case, and the baffle plate is located at air inlet and collector
Between, the shadow shield for preventing the jet at ultraviolet light direct irradiation spinning nozzle ejection end, institute are provided with the seal box
Shadow shield is stated between ultraviolet source and spinning nozzle ejection end, presses close to the setting of spinning nozzle ejection end, the roller is collected
The collection cylinder of pole docks linkage with the output shaft of DC brushless motor, in the output shaft of collection cylinder and DC brushless motor
Mandrel line coincides, the electric machine controller of DC brushless motor electric connection of power supply and controlled motor rotating speed.
The device is provided with oxygen barrier mechanism, need to first open oxygen barrier mechanism during the device use, reduce oxygen in seal box
Concentration, to build the spinning environment of few oxygen, solvent-free spinning precursor liquid is then injected into liquid storage mechanism again, opens ultraviolet source
And high voltage power supply, electrostatic spinning is carried out under few oxygen oxygen atmosphere, can effectively overcome oxygen inhibition phenomenon to photo-curing material micro-nano
The influence of rice fiber forming process.
In order to eliminate environmental pollution caused by organic solvent volatilization in conventional electrostatic spinning and be unfavorable for large-scale commercial applications life
The problem of production, design under few oxygen environment that nitrogen or two sample carbon, inert gas are built, using electrostatic spinning technique, with
Ultraviolet light triggers the acrylic ester prepolymer with chemical reactivity to be rapidly converted into the micro-/ nano fibre of solid-state as light source
Dimension, because raw material all in spinning precursor liquid both participates in polymerisation, realizes solvent-free electrostatic spinning.And received by roller
Collector obtains the relatively regular micro nanometer fiber of longer aligned orderly, good toughness, diameter, because gained fiber has enough length
Degree, toughness and homogeneity, can be made into the preferable twisted wire structure of pattern, make it have excellent extension recovery performance.
Further, the step (2) uses internal diameter first to be opened for 8~12 millimeters of airway tube before electro-spinning process starts
Open gas source and be passed through gas into seal box, cubic millimeter/second of gas flow rate 3~9, reach oxygen concentration in case to be sealed and be less than
Electrostatic spinning apparatus is then turned on after 5% few oxygen environment and opens spinning, the spacing of spinning nozzle to collection cylinder is 5~50 lis
Rice, 3~8 centimetres of collection cylinder radius, it is 70~200 revs/min that DC brushless motor, which drives the rotating speed of roller rotation, ultraviolet source
It it is 15~20 centimetres to collection cylinder distance, the spinning time is 3~10 minutes.
Beneficial effects of the present invention are：Prior art deficiency is overcome, compensate for technological gap, there is provided one kind has electricity
Flexible micro nanometer fiber twisted wire of magnetic property and preparation method thereof, the micro nanometer fiber twisted wire have excellent mechanical property, and
With good electromagnetic performance, while organic solvent need not be added in electrostatic spinning preparation process, preparation process is safer
Environmental protection, matters large-scale production.Specifically：
(1) it is compound micro- to prepare photo-curing material for this method selection progress electro-spinning process under the low few oxygen environment of oxygen concentration
Nanofiber, in spinning process, the spinning precursor liquid of prepolymer containing photo-curing material, conductive materials and magnetic nanoparticle exists
Under action of high voltage, sprayed from spinneret, formation jet, the light trigger in jet absorbs the energy of ultraviolet light and produces activity
Free radical, living radical trigger prepolymer occur polymerisation, jet fall during with fiber splitting, finally exist
Polymer micro-nanometer fiber is formed on collector, so as to realize solvent-free electrostatic spinning.The spinning environment of few oxygen, effectively prevent
It is good so as to which completion of cure, pliability largely be made in the oxygen inhibition phenomenon of electrostatic spinning, form rule and continuous photocuring material
Expect micro nanometer fiber, twisted wire is made by this fiber, enable gained micro nanometer fiber twisted wire that there is excellent stretch recovery, and
With good electromagnetic performance, electrical conductivity is 10 in its natural state-4The S/cm orders of magnitude, the flexible micro nanometer fiber twisted wire is most
Big extensibility is up to more than 200%.
