CN107687041A - Emitting red light electromagnetism three-function nano fiber yarn and preparation method thereof - Google Patents

Emitting red light electromagnetism three-function nano fiber yarn and preparation method thereof Download PDF

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CN107687041A
CN107687041A CN201710927782.7A CN201710927782A CN107687041A CN 107687041 A CN107687041 A CN 107687041A CN 201710927782 A CN201710927782 A CN 201710927782A CN 107687041 A CN107687041 A CN 107687041A
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pan
phen
nano
pani
red light
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董相廷
范丽冰
于文生
马千里
田娇
李丹
奚雪
王进贤
王昕璐
刘桂霞
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Changchun University of Science and Technology
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Changchun University of Science and Technology
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention relates to emitting red light electromagnetism three-function nano fiber yarn and preparation method thereof, belong to technical field of nanometer material preparation.The present invention includes four steps：(1) precipitation method prepare the Fe of Coated with Oleic Acid3O4It is nanocrystalline；(2) precipitation method prepare Eu (BA)3Phen complexs；(3) spinning solution is prepared；(4) [Fe is prepared3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn, prepared using conjugation single nozzle electrostatic spinning technique.Prepared nano-fibre yams have good emitting red light, conduction and the function of magnetic three simultaneously.The method of the present invention is simple for process, practical, non-environmental-pollution, can produce in batches, this new one-dimensional nano structure material has broad application prospects.

Description

Emitting red light electromagnetism three-function nano fiber yarn and preparation method thereof
Technical field
The present invention relates to technical field of nanometer material preparation, in particulars relate to emitting red light electromagnetism three-function nano silvalin Line and preparation method thereof.
Background technology
Simple function applications to nanostructures is limited in scope, and difunctional or multi-functional nanometer material application is more Extensively, this kind of material has more characteristic and attraction, and therefore, multi-functional nanometer material is paid high attention to by researcher.With nanometer The development of science and technology, nano material such as have the characteristics of luminescence, electric conductivity or magnetic, towards difunctional and more work(by simple function Can direction develop, such as there is magneto-optic, photoelectricity or electromagnetism is difunctional and the function of photoelectromagnetic three, so can be in a kind of nanostructured Difunctional or three functions are realized on material, the development to the science and technology of nano-device, nanometer technology and correlation has important Meaning.For example, magnetic-fluorescent dual-function nano composite material provides a kind of new platform for medical diagnosis on disease and treatment, due to Their difunctional property is integrally formed " it was found that-detection-treatment " of disease.The use of this nano composite material will enter one Step improves the efficiency of diagnosis and reduces side effect, causes the highest attention of researcher.Electromagnetism dual-functional nanometer compound is in thunder Had broad application prospects up to ripple absorption, electromagnetic shielding, antistatic coating and sensor etc..Photoelectromagnetic three-function nano Fiber yarn, due to its unique performance, abundant scientific meaning, wide application prospect and in following nano structure device In the important strategic status occupied, cause the great attention of people in recent years.Have no emitting red light, conduction and magnetic three at present The report of functional nano-fiber yarn.
Ferroso-ferric oxide Fe3O4It is a kind of important and wide variety of magnetic material.People use a variety of methods, such as The methods of precipitation method, sol-gel process, microemulsion method, hydro-thermal and solvent-thermal method, thermal decomposition method, method of electrostatic spinning, successfully makes It is standby gone out Fe3O4The nano materials such as nanocrystalline, nanometer rods, nano wire, nanometer film, hybrid structure, Core-shell Structure Nanoparticles, skill Art comparative maturity.Rare earth metal europium complex Eu (BA)3Phen, Eu3+For europium ion, BA is benzoate anion, and phen is adjacent Féraud Quinoline, turn into the red illuminating material of unique energy because of the unique electron configuration of europium ion, as luminous intensity is high, stability Well, the advantages that fluorescence quantum yield is high, monochromaticjty is good, is a kind of wide variety of fluorescent material.Polyaniline PANI is held due to it It is easily-synthesized, the advantages that electrical conductivity is high and environmental stability is good, has become one of focus of conducting polymer area research.People The polyaniline PANI of the one-dimensional nano structures such as nano wire, nanometer rods, nanotube and nanofiber has been synthesized, therefore, has been utilized Magnetic Fe3O4Nanocrystalline, rare-earth europium emitting complexes Eu (BA)3Phen and electrically conductive polyaniline PANI is constructed with the work(of photoelectromagnetic three The nano material of energy characteristic is preferable material.
