CN103225129A - Photo-electromagnetic three-functional three-strands-paralleled nanometer fiber bundle and its preparation method - Google Patents
Photo-electromagnetic three-functional three-strands-paralleled nanometer fiber bundle and its preparation method Download PDFInfo
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Abstract
The invention relates to a photo-electromagnetic three-functional three-strands-paralleled nanometer fiber bundle and its preparation method, and belongs to the technical field of nanomaterial preparation. The method comprises the following steps: 1, preparing an Eu(BA)3phen complex through a precipitation process; 2, preparing an Fe3O4 nanocrystal through the precipitation process; 3, preparing a spinning liquid; and 4, preparing an [Eu(BA)3phen/PVP]//[PANI/PVP]//[Fe3O4/PVP] photo-electromagnetic three-functional three-strands-paralleled nanometer fiber bundle, adopting a static spinning technology, and using a parallel three-spinning head. The prepared photo-electromagnetic three-functional three-strands-paralleled nanometer fiber bundle has a smooth surface and has good luminescent, conductive and magnetic functions, and the diameter and the length of a single-stranded nanofiber are 180nm and above 50mum respectively. The above nanostructured material has an important application prospect. The method is simple, is easy to implement, can realize batch production, and has a wide application prospect.
Description
Technical field
The present invention relates to the nano material preparation technical field, relate to three bursts of parallel bundles of nanofibers of a kind of photoelectromagnetic three functions and preparation method thereof specifically.
Background technology
Nanofiber is meant the filamentary material that has bidimensional to be in nanoscale on the three dimensions yardstick of material, radial dimension is a nanometer scale usually, and length is then bigger.Because the radial dimension of nanofiber is little of nanometer scale, demonstrate series of characteristics, the most outstanding is that specific area is big, thereby its surface energy and active the increase, and then produce small-size effect, surface or interfacial effect, quantum size effect, macro quanta tunnel effect etc., and therefore show a series of chemistry, physics specificity as aspects such as heat, light, sound, electricity, magnetic.In the prior art, a lot of methods that prepare nanofiber are arranged, the method for for example reeling off raw silk from cocoons, template synthetic method, split-phase method and self-assembly method etc.In addition, also has arc evaporation, laser high temperature inustion, compound pyrolysismethod.These three kinds of methods in fact all are after at high temperature making compound or simple substance evaporation, to make nanofiber or nanotube through pyrolysis or direct condensation, from essence, all belong to the compound steam sedimentation.
Three bursts of parallel bundles of nanofibers are nano-fiber materials of a kind of new structure, stick together by three strands of nanofibers and to form three bursts of parallel bundles of nanofibers, per share nanofiber has different functions, has lighting function as one fiber, one fiber has electric conductivity, one fiber has magnetic, this have that photoelectromagnetic is three difunctional, three bursts of parallel bundles of nanofibers of novel structure will have important use in following nano structure device and medical diagnosis treatment, and the research of this respect yet there are no report.
Polyaniline PANI is because advantage such as it is easily synthetic, electrical conductivity is high and environmental stability is good has become one of focus of conducting polymer area research.People have synthesized the polyaniline PANI[J.R.Araujo of one-dimensional nano structures such as nano wire, nanometer rods, nanotube and nanofiber, C.B.Adamo and Marco-A.De Paoli, Chem.Eng.J., 2011,174,425-431; J.Huang, S.Virji, B.H.Weiller and R.B.Kaner, Chem.Eur.J.2004,10,1314 – 1319; Q.Z.Yu, M.M.Shi, M.Deng, M.Wang and H.Z.Chen, Mater.Sci.Eng.B, 2008,150,70-76].
Rare-earth europium complex Eu (BA)
3Phen, Eu
3+Be europium ion, BA is a benzoate anion, and phen is a phenanthroline, because of the electron configuration of europium ion uniqueness becomes the light emitting ionic with special performance, Eu (BA)
3Phen has advantages such as luminous intensity height, good stability, fluorescence quantum yield height, monochromaticjty be good, is a kind of rare-earth luminescent material of extensive use.
Tri-iron tetroxide Fe
3O
4It is a kind of important and magnetic material of extensive use.People have adopted several different methods, have successfully prepared Fe as methods such as the precipitation method, sol-gel process, microemulsion method, hydro-thermal and solvent-thermal method, thermal decomposition method, method of electrostatic spinning
3O
4Nano materials such as nanocrystalline, nanometer rods, nano wire, nanometer film, hybrid structure, nuclear shell structure nano particle, the technology comparative maturity.