(2) collected using roller, the fiber ordered arrangement degree of collection is high, and the twisted wire structure and morphology of preparation is good.Using poly-
Twisted wire prepared by urethane acrylate has special mechanical property (flexible, impact resistance), is being doped with conductive materials and magnetic
After property particle, be obviously improved its electromagnetic performance, can be applied to the stealthy and energy absorbing material of electromagnetic wave, anti-static material,
The fields such as absorbing material, micromechanical component, sensor, electrode material, biochemical reaction catalyst.Simply, easily grasped with more equipment
Make, it is reproducible and be easy to promote the advantages that, especially have broad application prospects on military affairs, Aero-Space, anti-harmful material.It is real
Test is taken temperature bright, and the nano fiber twisted prepared by this method has a good electric conductivity, and its have it is anti-oxidant and
The advantages that corrosion resistance is good.
(3) precursor liquid used in spinning process is free of other organic solvents, and the utilization rate of raw material can reach 100%, nothing
It is VOC VOC emission, environment-friendly.
(4) preparation method of the flexible micro nanometer fiber twisted wire is simple, equipment is easy to operate, it is reproducible, be easy to promote.
Brief description of the drawings
Fig. 1 is the structural representation for the electrostatic spinning apparatus that embodiment 1 to 4 uses.
PANI/PUA/Fe prepared by Fig. 2 embodiments 12O3The stereoscan photograph of composite micro-nano rice fiber strands.
PANI/PUA/Fe prepared by Fig. 3 embodiments 12O3The hysteresis curve of composite micro-nano rice fiber strands.
In Fig. 1,1- high voltage power supplies, 2- ultraviolet sources, 3- gas cylinders, 31- gas cylinder pressure-reducing valves, 4- DC brushless motors, 41- electricity
Machine controller, 5- air inlets, 6- gas outlets, 7 collection cylinders, 8- spinning nozzles, 9- baffle plates, 10- shadow shields, 11- airway tubes,
12- liquid storage mechanisms, 13- wires, 14- seal boxs.
Embodiment
According to following embodiments, the present invention may be better understood.It is however, as it will be easily appreciated by one skilled in the art that real
Apply specific material proportion, process conditions and its result described by example be merely to illustrate the present invention without should also without limitation on
The present invention described in detail in claims.
Electrostatic spinning apparatus used in the embodiment of the present invention 1 to 4 is as shown in figure 1, including high voltage power supply 1, liquid storage mechanism
12nd, spinning nozzle 8, oxygen barrier mechanism, ultraviolet source 2 and collector, the positive pole of high voltage power supply 1 connect spinning nozzle 8, spinning spray
The liquid storage mechanism 12 of first 8 connection storage spinning precursor liquid, the liquid storage mechanism 12 is plastic injector needle tubing, and the collector connects
The negative pole of high voltage power supply 1 is connect, the oxygen barrier mechanism includes the seal box 14 of internal anaerobic or few oxygen, the spinning nozzle 8 and collection
Pole is located in seal box 14, and ultraviolet source 2 is located at outside seal box 14, and its ultraviolet light launched can be injected in seal box 14, purple
Outer light source 2 can be irradiated between spinning nozzle 8 and collector；Air inlet 5 is provided with the seal box 14 of the oxygen barrier mechanism and is gone out
Gas port 6, the seal box 14 are lucite case, and air inlet 5 and gas outlet 6 are separately positioned on two relative sides of seal box 14
On wall, the air inlet 5 connects gas source, and the gas source is gas cylinder 3, and the gas cylinder 3 of embodiment 1 is interior filled with nitrogen, described close
Be additionally provided with joint sealing 14 and hinder nitrogen to be directly blown into baffle plate 9 in case, the baffle plate 9 between air inlet 5 and collector,
Collection extremely roller collector, the collection cylinder 7 of the roller collector docks connection with the output shaft of DC brushless motor 4
Dynamic, the central axis of the output shaft of collection cylinder 7 and DC brushless motor 4 coincides, the electric connection of power supply of DC brushless motor 4 and
The electric machine controller 41 of controlled motor rotating speed, being provided with the seal box 14 prevents ultraviolet light direct irradiation spinning nozzle 8
The shadow shield 10 of jet at ejection end, the shadow shield 10 are located between ultraviolet source 2 and the ejection end of spinning nozzle 8, pressed close to
The ejection end of spinning nozzle 8 is set.