Existing research is it has been proved that work as dark colour electrically conductive polyaniline PANI and magnetic Fe3O4It is direct with rare earth compounding Mixing, can significantly reduce its illumination effect, therefore to obtain the good illumination effect of rare earth compounding, it is necessary to make rare earth compounding With PANI and Fe3O4Realization efficiently separates.If by conductive polymer polyanilinc PANI and Fe3O4Nanocrystalline and polyacrylonitrile (PAN) Nanofiber is compounded to form, by rare earth compounding Eu (BA)3Phen and PAN is compounded to form nanofiber, by both Nanowires Dimension twisting is threaded together, and forms nano-fibre yams, it is possible to realize polyaniline PANI and Fe3O4Effectively divide with rare earth compounding From so as to obtain emitting red light-conduction of good performance-magnetic three-function nano fiber yarn, this new 1-dimention nano Material has not yet to see related document report by with important application prospect.
One relevant electrospinning process (electrospinning) of the U.S. Patent Publication of Patent No. 1975504 Technical scheme, this method is to prepare a kind of effective ways of micro nanometer fiber that is continuous, having macro length, by Formhals was proposed first in 1934.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making powered Polymer Solution or melt are sprayed in electrostatic field by the traction of electrostatic force by nozzle, invest the receiving screen on opposite, so as to real Existing wire drawing, then, solvent evaporates at normal temperatures, or melt cooling solidifies to normal temperature, obtains micro nanometer fiber.People are Photoelectromagnetic simple function, difunctional and three-function nano fiber are prepared for using electrostatic spinning technique.Q.Z.Yu, et al. are used Polyaniline PANI nanofibers that electrostatic spinning technique is prepared for having single conducting function [Mater.Sci.Eng.B, 2008, 150,70-76]；The PAN/Eu (BA) that Dong Xiangting etc. is prepared for having single lighting function using electrostatic spinning technique3Phen is sent out Light nano fibrous membrane [New Chemical Materials, 2008,36 (9), 49-52]；Wang Ce etc. is prepared for magnetic using method of electrostatic spinning Property polyvinylpyrrolidone/ferroso-ferric oxide composite nano-fiber film [SCI, 2006,27 (10), 2002-2004]；Qingbiao Yang, et al. are prepared for Fe using electrostatic spinning technique2O3nanoparticles/Eu (DBM)3(Bath) compound difunctional magneto-optic nanofiber [Journal of Colloid and Interface Science, 2010,350,396-401], Dong Xiangting etc. is prepared for Fe using electrostatic spinning technique3O4/Eu(BA)3The double work(of phen/PVP magneto-optics Can composite nano fiber [Journal of Nanoparticle Research, 2012,14 (10):1203-1209]、Eu (BA)3The difunctional composite nano fiber of phen/PANI/PVP photoelectricity [SCI, 2012,33 (8), 1657- 1662] and Eu (BA)3phen/PANI/Fe3O4/ PVP photoelectromagnetic three-function nanos fiber [Journal of Materials Science:Materials in Electronics,2014,25(3),1309-1316].Wu, et al. use electrostatic spinning Technology is prepared for the nano-fibre yams with high cell viability, this yarn show with the adhesion for improving cell and Multiplication capacity [ACS Appl.Mater.Interfaces, 2016,8,16950-16960]；Wang, et al. use Static Spinning Silk technology be prepared for nano-fibre yams that PCL/silk fibroin/polyaniline align [ACS Nano, 2015, 9,9167-9179]；PAN is spun into nano-fibre yams so as to obtain carbon fiber by Xie, et al. by electrostatic spinning technique Presoma [RSC Adv., 2015,5,15147-15153].At present, have no and prepare emitting red light using electrostatic spinning technique, lead The electrically and magnetically relevant report of property three-function nano fiber yarn.