Existing research is verified, as magnetic compound Fe
3O
4Perhaps dark colour electrically conductive polyaniline PANI and rare earth compounding Eu (BA)
3Phen directly contacts the mixing meeting and significantly reduces its illumination effect, therefore will obtain Eu (BA)
3The illumination effect that phen is good must make Eu (BA)
3Phen and Fe
3O
4Or PANI realizes effectively separating and can not directly contact.If conductive polymer polyanilinc PANI is mixed with into nanofiber with PVP, conduction PANI is continuous, has guaranteed its high conductivity, and as three strands of one fibers that parallel nanofiber is intrafascicular, this strand fiber will have electric conductivity, with Fe
3O
4Nanocrystallinely be mixed with into nanofiber with PVP, as three strands of one fibers that parallel nanofiber is intrafascicular, this strand fiber will have magnetic, and with Eu (BA)
3Phen is scattered among the macromolecule PVP and is prepared into nanofiber, and as three strands of one fibers that parallel nanofiber is intrafascicular, this strand fiber will have luminescent properties, thereby can make Fe
3O
4Nanocrystalline and electrically conductive polyaniline PANI and Eu (BA)
3Phen has realized effective separation, so just can obtain three bursts of parallel bundles of nanofibers of well behaved photoelectromagnetic three functions.
At present, do not see by Eu (BA)
3Phen complex and polyvinylpyrrolidone PVP are compound, and polyaniline PANI and PVP are compound, Fe
3O
4Nanocrystalline and PVP are compound, construct the report of three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, i.e. three strands of parallel nanofibers formation bundles of nanofibers that sticks together side by side, and wherein one fiber is Eu (BA)
3Phen+PVP has the characteristics of luminescence, and one fiber is PANI+PVP, has electric conductivity, and one fiber is Fe
3O
4Nanocrystalline+PVP, have magnetic, promptly form [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, // representative is parallel, i.e. the material of front [Eu (BA)
3Phen/PVP] fiber that constitutes and the fiber of middle material [PANI/PVP] formation and the material [Fe of back
3O
4/ PVP] fiber that constitutes is all parallel mutually.This kind has three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions and has special structure, will have important application prospects in following nano structure device and medical diagnosis treatment.
The patent No. technical scheme of a relevant electrospinning process (electrospinning) that has been 1975504 U.S. Patent Publication, this method is a kind of effective ways that prepare continuous, as to have macro length micro nanometer fiber, is at first proposed in 1934 by Formhals.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making charged Polymer Solution or melt in electrostatic field, to be subjected to the traction of electrostatic force and spray by nozzle, invest the receiving screen on opposite, thereby realization wire drawing, solvent evaporation at normal temperatures then, perhaps melt is cooled to normal temperature and solidifies, and obtains micro nanometer fiber.Over nearly 10 years, occurred adopting electrospinning process to prepare the technical scheme of inorganic compound such as oxidate nano fiber at the inorfil preparing technical field, described oxide comprises TiO
2, ZrO
2, Y
2O
3, Y
2O
3: RE
3+(RE
3+=Eu
3+, Tb
3+, Er
3+, Yb
3+/ Er
3+), SnO
2, NiO, Co
3O
4, Mn
2O
3, Mn
3O
4, CuO, SiO
2, Al
2O
3, V
2O
5, ZnO, Nb
2O
5, MoO
3, CeO
2, LaMO
3(M=Fe, Cr, Mn, Co, Ni, Al), Y
3Al
5O
12, La
2Zr
2O
7Deng metal oxide and composite oxide of metal.Electrospinning process can prepare big L/D ratio micrometer fibers or nanofiber continuously.Q.Z.Yu, et al. adopt electrostatic spinning technique to prepare polyaniline PANI nanofiber [Mater.Sci.Eng.B, 2008,150,70-76]; The single spinning head of uses such as Dong Xiangting, employing electrostatic spinning technique have prepared Eu (BA)
3The difunctional composite nano fiber of phen/PANI/PVP photoelectricity [SCI, 2012,33 (8), 1657-1662]; Dong Xiangting etc. utilize electrostatic spinning technique to prepare Eu (BA)
3The difunctional two bursts of parallel bundles of nanofibers of phen/PVP//PANI/PVP photoelectricity [national inventing patent, application number: 201210407369.5]; Dong Xiangting etc. utilize electrostatic spinning technique to prepare Fe
3O
4/ PVP//Eu (BA)
3Two strands of parallel composite nano fiber bundles of phen/PVP magneto-optic double-function [national inventing patent, application number: 201110249651.0].At present, do not see and utilize electrostatic spinning technique preparation [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] relevant report of three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions.
