CN106283397A - Green emitting electromagnetism three function two-layer composite nano-fiber membrane and preparation method thereof - Google Patents
Green emitting electromagnetism three function two-layer composite nano-fiber membrane and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4374—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece using different kinds of webs, e.g. by layering webs
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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Abstract
The present invention relates to green emitting electromagnetism three function two-layer composite nano-fiber membrane and preparation method thereof, belong to technical field of nanometer material preparation.The present invention includes four steps: (1) sedimentation method prepare the Fe of Coated with Oleic Acid3O4Nanocrystalline；(2) sedimentation method prepare Tb (TTA)3(TPPO)2Coordination compound；(3) preparation spinning liquid；(4) [Tb (TTA) is prepared3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer composite nano-fiber membrane, use single shaft electrostatic spinning technique to prepare.Prepared green emitting electromagnetism three function two-layer composite nano-fiber membrane has good green emitting electroconductive magnetic three function simultaneously.The method of the present invention is simple, can produce in batches, and this novel nano structural material has broad application prospects.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, in particular relate to that green emitting electromagnetism three function two-layer is compound to be received
Rice fibrous membrane and preparation method thereof.
Background technology
Simple function applications to nanostructures is limited in scope, and the range of application of difunctional or multi-functional nanometer material is more
Extensively, this kind of material more characteristic and captivation, therefore, multi-functional nanometer material is paid high attention to by researcher.Along with nanometer
The development of science and technology, nano material is by simple function, as having the characteristics of luminescence, electric conductivity or magnetic, towards difunctional and many merits
Can develop in direction, as having, magneto-optic, photoelectricity or electromagnetism be difunctional and photoelectromagnetic three function, so can be in a kind of nanostructured
Realizing difunctional or three functions on material, the development to nano-device, nanotechnology and relevant science and technology has important
Meaning.Such as, magnetic-fluorescent dual-function nano composite material is that medical diagnosis on disease provides a kind of new platform with treatment, due to
Their difunctional character makes " the finding-detection-treatment " of disease to be integrally forming.The use of this nano composite material will enter one
Step is improved the efficiency of diagnosis and reduces side effect, causes the highest attention of researcher.Electromagnetism dual-functional nanometer complex is at thunder
Reach the aspects such as ripple absorption, electromagnetic shielding, antistatic coating and sensor to have broad application prospects.
Ferroso-ferric oxide Fe3O4It it is a kind of important and wide variety of magnetic material.People have used multiple method, as
The sedimentation method, sol-gel process, microemulsion method, hydro-thermal are successfully made with methods such as solvent-thermal method, thermal decomposition method, method of electrostatic spinning
For having 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 terbium coordination compound Tb (TTA)3(TPPO)2, Tb3+For europium ion, TTA is 2-thenoyl trifluoropropyl
Ketone root, TPPO is triphenylphosphine oxide, becomes the green emitting material of unique energy because of the electronic configuration of terbium ion uniqueness
Material, such as luminous intensity height, good stability, fluorescence quantum yield height, the advantage such as monochromaticity is good, is a kind of wide variety of phosphor
Material.Polyaniline PANI due to its be readily synthesized, the advantage such as electrical conductivity is high and environmental stability is good, have become as conducting polymer and lead
One of focus of territory research.People have synthesized the one-dimensional nano structures such as nano wire, nanometer rods, nanotube and nanofiber
Polyaniline PANI, therefore, utilizes magnetic Fe3O4Nanocrystalline, rare earth terbium emitting complexes Tb (TTA)3(TPPO)2And conducting polyaniline
Amine PANI constructs that to have the nano material of photoelectromagnetic three functional characteristic be preferable material.
Existing research is it has been proved that work as dark colour electrically conductive polyaniline PANI and magnetic Fe3O4Direct with rare earth compounding
Mixing, can significantly reduce its illumination effect, the illumination effect that rare earth compounding to be obtained is good, 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)
It is compounded to form nano fibrous membrane, by rare earth compounding Tb (TTA)3(TPPO)2It is compounded to form nanometer with polyvinylpyrrolidone PVP
Fibrous membrane, then by both Film laminateds to forming upper and lower two-layer composite membrane together, it is possible to realize polyaniline PANI and Fe3O4
Efficiently separate with rare earth compounding, thus it is fine to obtain green emitting of good performance-conduction-magnetic three function two-layer composite Nano
Dimension film, this novel membrane material will have important application prospect, have not yet to see relevant document report.