When preparing nano material using electrostatic spinning technique, the species of raw material, the molecular weight of high polymer templates, spinning solution Composition, the structure of spinning process parameter and spinning head all has a major impact to the pattern and size of final products.The present invention adopts With conjugation single nozzle electrostatic spinning technique, two high-voltage DC power supplies are exported using positive high voltage output and negative high voltage, are driven by motor Dynamic rotation brass bugle is twisted to fibre bundle, by the round metal bars of adjustable speed motor driving as collection device；By Eu (BA)3Phen and polyacrylonitrile (PAN) are added in DMF DMF, are configured to a Static Spinning with certain viscosity Silk liquid, referred to as spinning solution I, by the Fe of Coated with Oleic Acid3O4Nanocrystalline, aniline, camphorsulfonic acid, PAN, DMF and ammonium persulfate mixing structure Into another spinning solution, wherein aniline polymerization is into polyaniline PANI, referred to as spinning solution II；Control spinning solution viscosity to close weight Will, under optimal process conditions, obtain the novel [Fe of structure3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] nanometer Fiber yarn.
The content of the invention
It is fine that photoelectromagnetic simple function, difunctional and three-function nano are prepared for using electrostatic spinning technique in the introduction Dimension, the PAN Nanowires of the nano-fibre yams and carbon fiber precursor for biological field are prepared for using electrostatic spinning technique Yarn is tieed up, used raw material, template, solvent and final target product and the method for the present invention are different.The present invention [Fe is prepared for using conjugation single nozzle electrostatic spinning technique3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electricity Magnetic three-function nano fiber yarn, a kind of nano-fiber material with novel characteristics is added for nanofiber field.
The present invention is achieved in for preparing Eu (BA) using the precipitation method first3Phen complexs and Coated with Oleic Acid Fe3O4It is nanocrystalline, with Eu (BA)3The mixed liquor of phen complexs, PAN and DMF DMF is a kind of spinning solution, Referred to as spinning solution I, by the Fe of Coated with Oleic Acid3O4Nanocrystalline, PAN, aniline, camphorsulfonic acid, ammonium persulfate, DMF mixing, treat aniline Another spinning solution, referred to as spinning solution II are formed after aggregating into polyaniline, controls the viscosity of spinning solution, it is quiet using conjugation single nozzle Electrospinning carries out electrostatic spinning, under optimal process conditions, obtains [Fe3O4/PANI/PAN]//[Eu(BA)3phen/ PAN] emitting red light electromagnetism three-function nano fiber yarn, its step is：
(1) precipitation method prepare the Fe of Coated with Oleic Acid3O4It is nanocrystalline
By 32.8500g FeCl3·6H2O, 16.7000g FeSO4·7H2O, 24.2400g NH4NO3With 11.4000g points Son amount is dissolved in 600mL deionized waters for 20000 polyethylene glycol, is heated to 50 DEG C and is passed through argon gas 30min, is then slowly dripped Ammonification water to the pH value of solution is 11, continues logical argon gas 20min and obtains black suspension, after this suspension Magneto separate, with nothing Water-ethanol and deionized water are washed three times successively, and product is placed in 60 DEG C of vacuum drying chamber and dries 12h, obtains a diameter of 8- 10nm Fe3O4It is nanocrystalline；Take the Fe prepared by 2.0000g3O4It is nanocrystalline be dispersed in be passed through 30min argon gas 100mL go from In sub- water and ultrasonic disperse 20min, solution is then heated to 80 DEG C under argon gas protection, and adds 1mL oleic acid, is then proceeded to 40min is reacted, resulting precipitation is subjected to Magneto separate, water layer is removed and will be deposited in 60 DEG C of vacuum drying chambers and dry 12h, Obtain the Fe of Coated with Oleic Acid3O4It is nanocrystalline；