When utilizing electrostatic spinning technique to prepare nano material, the structure of the composition of the kind of raw material, the molecular weight of high polymer templates, spinning solution, spinning process parameter, Technology for Heating Processing and spinning head all has material impact to the pattern and the size of final products.The present invention adopts electrostatic spinning technique, and spinning head cuts three spinning heads arranged side by side that the identical syringe needle of flat diameter is close together and forms by three 8#, with Eu (BA)
3The mixed liquor of phen complex, PVP and DMF is spinning solution I, and aniline, camphorsulfonic acid, PVP, DMF and ammonium persulfate are mixed, and treats to constitute spinning solution II after aniline polymerization becomes polyaniline, with Fe
3O
4Nanocrystalline, PVP and DMF mix and constitute spinning solution III, and the viscosity of control spinning solution is most important, under the process conditions of the best, obtains [the Eu (BA) of novel structure
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions.
Summary of the invention
Various in background technology prepare in the method for nanofiber, the shortcoming of the method for reeling off raw silk from cocoons be solution viscosity is required too harsh; The shortcoming of template synthetic method is to prepare the continuous fibers that the root root separates; Split-phase method and self-assembly method production efficiency are all lower; And the compound steam sedimentation is owing to the demand to high temperature, so process conditions are difficult to control.And the nanofiber major diameter of above-mentioned several method preparation is than little.Employing electrostatic spinning technique in the background technology has prepared metal oxide nano fiber, composite oxide of metal nanofiber, polyaniline PANI nanofiber, Eu (BA)
3The difunctional composite nano fiber of phen/PANI/PVP photoelectricity, Eu (BA)
3Difunctional two bursts of parallel bundles of nanofibers of phen/PVP//PANI/PVP photoelectricity and Fe
3O
4/ PVP//Eu (BA)
3Two strands of parallel composite nano fiber bundles of phen/PVP magneto-optic double-function, but the character of employed raw material, template agent, solvent and final objective product is different with the present invention.The present invention adopts electrostatic spinning technique, uses three spinning heads arranged side by side to prepare the [Eu (BA) of novel structure
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, one is Eu (BA)
3The phen/PVP luminous nano fibre, one is the PANI/PVP conductive-nano-fibers, one is Fe
3O
4/ PVP magnetic Nano fiber, three strands of nanofibers stick together and form three bursts of parallel bundles of nanofibers, three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions that the present invention is prepared have increased a kind of nano-fiber material with photoelectromagnetic three functions of new construction new property for the nanofiber field.
The present invention is achieved in that and at first adopts the precipitation method to prepare Eu (BA)
3Phen complex and Fe
3O
4Nanocrystalline, with Eu (BA)
3The mixed liquor of phen complex, PVP and DMF is spinning solution I, and aniline, camphorsulfonic acid, PVP, DMF and ammonium persulfate are mixed, and treats to constitute spinning solution II after aniline polymerization becomes polyaniline, with Fe
3O
4Nanocrystalline, PVP and DMF mix and constitute spinning solution III, and the viscosity of control spinning solution is most important.Adopt three spinning heads arranged side by side, application electrostatic spinning technique to carry out electrostatic spinning, under the process conditions of the best, obtain [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions.The steps include:
(1) precipitation method prepare Eu (BA)
3The phen complex
With 0.1760g Eu
2O
3Be dissolved in the red fuming nitric acid (RFNA), add a certain amount of absolute ethyl alcohol behind the evaporate to dryness, be mixed with Eu (NO
3)
3Ethanolic solution, in an amount of absolute ethyl alcohol, add the 0.3664g benzoic acid and the 0.1982g phenanthroline is mixed with mixed ligand solution, be heated to 50-60 ° of C, with Eu (NO
3)
3Ethanolic solution dropwise be added in the ligand solution, drip dense NH again
3H
2It is between 6～6.5 that O regulates pH, produces white precipitate, and constantly stirring reaction 3h after the centrifugation of gained sediment, uses deionized water and absolute ethanol washing 3 times successively, in the dry 12h of 60 ° of C, obtains Eu (BA) with infrared drying oven
3The phen complex;