The United States Patent (USP) of Patent No. 1975504 discloses a relevant electrospinning process (electrospinning)
Technical scheme, the method is to prepare continuous print, have a kind of effective ways of the micro nanometer fiber of macro length, by
First Formhals proposed in 1934.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making charged
Macromolecular solution or melt are sprayed by nozzle by the traction of electrostatic force in electrostatic field, invest the receiving screen on opposite, thus real
Existing wire drawing, then, solvent evaporation, or melt cooling at normal temperatures solidifies to room temperature, obtains micro nanometer fiber, these fibers
It is stacked into and is the formation of micro nanometer fiber film together.People used electrostatic spinning technique be prepared for photoelectromagnetic simple function,
Difunctional and three-function nano fibrous membrane.Q.Z.Yu, et al. uses electrostatic spinning technique to be prepared for having single conducting function
Polyaniline PANI nano fibrous membrane [Mater.Sci.Eng.B, 2008,150,70-76]；Dong Xiangting etc. use electrostatic spinning skill
Art is prepared for the PAN/Eu (BA) with single lighting function3Phen luminous nano fibre film [New Chemical Materials, 2008,36
(9),49-52]；Wang Ce etc. use method of electrostatic spinning to be prepared for having magnetic polyvinylpyrrolidone/ferroso-ferric oxide and are combined
Nano-fiber film [SCI, 2006,27 (10), 2002-2004]；Qingbiao Yang, et al. uses
Electrostatic spinning technique is prepared for Fe2O3nanoparticles/Eu(DBM)3(Bath) Composite Double function magneto-optic nano fibrous membrane
[Journal of Colloid and Interface Science, 2010,350,396-401], Dong Xiangting etc. uses electrostatic
Spining technology is prepared for Fe3O4/Eu(BA)3Phen/PVP magneto-optic double-function composite nano-fiber membrane [Journal of
Nanoparticle Research,2012,14(10):1203-1209]、Eu(BA)3Phen/PANI/PVP photoelectricity is difunctional multiple
Close nano fibrous membrane [SCI, 2012,33 (8), 1657-1662] and Eu (BA)3phen/PANI/Fe3O4/
PVP photoelectromagnetic three-function nano fibrous membrane [Journal of Materials Science:Materials in
Electronics,2014,25(3),1309-1316].At present, have no and utilize electrostatic spinning technique to prepare green emitting electromagnetism three
The relevant report of function two-layer composite nano-fiber membrane.
When utilizing electrostatic spinning technique to prepare nano material, the kind of raw material, the molecular weight of high polymer templates, spinning liquid
The structure of composition, spinning process parameter and spinning head pattern and the size of final products are all had a major impact.The present invention adopts
With single spraying head electrostatic spinning technique, with Tb (TTA)3(TPPO)2Coordination compound, PVP and the mixed liquor of N,N-dimethylformamide DMF
For a kind of spinning liquid, referred to as spinning liquid I, by the Fe of Coated with Oleic Acid3O4Nanocrystalline, PAN, aniline, camphorsulfonic acid, Ammonium persulfate.,
DMF mixes, and constitutes another kind of spinning liquid, referred to as spinning liquid II after aniline polymerization becomes polyaniline.Control the viscosity of spinning liquid extremely
Close important, under optimal process conditions, first spinning liquid I is carried out electrostatic spinning, obtain Tb (TTA)3(TPPO)2/ PVP is green
Luminous nano fibre film, carries out electrostatic spinning by spinning liquid II afterwards, at Tb (TTA)3(TPPO)2/ PVP luminous nano fibre film
Upper compound PANI/Fe3O4/ PAN electromagnetism dual-functional nanometer fibrous membrane, has obtained [the Tb (TTA) of novel structure3(TPPO)2/
PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three functionally descends two-layer composite nano-fiber membrane.
Summary of the invention
Electrostatic spinning technique is prepared for photoelectromagnetic simple function, difunctional and three-function nano is fine in employing in the introduction
Dimension film, the raw material used, template, solvent and final target product are different with the method for the present invention.The present invention adopts
It is prepared for [Tb (TTA) with electrostatic spinning technique3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three is functionally
Lower two-layer composite nano-fiber membrane, adds for nano fibrous membrane field and a kind of has the nano combined thin of new features and new construction
Membrane material.