(2) precipitation method prepare Eu (BA)3Phen complexs
By 1.7600g Eu2O3Powder is dissolved in 20mL concentrated nitric acids, is heated to 120 DEG C, and the concentrated nitric acid of excess and water are steamed Hair removes, and adds 20mL absolute ethyl alcohols, obtains Eu (NO3)3Ethanol solution, 3.6640g benzoic acid and 1.8020g is adjacent luxuriant and rich with fragrance Sieve quinoline is dissolved in 200mL absolute ethyl alcohols jointly, then by Eu (NO3)3Ethanol solution be slowly added thereto, regulation pH 6-6.5 it Between, 3h then is stirred at 60 DEG C, resulting precipitation deionized water and absolute ethyl alcohol alternately washing 6 times put product 12h is heated in 60 DEG C of baking ovens, obtains Eu (BA)3Phen powder；
(3) spinning solution is prepared
By 0.0750g Eu (BA)3Phen is added in 5.0000g DMF, and it is 86000 that 0.5000g molecular weight is added after dissolving Polyacrylonitrile (PAN), magnetic agitation 3h at 60 DEG C, obtain spinning solution I；By the Fe of 0.9000g Coated with Oleic Acid3O4Nanocrystalline addition Into 7.000g DMF, ultrasonic disperse 20min, the polyacrylonitrile (PAN) that 0.9000g molecular weight is 86000 is added, at 60 DEG C Stirring 3h is completely dissolved it, adds 0.5400g aniline ANI and 0.6740g camphorsulfonic acid CSA, magnetic agitation 2h, will 1.3233g ammonium persulfates APS is dissolved in 2.0000g DMF, magnetic agitation 2h, and this two parts of solution are put into 0 DEG C of refrigerator 1h is refrigerated, this two parts of solution are mixed in ice-water bath afterwards, after magnetic agitation 3h, mixed liquor are put into cold in 5 DEG C of refrigerator 24h is hidden, obtains spinning solution II；
(4) [Fe is prepared3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano silvalin Line
Using conjugation single nozzle electrostatic spinning technique, electrostatic spinning is carried out using two high-voltage DC power supplies, one is just High-voltage DC power supply, positive high voltage is exported, another is negative high voltage dc source, negative high voltage is exported, by spinning solution I and spinning solution II Pour into respectively in two 5mL plastic injectors with plastic spray gun head, electrode, one end of one section of copper cash are done respectively with two sections of copper cash Insert in spinning solution I, the other end is connected with the positive high voltage output end of positive high voltage dc source, and one end insertion of another section of copper cash is spun In silk liquid II, the other end is connected with the negative high voltage output end of negative high voltage dc source, with wire by positive and negative high-voltage DC power supply Zero potential end is connected with ground wire respectively, plastic injector be positioned symmetrically in ground connection by it is motor-driven inversion brass bugle two Side, the distance at loudspeaker Edge Distance lance head tip is 10cm, and when starting spinning, a metal is placed in the underface of loudspeaker Silk, the taper fibre bundle of a handstand can be formed between the tip of wire and the edge of loudspeaker, by motor-driven rotation Loudspeaker are twisted to fibre bundle, obtain nano-fibre yams, slowly downward drawing metal, yarn is drawn to by adjustable speed motor For the round metal bars of driving as being collected on collection device, collection device round metal bars and the distance of loudspeaker lower end are 18cm, Spinning voltage is ± 15kV, and loudspeaker rotating speed is 100r/min, and gathering speed 0.03m/min, environment temperature is 15-25 DEG C, phase It is 15%-25% to humidity, obtains [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three function receive Rice fiber yarn.