(2) precipitation method prepare Fe
3O
4Nanocrystalline
With 5.4060g FeCl
36H
2O, 2.7800g FeSO
47H
2O, 4.04g NH
4NO
3With the 1.9g molecular weight be that 20000 polyethylene glycol is dissolved in the 100mL deionized water, be heated to 50 ° of C and feed argon gas 30min, slow then dropping ammonia to the pH value of solution is 11, continue logical argon gas 20min and obtain black suspension, after this turbid liquid magnetic separation, wash successively three times with absolute ethyl alcohol and deionized water, product is placed the dry 12h of vacuum drying chamber of 60 ° of C, obtain the Fe that diameter is 8-10nm
3O
4Nanocrystalline;
(3) preparation spinning solution
High polymer templates adopts polyvinylpyrrolidone PVP in the spinning solution, and molecular weight is 90000, with 0.225g Eu (BA)
3Phen and 1.5g PVP join among the 8.5g DMF magnetic agitation 12h, obtain spinning solution I, 0.75g aniline and 0.9336g camphorsulfonic acid joined among the 6g DMF, add 1.5g PVP under the magnetic agitation after, put into the refrigerator 30min of 0 ° of C, the 1.84g ammonium persulfate is dissolved into 5g DMF, put into the refrigerator 30min of 0 ° of C after, dropwise join in the aniline solution, magnetic agitation 10min, the refrigerator of putting into 0 ° of C reacts 24h, obtains spinning solution II, with 1.5g Fe
3O
4Nanocrystalline being scattered among the 11g DMF, ultrasonic dispersion 15min adds 1.5g PVP then under the magnetic agitation, obtain spinning solution III;
(4) preparation [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions
Spinning head cuts three spinning heads arranged side by side that the flat identical syringe needle of diameter is close together and forms by three, three syringe needles are for cutting the 8# stainless steel syringe needle after putting down, external diameter is 0.8mm, internal diameter is 0.49mm, three spinning solutions that prepare are joined respectively in three syringe tubes, adopt electrostatic spinning technique, use perpendicular spray mode, shower nozzle is vertical with horizontal plane, and applying voltage is 16kV, and shower nozzle is 15cm to the curing distance of receiving screen wire netting, 15 ° of C～20 ° C of indoor temperature, relative humidity is 40%～50%, along with the volatilization of solvent, just can collect ganoid [Eu (BA) on as the wire netting of negative pole
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, the diameter of sub-thread nanofiber is 180nm, length is greater than 50 μ m.
Prepared [Eu (BA) in said process
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, the diameter of sub-thread nanofiber is 180nm, and length under the ultraviolet excitation of 276nm, is launched the bright red that main peak is positioned at 615nm greater than 50 μ m, and its electrical conductivity is 1.524 * 10
-6S/cm, saturation magnetization is 6.10emu/g, has good luminous, conduction and magnetic three functions, has realized goal of the invention.
Description of drawings
Fig. 1 is Fe
3O
4Nanocrystalline TEM photo;
Fig. 2 is Fe
3O
4Nanocrystalline XRD spectra;
Fig. 3 is [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] XRD spectra of three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions;
Fig. 4 is [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] the SEM photo of three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, this figure double as Figure of abstract;
Fig. 5 is [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] the EDS spectrogram of three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions;
Fig. 6 is [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] the exciting light spectrogram of three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions;
Fig. 7 is [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] the emission spectrum figure of three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions;
Fig. 8 is [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] the hysteresis curve figure of three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions.
The specific embodiment
The europium oxide Eu that the present invention is selected
2O
3Purity be 99.99%, polyvinylpyrrolidone PVP, molecular weight 90000, N, dinethylformamide DMF, aniline, camphorsulfonic acid, ammonium persulfate, nitric acid, benzoic acid HBA, phenanthroline phen, Iron(III) chloride hexahydrate, green vitriol, ammonium nitrate, molecular weight are 20000 polyethylene glycol, argon gas, absolute ethyl alcohol, NH
3H
2O is commercially available analysis net product, the self-control of deionized water laboratory; Used glass apparatus and equipment are instrument and equipments commonly used in the laboratory.