The present invention is achieved in that and prepares Tb (TTA) initially with the sedimentation method3(TPPO)2Coordination compound and Coated with Oleic Acid
Fe3O4Nanocrystalline, with Tb (TTA)3(TPPO)2The mixed liquor of coordination compound, PVP and N,N-dimethylformamide DMF is that one is spun
Silk liquid, referred to as spinning liquid I, by the Fe of Coated with Oleic Acid3O4Nanocrystalline, PAN, aniline, camphorsulfonic acid, Ammonium persulfate., DMF mixing, treats
Aniline polymerization constitutes another kind of spinning liquid, referred to as spinning liquid II after becoming polyaniline, the viscosity controlling spinning liquid is most important.Use
Single spinning head electrostatic spinning technique carries out electrostatic spinning, under optimal process conditions, it is thus achieved that [Tb (TTA)3(TPPO)2/PVP]/
[PANI/Fe3O4/ PAN] green emitting electromagnetism three functionally descends two-layer composite nano-fiber membrane, the steps include:
(1) sedimentation method prepare the Fe of Coated with Oleic Acid3O4Nanocrystalline
By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3With 1.9000g molecular weight it is
The Polyethylene Glycol of 20000 is dissolved in 100mL deionized water, is heated to 50 DEG C and is passed through argon 30min, being then slowly added dropwise ammonia
PH value to solution is 11, continues logical argon 20min and obtains black suspension, after this suspension Magneto separate, uses dehydrated alcohol
Wash successively with deionized water three times, product is placed in the vacuum drying oven of 60 DEG C and is dried 12h, obtain a diameter of 8-10nm's
Fe3O4Nanocrystalline；Take the Fe prepared by 2.0000g3O4Nanocrystalline it is dispersed in the 100mL deionized water being passed through 30min argon
And ultrasonic disperse 20min, then solution is heated to 80 DEG C under argon shield, and adds 1mL oleic acid, then proceed to reaction
40min, carries out Magneto separate by obtained precipitation, removes water layer and will be deposited in 60 DEG C of vacuum drying ovens dry 6h, obtaining
The Fe of Coated with Oleic Acid3O4Nanocrystalline；
(2) sedimentation method prepare Tb (TTA)3(TPPO)2Coordination compound
By 1.8690g Tb4O7Powder is dissolved in 20mL concentrated nitric acid, and heating is evaporated the unnecessary nitric acid of removing and obtains Tb
(NO3)3·6H2O crystal, adds 20mL dehydrated alcohol, is configured to Tb (NO3)3Ethanol solution；By 6.6670g 2-thenoyl
Trifluoroacetone HTTA and 5.5680g triphenylphosphine oxide TPPO is dissolved in the dehydrated alcohol of 100mL jointly, then by prepared Tb
(NO3)3Ethanol solution is slowly added thereto, and the pH value of regulation solution is between 6.5-7.0, is heated to 60 DEG C, stirs 3h, by institute
The precipitation water obtained and dehydrated alcohol wash 3 times successively, are placed on by product in 60 DEG C of baking ovens and are dried 12h, obtain Tb (TTA)3
(TPPO)2Powder；
(3) preparation spinning liquid
By 0.1000g Tb (TTA)3(TPPO)2Joining in 4.5000g DMF, adding 1.0000g molecular weight after dissolving is
The polyvinylpyrrolidone PVP of 90000, magnetic agitation 24h, obtain spinning liquid I；Fe by 0.9000g Coated with Oleic Acid3O4Nanometer
Crystalline substance joins in 7.000g DMF, ultrasonic disperse 20min, adds the polyacrylonitrile (PAN) that 0.9000g molecular weight is 86000, in
Stir 5h at 60 DEG C, dissolved and obtain uniform Colloidal fluid, add 0.6300g aniline ANI and 0.7856g camphorsulfonic acid
CSA, magnetic agitation 2h, 1.5437g Ammonium persulfate. APS is dissolved in 2.0000g DMF, magnetic agitation 2h, molten by these two parts
Liquid puts into cold preservation 1h in the refrigerator of 5 DEG C, mixes, these two parts of solution after magnetic agitation 3h, by mixed liquor afterwards in ice-water bath
Put into cold preservation 24h in the refrigerator of 5 DEG C, obtain spinning liquid II；
(4) [Tb (TTA) is prepared3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer is again
Close nano fibrous membrane
Spinning liquid I is injected in a 5mL syringe with 1mL plastic spray gun head, the positive pole of high-voltage DC power supply with
In syringe, copper wire electrode is connected, and negative pole is connected with receiving device wire gauze, use perpendicular spray mode, lance head and wire gauze away from
From for 10cm, spinning voltage is 13kV, and ambient temperature is 20-25 DEG C, and relative humidity is 20%-50%, carries out electrostatic spinning and obtains
To Tb (TTA)3(TPPO)2/ PVP luminous nano fibre film, after spinning liquid I exhausts, is injected into spinning liquid II in syringe,
Proceed electrostatic spinning, at Tb (TTA)3(TPPO)2PANI/Fe is obtained on/PVP luminous nano fibre film3O4/ PAN electromagnetism is received
Rice fibrous membrane, along with the volatilization of solvent, finally gives [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting
Electromagnetism three function two-layer composite nano-fiber membrane.