Prepared [Fe in above process3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] nano-fibre yams Average diameter is 201 μm, by the Fe aligned3O4/ PANI/PAN function solenoids nanofiber and Eu (BA)3Phen/PAN is glimmering The different nanofiber twisting of two kinds of light nanofiber forms, a diameter of 508 ± 8nm of nanofiber；In 278nm ultraviolet light Excite down, [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] nano-fibre yams launch main peak and are located at the bright of 616nm Azarin light；[Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] nano-fibre yams average conductivity be 1.50 × 10- 3S·cm-1；[Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] saturation magnetizations of nano-fibre yams is 11.08emu/g, prepared [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] nano-fibre yams have simultaneously it is good The function of emitting red light electromagnetism three, realize goal of the invention.
Brief description of the drawings
Fig. 1 is [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn XRD spectra；
Fig. 2 is [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn SEM photograph, the figure also serves as Figure of abstract；
Fig. 3 is [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn High magnification SEM photograph；
Fig. 4 is [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn Middle nanofiber diameter distribution histogram；
Fig. 5 is [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn EDS spectrograms；
Fig. 6 is [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn Exciting light spectrogram；
Fig. 7 is [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn Launching light spectrogram；
Fig. 8 is [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn Hysteresis curve figure.
Embodiment
Europium oxide Eu selected by the present invention2O3Purity be 99.99%, benzoic acid, Phen, N, N- dimethyl methyls Acid amides, Iron(III) chloride hexahydrate, green vitriol, ammonium nitrate, molecular weight be 20000 polyethylene glycol, nitric acid, molecular weight It is commercially available analysis for 86000 polyacrylonitrile, absolute ethyl alcohol, ammoniacal liquor, aniline, camphorsulfonic acid, ammonium persulfate, oleic acid, argon gas Net product；Make by oneself in deionized water laboratory；Glass apparatus and equipment used is the instrument and equipment commonly used in laboratory.
Embodiment：By 32.8500g FeCl3·6H2O, 16.7000g FeSO4·7H2O, 24.2400g NH4NO3With The polyethylene glycol that 11.4000g molecular weight is 20000 is dissolved in 600mL deionized waters, is heated to 50 DEG C and is passed through argon gas 30min, Then the pH value that ammoniacal liquor is slowly added dropwise to solution is 11, continues logical argon gas 20min and obtains black suspension, by this suspension magnetic point From rear, washed successively three times with absolute ethyl alcohol and deionized water, product is placed in 60 DEG C of vacuum drying chamber and dries 12h, is obtained To a diameter of 8-10nm Fe3O4It is nanocrystalline；Take the Fe prepared by 2.0000g3O4Nanocrystalline be dispersed in has been passed through 30min argon gas 100mL deionized waters in and ultrasonic disperse 20min, then by solution argon gas protection under be heated to 80 DEG C, and add 1mL oil Acid, is then proceeded to react 40min, and resulting precipitation is carried out into Magneto separate, is removed water layer and will be deposited in 60 DEG C of vacuum drying 12h is dried in case, obtains the Fe of Coated with Oleic Acid3O4It is nanocrystalline；By 1.7600g Eu2O3Powder is dissolved in 20mL concentrated nitric acids, is added The concentrated nitric acid of excess and water evaporation are removed to 120 DEG C, add 20mL absolute ethyl alcohols, obtain Eu (NO by heat3)3Ethanol it is molten Liquid, 3.6640g benzoic acid and 1.8020g Phens are dissolved in 200mL absolute ethyl alcohols jointly, then by Eu (NO3)3Ethanol Solution is slowly added thereto, and pH is between 6-6.5 for regulation, then 3h is stirred at 60 DEG C, by resulting precipitation deionization Water and absolute ethyl alcohol alternately washing 6 times, product is placed in 60 DEG C of baking ovens and heats 12h, obtains Eu (BA)3Phen powder；Will 0.0750g Eu(BA)3Phen is added in 5.0000g DMF, and the polyacrylonitrile that 0.5000g molecular weight is 86000 is added after dissolving PAN, magnetic agitation 3h at 60 DEG C, obtains spinning solution I；By the Fe of 0.9000g Coated with Oleic Acid3O4It is nanocrystalline to be added to 7.000g In DMF, ultrasonic disperse 20min adds the polyacrylonitrile (PAN) that 0.9000g molecular weight is 86000, and 3h is stirred at 60 DEG C to be made It is completely dissolved, and 0.5400g aniline ANI and 