Embodiment 1
A kind of flexible micro nanometer fiber twisted wire with electromagnetic performance, comprises the following steps：
(1) spinning precursor liquid is configured：8 grams of urethane acrylate (DR-U301, Changxing chemical industry is added in conical flask
Industry Stock Company (Taiwan)), 0.4 gram of Liquid photoinitiators (photoinitiator 1173,2- hydroxy-2-methyl -1-
Phenyl -1- acetone, Aldrich), and 2 grams of polyaniline powders (PANI, average molecular weight Mws>15,000, Aladdin), 0.3 gram
Ferric oxide powder carries out shading stirring with agitator, using 40 degree of heating water baths, stirs 3 hours, makes light trigger, poly- ammonia
Ester acrylate, polyaniline and di-iron trioxide are well mixed, and stand 1 day at room temperature, urethane acrylate is occurred one
Determine the pre-polymerization in degree, spinning precursor liquid is made；
(2) twisted wire is prepared：The spinning precursor liquid that step (1) prepares is poured into the aluminum spinneret that internal diameter is 1.2 centimetres
In, 2 millimeters of spinneret tip size, nitrogen is passed through into closed casing, cubic millimeter/second of nitrogen flow rate 9, is passed through 3 minutes
After reach and carry out electrostatic spinning after oxygen barrier effect again, the distance of spinneret to roller collector is 12 centimetres, spinning voltage 22,000
Volt, 90 revs/min of motor speed, with 300 watts of ultraviolet source power, the fiber sprayed to spinneret is irradiated, and ultraviolet source arrives
It is 15 centimetres that roller, which collects distance, and by 10 minutes, the continuous P ANI/PUA/ of aligned orderly is collected on roller collector
Fe2O3Micro nanometer fiber, wound and twisted wire is made, the flexible micro nanometer fiber twisted wire as with electromagnetic performance, it scans electricity
Mirror photo is as shown in Figure 2.
The maximum tension rate for calculating the flexible micro nanometer fiber twisted wire after tested is 200%, and electrical conductivity is 2.4 × 10-4S/
cm.Fig. 3 is the hysteresis curve of the flexible micro nanometer fiber twisted wire of embodiment 1, and hysteresis curve test shows, is prepared by this method
Nano fiber twisted there is good magnetic performance.
Embodiment 2
A kind of flexible micro nanometer fiber twisted wire with electromagnetic performance, comprises the following steps：
(1) spinning precursor liquid is configured：8 grams of urethane acrylate (DR-U301, Changxing chemical industry is added in conical flask
Industry Stock Company (Taiwan)), 0.4 gram of Liquid photoinitiators (photo initiator 1173,2- hydroxy-2-methyl -1-
Phenyl -1- acetone, Aldrich), 2g ferroferric oxide powders (Aladdin), and 1 gram of PEDOT solution (Aladdin), with stirring
Device carries out shading stirring, using 50 degree of heating water baths, stirs 1 hour, mixes light trigger, urethane acrylate and polyaniline
Close uniformly, stand 2 days at room temperature, make the pre-polymerization of urethane acrylate generation to a certain extent, it is molten that spinning presoma is made
Liquid；
(2) twisted wire is prepared：The spinning precursor liquid prepared is poured into the aluminum spinneret that internal diameter is 1.2 centimetres, spinneret
Sharp-tongued 3 millimeters of end size, is passed through nitrogen into closed casing, cubic millimeter/second of nitrogen flow rate 3, reach after being passed through 5 minutes every
Electrostatic spinning is carried out after oxygen effect again, the distance of spinneret to roller collector is 10 centimetres, and 30 kilovolts of spinning voltage, motor turns
100 revs/min of speed, with 400 watts of ultraviolet source power, the fiber sprayed to spinneret is irradiated, and ultraviolet source to roller is collected
Distance is 20 centimetres, and by 3 minutes, the continuous P EDOT/PUA/Fe of aligned orderly is collected on roller collector3O4It is micro-nano
Fiber, wound and twisted wire is made, the flexible micro nanometer fiber twisted wire as with electromagnetic performance.