Embodiment: with 0.1760g Eu
2O
3Be dissolved in the red fuming nitric acid (RFNA), add a certain amount of absolute ethyl alcohol behind the evaporate to dryness, be mixed with Eu (NO
3)
3Ethanolic solution, in an amount of absolute ethyl alcohol, add the 0.3664g benzoic acid and the 0.1982g phenanthroline is mixed with mixed ligand solution, be heated to 50-60 ° of C, with Eu (NO
3)
3Ethanolic solution dropwise be added in the ligand solution, drip dense NH again
3H
2It is between 6～6.5 that O regulates pH, produces white precipitate, and constantly stirring reaction 3h after the centrifugation of gained sediment, uses deionized water and absolute ethanol washing 3 times successively, in the dry 12h of 60 ° of C, obtains Eu (BA) with infrared drying oven
3The phen complex; With 5.4060g FeCl
36H
2O, 2.7800g FeSO
47H
2O, 4.04g NH
4NO
3With the 1.9g molecular weight be that 20000 polyethylene glycol is dissolved in the 100mL deionized water, be heated to 50 ° of C and feed argon gas 30min, slow then dropping ammonia to the pH value of solution is 11, continue logical argon gas 20min and obtain black suspension, after this turbid liquid magnetic separation, wash successively three times with absolute ethyl alcohol and deionized water, product is placed the dry 12h of vacuum drying chamber of 60 ° of C, obtain the Fe that diameter is 8-10nm
3O
4Nanocrystalline, see shown in Figure 1; Prepared Fe
3O
4Nanocrystalline have good crystallinity, the d value of its diffraction maximum and relative intensity and a Fe
3O
4The listed d value of PDF standard card (74-0748) consistent with relative intensity, belong to cubic system, see shown in Figure 2; High polymer templates adopts polyvinylpyrrolidone PVP in the spinning solution, and molecular weight is 90000, with 0.225g Eu (BA)
3Phen and 1.5g PVP join among the 8.5g DMF magnetic agitation 12h, obtain spinning solution I, 0.75g aniline and 0.9336g camphorsulfonic acid joined among the 6g DMF, add 1.5g PVP under the magnetic agitation after, put into the refrigerator 30min of 0 ° of C, the 1.84g ammonium persulfate is dissolved into 5g DMF, put into the refrigerator 30min of 0 ° of C after, dropwise join in the aniline solution, magnetic agitation 10min, the refrigerator of putting into 0 ° of C reacts 24h, obtains spinning solution II, with 1.5g Fe
3O
4Nanocrystalline being scattered among the 11g DMF, ultrasonic dispersion 15min adds 1.5g PVP then under the magnetic agitation, obtain spinning solution III; Spinning head cuts three spinning heads arranged side by side that the flat identical syringe needle of diameter is close together and forms by three, three syringe needles are for cutting the 8# stainless steel syringe needle after putting down, external diameter is 0.8mm, internal diameter is 0.49mm, three spinning solutions that prepare are joined respectively in three syringe tubes, adopt electrostatic spinning technique, use perpendicular spray mode, shower nozzle is vertical with horizontal plane, and applying voltage is 16kV, and shower nozzle is 15cm to the curing distance of receiving screen wire netting, 15 ° of C～20 ° C of indoor temperature, relative humidity is 40%～50%, along with the volatilization of solvent, just can collect ganoid [Eu (BA) on as the wire netting of negative pole
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, using Hall effect Department of Survey its electrical conductivity of unified test is 1.524 * 10
-6S/cm.Prepared [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions have tangible Fe
3O
4Diffraction maximum, show three gangs of intrafascicular Fe of containing of parallel nanofiber of prepared photoelectromagnetic three functions
3O
4Nanocrystalline, see shown in Figure 3; Prepared [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, be three bursts of parallel bundles of nanofibers structures, the diameter of sub-thread nanofiber is 180nm, length is seen shown in Figure 4 greater than 50 μ m; Prepared [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions are made up of C, N, O, Eu and Fe element, and S derives from initiator ammonium persulfate, and the Au conductive layer of surface plating was seen shown in Figure 5 when Au derived from the SEM sample preparation; When the monitoring wavelength is 615nm, [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] the excitation spectrum highest peak of three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions is positioned at the 276nm place, belongs to the π → π of part
*Transition is seen shown in Figure 6; Under the ultraviolet excitation of 276nm, [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions launch the bright red that main peak is positioned at 615nm, and it is corresponding to Eu
3+Ion
5D
0→
7F
2Transition belongs to Eu
3+Force electric dipole transition, see shown in Figure 7; [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions have stronger magnetic, and its hysteresis curve is seen shown in Figure 8, and saturation magnetization is 6.10emu/g.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (2)
1. three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, it is characterized in that nano-fiber material presents three bursts of parallel bundles of nanofibers structures, have luminous, conduction and three kinds of functions of magnetic, the diameter of three strands of intrafascicular sub-thread nanofibers of parallel nanofiber is 180nm, and length is greater than 50 μ m.