0.6740g camphorsulfonic acid CSA, magnetic agitation 2h is added, by 1.3233g over cures Sour ammonium APS is dissolved in 2.0000g DMF, magnetic agitation 2h, and this two parts of solution are put into 0 DEG C of refrigerator and refrigerate 1h, afterwards This two parts of solution are mixed in ice-water bath, after magnetic agitation 3h, mixed liquor is put into 5 DEG C of refrigerator and refrigerates 24h, is spun Silk liquid II；Using conjugation single nozzle electrostatic spinning technique, electrostatic spinning is carried out using two high-voltage DC power supplies, one is positive height Dc source is pressed, exports positive high voltage, another is negative high voltage dc source, exports negative high voltage, by II points of spinning solution I and spinning solution Do not pour into two 5mL plastic injectors with plastic spray gun head, do electrode respectively with two sections of copper cash, one end of one section of copper cash is inserted Enter in spinning solution I, the other end is connected with the positive high voltage output end of positive high voltage dc source, one end insertion spinning of another section of copper cash In liquid II, the other end is connected with the negative high voltage output end of negative high voltage dc source, with wire by the zero of positive and negative high-voltage DC power supply Potential end is connected with ground wire respectively, plastic injector be positioned symmetrically in ground connection by it is motor-driven inversion brass bugle two Side, the distance at loudspeaker Edge Distance lance head tip is 10cm, and when starting spinning, a metal is placed in the underface of loudspeaker Silk, the taper fibre bundle of a handstand can be formed between the tip of wire and the edge of loudspeaker, by motor-driven rotation Loudspeaker are twisted to fibre bundle, obtain nano-fibre yams, slowly downward drawing metal, yarn is drawn to by adjustable speed motor For the round metal bars of driving as being collected on collection device, collection device round metal bars and the distance of loudspeaker lower end are 18cm, Spinning voltage is ± 15kV, and loudspeaker rotating speed is 100r/min, and gathering speed 0.03m/min, environment temperature is 15-25 DEG C, phase It is 15%-25% to humidity, obtains [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three function receive Rice fiber yarn.Described [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber Contain Emission in Cubic Fe in yarn3O4It is nanocrystalline, as shown in Figure 1；Described [Fe3O4/PANI/PAN]//[Eu(BA)3phen/PAN] The average diameter of emitting red light electromagnetism three-function nano fiber yarn is 201 μm, as shown in Figure 2；Described [Fe3O4/PANI/ PAN]//[Eu(BA)3Phen/PAN] in emitting red light electromagnetism three-function nano fiber yarn, include the Fe aligned3O4/ PANI/PAN function solenoids nanofiber and Eu (BA)3Two kinds of different nanofibers of phen/PAN fluorescent nano-fibers, are shown in Fig. 3 It is shown；[Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] Nanowire in emitting red light electromagnetism three-function nano fiber yarn A diameter of 508 ± 8nm of dimension, as shown in Figure 4；[Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three Functional nano-fiber yarn is made up of Fe, Eu, C, O, N, S, and Pt derives from the conducting film that surface is plated when observing sample with SEM, sees Shown in Fig. 5；Monitoring wavelength, [Fe are used as using 616nm3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three Functional nano-fiber yarn has a wide excitation band at 200-350nm, its peak value at 278nm, can be classified as the π of part → π * transition, as shown in Figure 6；Under 278nm ultraviolet excitation, [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] it is red Luminesced electromagnetic three-function nano fiber yarn launches the bright red that main peak is located at 616nm, and it corresponds to Eu ions5D0→7F2Transition, as shown in Figure 7；Made [the Fe stated3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] three function of emitting red light electromagnetism Nano-fibre yams have stronger magnetic, saturation magnetization 11.08emu/g, as shown in Figure 8；Using four probe tests Instrument measures [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn is averaged Electrical conductivity is 1.50 × 10-3S·cm-1。
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence Know those skilled in the art when can be made according to the present invention it is various it is corresponding change and deformation, but these corresponding change and become Shape should all belong to the protection domain of appended claims of the invention.