The maximum tension rate for calculating the flexible micro nanometer fiber twisted wire after tested is 320%, and electrical conductivity is 4.6 × 10-4S/
cm。
Embodiment 3
A kind of flexible micro nanometer fiber twisted wire with electromagnetic performance, comprises the following steps：
(1) spinning precursor liquid is configured：8 grams of polyester acrylate (CN750, Sartomer (Guangzhou) is added in conical flask
Chemical Co., Ltd.), 0.4 gram of Liquid photoinitiators (photoinitiator 1173,2- hydroxy-2-methyl -1- phenyl -1-
Acetone, Aldrich), 0.5g cobalt powders and 0.1 gram of graphene solution (Aladdin), shading stirring is carried out with agitator, using 45
Heating water bath is spent, stirs 1.5 hours, is well mixed light trigger, urethane acrylate and graphene, in room temperature natural light
1.5 days are stood under line, the pre-polymerization that polyester acrylate occurs to a certain extent is obtained precursor solution；
(2) twisted wire is prepared：The spinning precursor liquid that step (1) prepares is poured into the aluminum spinneret that internal diameter is 1.2 centimetres
In, 2.5 millimeters of spinneret tip size, nitrogen is passed through into closed casing, cubic millimeter/second of nitrogen flow rate 5, is passed through 4 points
Electrostatic spinning is carried out again after reaching oxygen barrier effect after clock, and the distance of spinneret to roller collector is 5 centimetres, spinning voltage 10,000
Volt, 100 revs/min of motor speed, with 500 watts of ultraviolet source power, the fiber sprayed to spinneret is irradiated, and ultraviolet source arrives
It is 17 centimetres that roller, which collects distance, and by 7 minutes, the continuous Graphene/ of aligned orderly is collected on roller collector
PUA/Co micro nanometer fibers, wound and twisted wire is made, the flexible micro nanometer fiber twisted wire as with electromagnetic performance.
The maximum tension rate for calculating the flexible micro nanometer fiber twisted wire after tested is 280%, and electrical conductivity is 3.3 × 10-4S/
cm。
Embodiment 4
A kind of flexible micro nanometer fiber twisted wire with electromagnetic performance, comprises the following steps：
(1) spinning precursor liquid is configured：8 grams of urethane acrylate (DR-U301, Changxing chemical industry is added in conical flask
Industry Stock Company (Taiwan)), 0.4 gram of Liquid photoinitiators (photoinitiator 1173,2- hydroxy-2-methyl -1-
Phenyl -1- acetone, Aldrich), 0.3g grams of ferric oxide powder and 5 grams of carbon nanotube powders (Aladdin), use agitator
Shading stirring is carried out, using 45 degree of heating water baths, stirs 5 hours, mixes light trigger, urethane acrylate and CNT
Close uniformly, stand 2 days at room temperature, make the pre-polymerization of urethane acrylate generation to a certain extent, it is molten that spinning presoma is made
Liquid；
(2) twisted wire is prepared：The spinning precursor liquid prepared is poured into the aluminum spinneret that internal diameter is 0.8 centimetre, spinneret
Sharp-tongued 3 millimeters of end size, is passed through nitrogen into closed casing, cubic millimeter/second of nitrogen flow rate 4, reach after being passed through 5 minutes every
Electrostatic spinning is carried out after oxygen effect again, the distance of spinneret to roller collector is 50 centimetres, and 24 kilovolts of spinning voltage, motor turns
70 revs/min of speed, with 300 watts of ultraviolet source power, the fiber sprayed to spinneret is irradiated, ultraviolet source to roller collection away from
From for 16 centimetres, by 7 minutes, the continuous CNTs/PUA/Fe of aligned orderly is collected on roller collector2O3Micro-nano fibre
Dimension, is wound and twisted wire is made, the flexible micro nanometer fiber twisted wire as with electromagnetic performance.