[Tb (TTA) prepared in above process3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism
Three function two-layer composite nano-fiber membranes, are composited by double-layer films, Tb (TTA)3(TPPO)2/ PVP green emitting Nanowire
The average thickness of dimension layer is 122.59 μm, PANI/Fe3O4The average thickness of/PAN electromagnetism nanofiber layer is 300.63 μm；?
Under the ultraviolet excitation of 357nm, [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two
In layer composite nano-fiber membrane, luminous side is launched main peak and is positioned at the bright green glow of 545nm；[Tb(TTA)3(TPPO)2/PVP]/
[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer composite nano-fiber membrane conducts electricity the average conductivity of side it is
5.12×10-3S·cm-1；[Tb(TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer is again
The saturation magnetization closing nano fibrous membrane is 3.785emu/g, and prepared two-layer composite nano-fiber membrane has good sending out
Light-conduction-magnetic three function, it is achieved that goal of the invention.
Accompanying drawing explanation
Fig. 1 is [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer be combined
The XRD spectra of nano fibrous membrane；
Fig. 2 is [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer be combined
The SEM photograph of nano fibrous membrane, this figure also serves as Figure of abstract；
Fig. 3 is [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer be combined
The optical microscope photograph of nano fibrous membrane；
Fig. 4 is [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer be combined
The exciting light spectrogram of nano fibrous membrane；
Fig. 5 is [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer be combined
The emission spectrum figure of nano fibrous membrane；
Fig. 6 is [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer be combined
The hysteresis curve figure of nano fibrous membrane.
Detailed description of the invention
Terbia. Diterbium trioxide Tb selected by the present invention4O7Purity be 99.99%, 2-thenoyltrifluoroacetone, triphenyl aoxidize
Phosphine, DMF, Iron(III) chloride hexahydrate, green vitriol, ammonium nitrate, molecular weight is the poly-second of 20000
Glycol, nitric acid, molecular weight is the polyvinylpyrrolidone of 90000, and molecular weight is the polyacrylonitrile of 86000, dehydrated alcohol, ammonia
Water, aniline, camphorsulfonic acid, Ammonium persulfate., oleic acid, argon is commercially available analytical pure product；Deionized water laboratory is made by oneself；Used
Glass apparatus and equipment be instrument and equipment conventional in laboratory.