Claims (2)

1. emitting red light electromagnetism three-function nano fiber yarn, it is characterised in that by the Fe aligned3O4/ PANI/PAN electromagnetism Functional nano-fiber and Eu (BA)3The different nanofiber twisting of two kinds of phen/PAN fluorescent nano-fibers forms, and yarn is simultaneously With three kinds of emitting red light, conduction and magnetic functions, the average diameter of yarn is 201 μm.
2. a kind of preparation method of emitting red light electromagnetism three-function nano fiber yarn as claimed in claim 1, its feature exist In using conjugation single nozzle electrostatic spinning technique, it is [Fe to prepare product3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] it is red Color luminesced electromagnetic three-function nano fiber yarn, its step are：
(1) precipitation method prepare the Fe of Coated with Oleic Acid3O4It is nanocrystalline
By 32.8500g FeCl3·6H2O, 16.7000g FeSO4·7H2O, 24.2400g NH4NO3With 11.4000g molecular weight It is dissolved in for 20000 polyethylene glycol in 600mL deionized waters, is heated to 50 DEG C and is passed through argon gas 30min, ammonia is then slowly added dropwise Water to the pH value of solution is 11, continues logical argon gas 20min and obtains black suspension, after this suspension Magneto separate, with anhydrous second Alcohol and deionized water are washed three times successively, and product is placed in 60 DEG C of vacuum drying chamber and dries 12h, obtains a diameter of 8-10nm Fe3O4It is nanocrystalline；Take the Fe prepared by 2.0000g3O4It is nanocrystalline to be dispersed in the 100mL deionized waters for being passed through 30min argon gas In and ultrasonic disperse 20min, solution is then heated to 80 DEG C under argon gas protection, and 1mL oleic acid is added, then proceedes to react 40min, resulting precipitation is subjected to Magneto separate, removes water layer and will be deposited in 60 DEG C of vacuum drying chambers and dry 12h, obtain The Fe of Coated with Oleic Acid3O4It is nanocrystalline；
(2) precipitation method prepare Eu (BA)3Phen complexs
By 1.7600g Eu2O3Powder is dissolved in 20mL concentrated nitric acids, is heated to 120 DEG C, and the concentrated nitric acid of excess and water evaporation are removed Go, add 20mL absolute ethyl alcohols, obtain Eu (NO3)3Ethanol solution, by 3.6640g benzoic acid and 1.8020g Phens It is dissolved in jointly in 200mL absolute ethyl alcohols, then by Eu (NO3)3Ethanol solution be slowly added thereto, regulation pH between 6-6.5, Then 3h is stirred at 60 DEG C, by resulting precipitation deionized water and absolute ethyl alcohol alternately washing 6 times, product is placed on 60 12h is heated in DEG C baking oven, obtains Eu (BA)3Phen powder；
(3) spinning solution is prepared
By 0.0750g Eu (BA)3Phen is added in 5.0000g DMF, added after dissolving 0.5000g molecular weight be 86000 it is poly- Acrylonitrile PAN, magnetic agitation 3h at 60 DEG C, obtains spinning solution I；By the Fe of 0.9000g Coated with Oleic Acid3O4It is nanocrystalline to be added to In 7.000g DMF, ultrasonic disperse 20min, the polyacrylonitrile (PAN) that 0.9000g molecular weight is 86000 is added, is stirred at 60 DEG C Mixing 3h is completely dissolved it, adds 0.5400g aniline ANI and 0.6740g camphorsulfonic acid CSA, magnetic agitation 2h, will 1.3233g ammonium persulfates APS is dissolved in 2.0000g DMF, magnetic agitation 2h, and this two parts of solution are put into 0 DEG C of refrigerator 1h is refrigerated, this two parts of solution are mixed in ice-water bath afterwards, after magnetic agitation 3h, mixed liquor are put into cold in 5 DEG C of refrigerator 24h is hidden, obtains spinning solution II；
(4) [Fe is prepared3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber yarn