The maximum tension rate for calculating the flexible micro nanometer fiber twisted wire after tested is 260%, and electrical conductivity is 1.6 × 10-4S/
cm。
It is described above, it is only the explanation embodiment of the present invention, formal and substantial limitation not any to the present invention,
It should be pointed out that for those skilled in the art, on the premise of the inventive method is not departed from, that makes some changes
Enter and supplement and also should be regarded as protection scope of the present invention, the place of not elaborating not is known in those skilled in the art to the present invention
Prior art, all those skilled in the art, without departing from the spirit and scope of the present invention, utilize above institute
The equivalent variations for a little variation, modification and evolution that the technology contents of announcement are made, it is the equivalent embodiment of the present invention；Together
When, the variation, modification and evolution for any equivalent variations that all substantial technologicals according to the present invention are done to above-described embodiment, still
Belong to the scope of technical scheme.
Claims (9)
1. a kind of flexible micro nanometer fiber twisted wire with electromagnetic performance, it is characterised in that be wound in the micro-nano fibre of flexibility
The micro nanometer fiber of dimension twisted wire contains photocuring high polymer material, conductive materials and magnetic nanoparticle, the micro nanometer fiber
Be made by solvent-free electrospinning spinning precursor liquid, the spinning precursor liquid by photocuring high polymer material prepolymer, light trigger,
Conductive materials, magnetic nanoparticle, which directly mix, to be made, and electro-spinning process is carried out under few oxygen ultraviolet lighting environment, the spinning
Silk precursor liquid contains liquid prepolymer, light trigger, conductive materials and the magnetic nanoparticle of photo-curing material, without organic molten
Agent；The preparation method of the described flexible micro nanometer fiber twisted wire with electromagnetic performance comprises the following steps：
(1) spinning precursor liquid is configured：The urethane acrylate of 8 grams of addition in conical flask, 0.4 gram of Liquid photoinitiators,
With 2 grams of polyaniline powders, 0.3 gram of ferric oxide powder carries out shading stirring with agitator, using 40~50 degree of heating water baths,
Stirring 2~3 hours, make it well mixed, stand 1~2 day at room temperature, spinning precursor liquid is made；
(2) twisted wire is prepared：The spinning precursor solution that step (1) is matched somebody with somebody is placed in the electrostatic spinning for preparing orderly micro nanometer fiber
In the liquid storage mechanism of device connection spinning nozzle, and the spinning nozzle of the electrostatic spinning apparatus and collector are placed in few oxygen ring
Electrospinning is carried out under border, the jet and the collector of electrostatic spinning apparatus sprayed in electro-spinning process with ultraviolet source to spinning nozzle enters
Row irradiation, collects the micro nanometer fiber of ordered arrangement on collector, and the twisted wire for being wound in even thickness is produced with electromagnetism
The flexible micro nanometer fiber twisted wire of performance.