Embodiment: by 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3And 1.9000g
Molecular weight be 20000 Polyethylene Glycol be dissolved in 100mL deionized water, be heated to 50 DEG C and be passed through argon 30min, the most slowly
Dropping ammonia is 11 to the pH value of solution, continues logical argon 20min and obtains black suspension, after this suspension Magneto separate, uses
Dehydrated alcohol and deionized water wash three times successively, are placed in by product in the vacuum drying oven of 60 DEG C and are dried 12h, obtain a diameter of
The Fe of 8-10nm3O4Nanocrystalline；Take the Fe prepared by 2.0000g3O4Nanocrystalline being dispersed in is passed through the 100mL of 30min argon
In ionized water and ultrasonic disperse 20min, then solution is heated to 80 DEG C under argon shield, and adds 1mL oleic acid, then continue
Continuous reaction 40min, carries out Magneto separate by obtained precipitation, removes water layer and will be deposited in 60 DEG C of vacuum drying ovens dry
6h, obtains the Fe of Coated with Oleic Acid3O4Nanocrystalline；By 1.8690g Tb4O7Powder is dissolved in 20mL concentrated nitric acid, and heating is evaporated and removes
Unnecessary nitric acid is gone to obtain Tb (NO3)3·6H2O crystal, adds 20mL dehydrated alcohol, is configured to Tb (NO3)3Ethanol solution；Will
6.6670g 2-thenoyltrifluoroacetone HTTA and 5.5680g triphenylphosphine oxide TPPO are dissolved in the anhydrous second of 100mL jointly
In alcohol, then by prepared Tb (NO3)3Ethanol solution is slowly added thereto, and the pH value of regulation solution is between 6.5-7.0, heating
To 60 DEG C, stir 3h, obtained precipitation water and dehydrated alcohol are washed 3 times successively, product is placed in 60 DEG C of baking ovens dry
Dry 12h, obtains Tb (TTA)3(TPPO)2Powder；By 0.1000g Tb (TTA)3(TPPO)2Join in 4.5000g DMF, molten
Add the polyvinylpyrrolidone PVP that 1.0000g molecular weight is 90000, magnetic agitation 24h after solution, obtain spinning liquid I；Will
The Fe of 0.9000g Coated with Oleic Acid3O4Nanocrystalline join in 7.000g DMF, ultrasonic disperse 20min, add 0.9000g molecule
Amount is the polyacrylonitrile (PAN) of 86000, stirs 5h, dissolved and obtain uniform Colloidal fluid, add 0.6300g at 60 DEG C
Aniline ANI and 0.7856g camphorsulfonic acid CSA, magnetic agitation 2h, 1.5437g Ammonium persulfate. APS is dissolved in 2.0000g DMF
In, magnetic agitation 2h, these two parts of solution are put into cold preservation 1h in the refrigerator of 5 DEG C, afterwards these two parts of solution is mixed in ice-water bath
Close, after magnetic agitation 3h, mixed liquor is put into cold preservation 24h in the refrigerator of 5 DEG C, obtains spinning liquid II；Spinning liquid I is injected one
In 5mL syringe with 1mL plastic spray gun head, the positive pole of high-voltage DC power supply is connected with copper wire electrode in syringe, negative pole
Being connected with receiving device wire gauze, use perpendicular spray mode, lance head is 10cm with the distance of wire gauze, and spinning voltage is 13kV,
Ambient temperature is 20-25 DEG C, and relative humidity is 20%-50%, carries out electrostatic spinning and obtains Tb (TTA)3(TPPO)2/ PVP is luminous
Nano fibrous membrane, after spinning liquid I exhausts, is injected into spinning liquid II in syringe, proceeds electrostatic spinning, at Tb
(TTA)3(TPPO)2PANI/Fe is obtained on/PVP luminous nano fibre film3O4/ PAN electromagnetism nano fibrous membrane, along with waving of solvent
Send out, finally give [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer is compound receives
Rice fibrous membrane.Described [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer is again
Close in nano fibrous membrane containing Emission in Cubic Fe3O4Nanocrystalline, as shown in Figure 1；Described [Tb (TTA)3(TPPO)2/PVP]/
[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer composite nano-fiber membrane, double-layer films it is composited, Tb
(TTA)3(TPPO)2The average thickness of/PVP green emitting nanofiber layer is 122.59 μm, PANI/Fe3O4/ PAN electromagnetism nanometer
Fibrolaminar average thickness is 300.63 μm, as shown in Figure 2；Described [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/
PAN] the side color of green emitting electromagnetism three function two-layer composite nano-fiber membrane is relatively deep, comprises polyaniline and Fe3O4Nanometer
Crystalline substance, opposite side color is shallower, comprises colourless Tb (TTA)3(TPPO)2Coordination compound, as shown in Figure 3；Using 545nm as monitoring ripple
Long, [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer composite nano-fiber membrane
Having a wide excitation band at 200-450nm, its peak value, at 357nm, can be classified as π → π * transition of part, see Fig. 4 institute
Show；Under the ultraviolet excitation of 357nm, [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three
Function two-layer composite nano-fiber membrane is launched main peak and is positioned at the bright green glow of 545nm, and it is corresponding to Tb ion5D4→7F5Jump
Move, as shown in Figure 5；Made [the Tb (TTA) stated3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function
Two-layer composite nano-fiber membrane has stronger magnetic, and saturation magnetization is 3.785emu/g, as shown in Figure 6；Application Hall
Effect tester records [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer be combined
The average conductivity of side of conducting electricity in nano fibrous membrane is 5.12 × 10-3S·cm-1。
Certainly, the present invention also can have other various embodiments, in the case of without departing substantially from present invention spirit and essence thereof, ripe
Know those skilled in the art to work as and can make various corresponding change and deformation according to the present invention, but these change accordingly and become
Shape all should belong to the protection domain of appended claims of the invention.