2. the preparation method of three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions as claimed in claim 1, it is characterized in that, adopt electrostatic spinning technique, use three spinning heads arranged side by side, high polymer templates is the polyvinylpyrrolidone PVP of molecular weight 90000, N, dinethylformamide DMF are solvent, and the preparation product is [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, the steps include:
(1) precipitation method prepare Eu (BA)
3The phen complex
With 0.1760g Eu
2O
3Be dissolved in the red fuming nitric acid (RFNA), add a certain amount of absolute ethyl alcohol behind the evaporate to dryness, be mixed with Eu (NO
3)
3Ethanolic solution, in an amount of absolute ethyl alcohol, add the 0.3664g benzoic acid and the 0.1982g phenanthroline is mixed with mixed ligand solution, be heated to 50-60 ° of C, with Eu (NO
3)
3Ethanolic solution dropwise be added in the ligand solution, drip dense NH again
3H
2It is between 6～6.5 that O regulates pH, produces white precipitate, and constantly stirring reaction 3h after the centrifugation of gained sediment, uses deionized water and absolute ethanol washing 3 times successively, in the dry 12h of 60 ° of C, obtains Eu (BA) with infrared drying oven
3The phen complex;
(2) precipitation method prepare Fe
3O
4Nanocrystalline
With 5.4060g FeCl
36H
2O, 2.7800g FeSO
47H
2O, 4.04g NH
4NO
3With the 1.9g molecular weight be that 20000 polyethylene glycol is dissolved in the 100mL deionized water, be heated to 50 ° of C and feed argon gas 30min, slow then dropping ammonia to the pH value of solution is 11, continue logical argon gas 20min and obtain black suspension, after this turbid liquid magnetic separation, wash successively three times with absolute ethyl alcohol and deionized water, product is placed the dry 12h of vacuum drying chamber of 60 ° of C, obtain the Fe that diameter is 8-10nm
3O
4Nanocrystalline;
(3) preparation spinning solution
High polymer templates adopts polyvinylpyrrolidone PVP in the spinning solution, and molecular weight is 90000, with 0.225g Eu (BA)
3Phen and 1.5g PVP join among the 8.5g DMF magnetic agitation 12h, obtain spinning solution I, 0.75g aniline and 0.9336g camphorsulfonic acid joined among the 6g DMF, add 1.5g PVP under the magnetic agitation after, put into the refrigerator 30min of 0 ° of C, the 1.84g ammonium persulfate is dissolved into 5g DMF, put into the refrigerator 30min of 0 ° of C after, dropwise join in the aniline solution, magnetic agitation 10min, the refrigerator of putting into 0 ° of C reacts 24h, obtains spinning solution II, with 1.5g Fe
3O
4Nanocrystalline being scattered among the 11g DMF, ultrasonic dispersion 15min adds 1.5g PVP then under the magnetic agitation, obtain spinning solution III;
(4) preparation [Eu (BA)
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions
Spinning head cuts three spinning heads arranged side by side that the flat identical syringe needle of diameter is close together and forms by three, three syringe needles are for cutting the 8# stainless steel syringe needle after putting down, external diameter is 0.8mm, internal diameter is 0.49mm, three spinning solutions that prepare are joined respectively in three syringe tubes, adopt electrostatic spinning technique, use perpendicular spray mode, shower nozzle is vertical with horizontal plane, and applying voltage is 16kV, and shower nozzle is 15cm to the curing distance of receiving screen wire netting, 15 ° of C～20 ° C of indoor temperature, relative humidity is 40%～50%, along with the volatilization of solvent, just can collect ganoid [Eu (BA) on as the wire netting of negative pole
3Phen/PVP] // [PANI/PVP] // [Fe
3O
4/ PVP] three bursts of parallel bundles of nanofibers of photoelectromagnetic three functions, the diameter of sub-thread nanofiber is 180nm, and length under the ultraviolet excitation of 276nm, is launched the bright red that main peak is positioned at 615nm greater than 50 μ m, and its electrical conductivity is 1.524 * 10
-6S/cm, saturation magnetization is 6.10emu/g, that these three bursts of parallel bundles of nanofibers have is luminous, conduction and magnetic three functions.
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| CN104532394A (en) * | 2014-12-18 | 2015-04-22 | 长春理工大学 | Janus nano-belt array with three functions of anisotropy, conductivity and magneto-optic and preparation method thereof |
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| CN108374209A (en) * | 2018-02-02 | 2018-08-07 | 长春理工大学 | Three function Janus nanofiber array films of anisotropic conductive magneto-optic |
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