2. a kind of flexible micro nanometer fiber twisted wire with electromagnetic performance, it is characterised in that be wound in the micro-nano fibre of flexibility
The micro nanometer fiber of dimension twisted wire contains photocuring high polymer material, conductive materials and magnetic nanoparticle, the micro nanometer fiber
Be made by solvent-free electrospinning spinning precursor liquid, the spinning precursor liquid by photocuring high polymer material prepolymer, light trigger,
Conductive materials, magnetic nanoparticle, which directly mix, to be made, and electro-spinning process is carried out under few oxygen ultraviolet lighting environment, the spinning
Silk precursor liquid contains liquid prepolymer, light trigger, conductive materials and the magnetic nanoparticle of photo-curing material, without organic molten
Agent；The preparation method of the described flexible micro nanometer fiber twisted wire with electromagnetic performance comprises the following steps：
(1) spinning precursor liquid is configured：The urethane acrylate of 8 grams of addition in conical flask, 0.4 gram of Liquid photoinitiators,
2g ferroferric oxide powders and 1 gram of PEDOT solution, shading stirring is carried out with agitator, small using 50 degree of heating water baths, stirring 1
When, light trigger, urethane acrylate and ferroferric oxide powder, PEDOT solution are well mixed, stands 2 at room temperature
My god, make the pre-polymerization of urethane acrylate generation to a certain extent, spinning precursor solution is made；
(2) twisted wire is prepared：The spinning precursor solution that step (1) is matched somebody with somebody is placed in the electrostatic spinning for preparing orderly micro nanometer fiber
In the liquid storage mechanism of device connection spinning nozzle, and the spinning nozzle of the electrostatic spinning apparatus and collector are placed in few oxygen ring
Electrospinning is carried out under border, the jet and the collector of electrostatic spinning apparatus sprayed in electro-spinning process with ultraviolet source to spinning nozzle enters
Row irradiation, collects the micro nanometer fiber of ordered arrangement on collector, and the twisted wire for being wound in even thickness is produced with electromagnetism
The flexible micro nanometer fiber twisted wire of performance.
3. a kind of flexible micro nanometer fiber twisted wire with electromagnetic performance, it is characterised in that be wound in the micro-nano fibre of flexibility
The micro nanometer fiber of dimension twisted wire contains photocuring high polymer material, conductive materials and magnetic nanoparticle, the micro nanometer fiber
Be made by solvent-free electrospinning spinning precursor liquid, the spinning precursor liquid by photocuring high polymer material prepolymer, light trigger,
Conductive materials, magnetic nanoparticle, which directly mix, to be made, and electro-spinning process is carried out under few oxygen ultraviolet lighting environment, the spinning
Silk precursor liquid contains liquid prepolymer, light trigger, conductive materials and the magnetic nanoparticle of photo-curing material, without organic molten
Agent；The preparation method of the described flexible micro nanometer fiber twisted wire with electromagnetic performance comprises the following steps：
(1) spinning precursor liquid is configured：The polyester acrylate of 8 grams of addition in conical flask, 0.4 gram of Liquid photoinitiators,
0.5g cobalt powders and 0.1 gram of graphene solution, shading stirring is carried out with agitator, using 45 degree of heating water baths, is stirred 1.5 hours,
Light trigger, urethane acrylate and cobalt powder, graphene are well mixed, 1.5 days is stood under room temperature available light, makes to gather
The pre-polymerization that ester acrylate occurs to a certain extent obtains precursor solution；
(2) twisted wire is prepared：The spinning precursor solution that step (1) is matched somebody with somebody is placed in the electrostatic spinning for preparing orderly micro nanometer fiber
In the liquid storage mechanism of device connection spinning nozzle, and the spinning nozzle of the electrostatic spinning apparatus and collector are placed in few oxygen ring
Electrospinning is carried out under border, the jet and the collector of electrostatic spinning apparatus sprayed in electro-spinning process with ultraviolet source to spinning nozzle enters
Row irradiation, collects the micro nanometer fiber of ordered arrangement on collector, and the twisted wire for being wound in even thickness is produced with electromagnetism
The flexible micro nanometer fiber twisted wire of performance.