Using conjugation single nozzle electrostatic spinning technique, electrostatic spinning is carried out using two high-voltage DC power supplies, one is positive high voltage Dc source, positive high voltage is exported, another is negative high voltage dc source, exports negative high voltage, and spinning solution I and spinning solution II is distinguished Pour into two 5mL plastic injectors with plastic spray gun head, electrode, one end insertion of one section of copper cash are done respectively with two sections of copper cash In spinning solution I, the other end is connected with the positive high voltage output end of positive high voltage dc source, one end insertion spinning solution of another section of copper cash In II, the other end is connected with the negative high voltage output end of negative high voltage dc source, electric by the zero of positive and negative high-voltage DC power supply with wire Gesture end is connected with ground wire respectively, and plastic injector is positioned symmetrically in the both sides by motor-driven inversion brass bugle of ground connection, The distance at loudspeaker Edge Distance lance head tip is 10cm, and when starting spinning, an one metal wire is placed in the underface of loudspeaker, The taper fibre bundle of a handstand can be formed between the tip of wire and the edge of loudspeaker, is given by motor-driven rotation loudspeaker Fibre bundle is twisted, and obtains nano-fibre yams, slowly downward drawing metal, and yarn is drawn to by adjustable speed motor driving Round metal bars on collection device as being collected, and the distance of collection device round metal bars and loudspeaker lower end is 18cm, and spinning is electric It is 100r/min to press as ± 15kV, loudspeaker rotating speed, and gathering speed 0.03m/min, environment temperature is 15-25 DEG C, relative humidity For 15%-25%, [Fe is obtained3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] emitting red light electromagnetism three-function nano fiber Yarn, average diameter is 201 μm, by the Fe aligned3O4/ PANI/PAN function solenoids nanofiber and Eu (BA)3phen/ The different nanofiber twisting of two kinds of PAN fluorescent nano-fibers forms, a diameter of 508 ± 8nm of nanofiber, 278nm's Under ultraviolet excitation, [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] nano-fibre yams launch main peak and are located at 616nm bright red, [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] average conductivities of nano-fibre yams is 1.50×10-3S·cm-1, [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] nano-fibre yams saturation magnetization For 11.08emu/g, prepared [Fe3O4/PANI/PAN]//[Eu(BA)3Phen/PAN] nano-fibre yams simultaneously have it is good The good function of emitting red light electromagnetism three.
CN201710927782.7A 2017-10-09 2017-10-09 Emitting red light electromagnetism three-function nano fiber yarn and preparation method thereof Withdrawn CN107687041A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109537164A (en) * 2018-12-24 2019-03-29 长春理工大学 Three function sandwich structure composite membrane of anisotropic conductive magneto-optic and preparation method thereof
CN109706621A (en) * 2018-12-24 2019-05-03 长春理工大学 Anisotropic conductive magnetism red and green color fluorescence sandwich structure multifunctional composite film

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109537164A (en) * 2018-12-24 2019-03-29 长春理工大学 Three function sandwich structure composite membrane of anisotropic conductive magneto-optic and preparation method thereof
CN109706621A (en) * 2018-12-24 2019-05-03 长春理工大学 Anisotropic conductive magnetism red and green color fluorescence sandwich structure multifunctional composite film
CN109706621B (en) * 2018-12-24 2021-07-16 长春理工大学 Anisotropic conductive magnetic red-green double-color fluorescent sandwich structure multifunctional composite film

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