4. a kind of flexible micro nanometer fiber twisted wire with electromagnetic performance, it is characterised in that be wound in the micro-nano fibre of flexibility
The micro nanometer fiber of dimension twisted wire contains photocuring high polymer material, conductive materials and magnetic nanoparticle, the micro nanometer fiber
Be made by solvent-free electrospinning spinning precursor liquid, the spinning precursor liquid by photocuring high polymer material prepolymer, light trigger,
Conductive materials, magnetic nanoparticle, which directly mix, to be made, and electro-spinning process is carried out under few oxygen ultraviolet lighting environment, the spinning
Silk precursor liquid contains liquid prepolymer, light trigger, conductive materials and the magnetic nanoparticle of photo-curing material, without organic molten
Agent；The preparation method of the described flexible micro nanometer fiber twisted wire with electromagnetic performance comprises the following steps：
(1) spinning precursor liquid is configured：The urethane acrylate of 8 grams of addition in conical flask, 0.4 gram of Liquid photoinitiators,
0.3g grams of ferric oxide powder and 5 grams of carbon nanotube powders, shading stirring is carried out with agitator, using 45 degree of heating water baths,
Stirring 5 hours, is well mixed light trigger, urethane acrylate and di-iron trioxide, CNT, stands at room temperature
2 days, make the pre-polymerization of urethane acrylate generation to a certain extent, spinning precursor solution is made；
(2) twisted wire is prepared：The spinning precursor solution that step (1) is matched somebody with somebody is placed in the electrostatic spinning for preparing orderly micro nanometer fiber
In the liquid storage mechanism of device connection spinning nozzle, and the spinning nozzle of the electrostatic spinning apparatus and collector are placed in few oxygen ring
Electrospinning is carried out under border, the jet and the collector of electrostatic spinning apparatus sprayed in electro-spinning process with ultraviolet source to spinning nozzle enters
Row irradiation, collects the micro nanometer fiber of ordered arrangement on collector, and the twisted wire for being wound in even thickness is produced with electromagnetism
The flexible micro nanometer fiber twisted wire of performance.
5. a kind of flexible micro nanometer fiber twisted wire with electromagnetic performance as any one of Claims 1-4, its feature
It is, the flexible micro nanometer fiber twisted wire has magnetic, and electrical conductivity is 10 in its natural state-4The S/cm orders of magnitude.
6. a kind of flexible micro nanometer fiber twisted wire with electromagnetic performance as any one of Claims 1-4, its feature
It is, the maximum tension rate of the flexible micro nanometer fiber twisted wire is more than or equal to 200%.
7. a kind of flexible micro nanometer fiber twisted wire with electromagnetic performance as any one of Claims 1-4, its feature
It is, few oxygen environment of the step (2) is less than 5% spinning environment for oxygen concentration, the electro-spinning process of the step (2)
Spinning voltage is 10~30 kilovolts, and spinning distance is 5~50 centimetres, and the power of ultraviolet source is 300~500 watts.
8. a kind of flexible micro nanometer fiber twisted wire with electromagnetic performance as any one of Claims 1-4, its feature
It is, the electrostatic spinning apparatus in the step (2) includes high voltage power supply, liquid storage mechanism, spinning nozzle, oxygen barrier mechanism, ultraviolet
Light source and roller collector, the high-voltage power cathode connect spinning nozzle, the storage of spinning nozzle connection storage spinning precursor liquid
Liquid mechanism, the roller collector connect high voltage power supply negative pole or are directly grounded, and the oxygen barrier mechanism includes seal box, the spinning
Silk shower nozzle and roller collector be located in seal box, ultraviolet source be located at that seal box is interior or its ultraviolet light launched can inject it is close
In joint sealing, ultraviolet source can irradiate spinning nozzle and roller collects interelectrode space, and air inlet is provided with the seal box and is gone out
Gas port, the air inlet connect gas source, and the gas source is source nitrogen, carbon dioxide source or inert gas source, the sealing
It is additionally provided with case and hinders gas to be directly blown into the baffle plate in case, the baffle plate is described close between air inlet and collector
Being provided with joint sealing prevents the shadow shield of the jet at ultraviolet light direct irradiation spinning nozzle ejection end, and the shadow shield is located at
Between ultraviolet source and spinning nozzle ejection end, press close to the setting of spinning nozzle ejection end, the collection cylinder of the roller collector
Linkage is docked with the output shaft of DC brushless motor, collection cylinder is mutually overlapping with the central axis of the output shaft of DC brushless motor
Close, the electric machine controller of DC brushless motor electric connection of power supply and controlled motor rotating speed.
A kind of 9. flexible micro nanometer fiber twisted wire with electromagnetic performance as claimed in claim 8, it is characterised in that the step
Suddenly (2) use internal diameter first to open gas source for 8~12 millimeters of airway tube and be passed through into seal box before electro-spinning process starts
Gas, cubic millimeter/second of gas flow rate 3~9, it is then turned on after few oxygen environment of the oxygen concentration less than 5% is reached in case to be sealed
Electrostatic spinning apparatus opens spinning, and the spacing of spinning nozzle to collection cylinder is 5~50 centimetres, 3~8 lis of collection cylinder radius
Rice, DC brushless motor drive roller rotation rotating speed be 70~200 revs/min, ultraviolet source to collection cylinder distance be 15~
20 centimetres, the spinning time is 3~10 minutes.
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| CN105862156B (en) * | 2016-05-27 | 2018-05-08 | 北京林业大学 | A kind of cellulose/hydroxyl multi-walled carbon nano-tube/Fe3O4Nano-particles reinforcement fiber and preparation method thereof |
| CN107574493B (en) * | 2017-07-25 | 2020-04-10 | 青岛农业大学 | Flexible tensile strain sensor of spiral winding structure based on electrospinning |
| CN107904676B (en) * | 2017-12-05 | 2020-05-29 | 青岛大学 | Double-component reaction curing type solvent-free electrospinning device |
| CN108707976A (en) * | 2018-04-09 | 2018-10-26 | 南京捷纳思新材料有限公司 | A kind of the microfluid device for spinning and technique of solvent-free spinning |
| CN109023723B (en) * | 2018-09-10 | 2020-12-11 | 中原工学院 | Method for applying photocuring technology to electrostatic spinning |
| CN109403019B (en) * | 2018-09-30 | 2021-02-12 | 河南工程学院 | Method for preparing flexible and durable conductive fabric by graphene oxide electrostatic flocking method |
| CN111074417A (en) * | 2019-11-28 | 2020-04-28 | 江苏品创纺织科技有限公司 | Preparation method of fabric with electromagnetic shielding function |
| CN111155197B (en) * | 2020-01-10 | 2021-01-19 | 华南理工大学 | Magnetic fiber material and preparation method and application thereof |
| CN111197184B (en) * | 2020-01-17 | 2022-04-05 | 西安交通大学 | Electrostatic spinning device |
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| CN100429335C (en) * | 2006-04-26 | 2008-10-29 | 北京化工大学 | Electric spinning-in-situ photopolymerization apparatus and process for preparing nanometer fiber |
| CN100526524C (en) * | 2007-02-02 | 2009-08-12 | 吉林大学 | No-solvent electrically spinning process for preparing micron and nanometer fiber |
| US10221503B2 (en) * | 2011-04-07 | 2019-03-05 | Board Of Regents Of The University Of Texas System | Photopolymerizable compositions for solventless fiber spinning |
| CN104532367B (en) * | 2014-12-19 | 2016-08-24 | 青岛大学 | A kind of method that solvent-free electrostatic spinning prepares polyurethane micro nanometer fiber |
| CN104804146A (en) * | 2015-04-27 | 2015-07-29 | 北京印刷学院 | Hybrid light curing material for production of flexible plate as well as preparation method and application of hybrid light curing material |
| CN104878456B (en) * | 2015-05-26 | 2017-02-22 | 青岛大学 | Magnetic spinning device and method using device for manufacturing micro-nano-meter fibers |
| CN104862799B (en) * | 2015-05-26 | 2017-01-18 | 青岛大学 | Method for preparing graphene/polymer orderly micro-nanometer composite fiber through magnetic spinning |
| CN105088367B (en) * | 2015-08-25 | 2017-12-22 | 青岛大学 | A kind of solvent-free electrostatic spinning apparatus based on UV solidifications |
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