Claims (2)
1. green emitting electromagnetism three function two-layer composite nano-fiber membrane, it is characterised in that by Tb (TTA)3(TPPO)2/ PVP is green
Color luminous nano fibre layer and PANI/Fe3O4/ PAN electromagnetism nanofiber layer is composited up and down, two-layer composite nano-fiber membrane
There is green emitting, conduction and three kinds of functions of magnetic, Tb (TTA) simultaneously3(TPPO)2The average thickness of/PVP luminous nano fibre layer
Degree is 122.59 μm, PANI/Fe3O4The average thickness of/PAN electromagnetism nanofiber layer is 300.63 μm.
2. a preparation method for green emitting electromagnetism three function two-layer composite nano-fiber membrane as claimed in claim 1, its
Being characterised by, using single spinning head electrostatic spinning technique, preparing product is [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/
PAN] green emitting electromagnetism three function two-layer composite nano-fiber membrane, the steps include:
(1) sedimentation method prepare the Fe of Coated with Oleic Acid3O4Nanocrystalline
By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3With 1.9000g molecular weight it is
The Polyethylene Glycol of 20000 is dissolved in 100mL deionized water, is heated to 50 DEG C and is passed through argon 30min, being then slowly added dropwise ammonia
PH value to solution is 11, continues logical argon 20min and obtains black suspension, after this suspension Magneto separate, uses dehydrated alcohol
Wash successively with deionized water three times, product is placed in the vacuum drying oven of 60 DEG C and is dried 12h, obtain a diameter of 8-10nm's
Fe3O4Nanocrystalline；Take the Fe prepared by 2.0000g3O4Nanocrystalline it is dispersed in the 100mL deionized water being passed through 30min argon
And ultrasonic disperse 20min, then solution is heated to 80 DEG C under argon shield, and adds 1mL oleic acid, then proceed to reaction
40min, carries out Magneto separate by obtained precipitation, removes water layer and will be deposited in 60 DEG C of vacuum drying ovens dry 6h, obtaining
The Fe of Coated with Oleic Acid3O4Nanocrystalline；
(2) sedimentation method prepare Tb (TTA)3(TPPO)2Coordination compound
By 1.8690g Tb4O7Powder is dissolved in 20mL concentrated nitric acid, and heating is evaporated the unnecessary nitric acid of removing and obtains Tb (NO3)3·
6H2O crystal, adds 20mL dehydrated alcohol, is configured to Tb (NO3)3Ethanol solution；By 6.6670g 2-thenoyl trifluoropropyl
Ketone HTTA and 5.5680g triphenylphosphine oxide TPPO is dissolved in the dehydrated alcohol of 100mL jointly, then by prepared Tb (NO3)3
Ethanol solution is slowly added thereto, and the pH value of regulation solution is between 6.5-7.0, is heated to 60 DEG C, stirs 3h, by obtained
Precipitation water and dehydrated alcohol wash 3 times successively, are placed on by product in 60 DEG C of baking ovens and are dried 12h, obtain Tb (TTA)3(TPPO)2
Powder；
(3) preparation spinning liquid
By 0.1000g Tb (TTA)3(TPPO)2Joining in 4.5000g DMF, adding 1.0000g molecular weight after dissolving is
The polyvinylpyrrolidone PVP of 90000, magnetic agitation 24h, obtain spinning liquid I；Fe by 0.9000g Coated with Oleic Acid3O4Nanometer
Crystalline substance joins in 7.000g DMF, ultrasonic disperse 20min, adds the polyacrylonitrile (PAN) that 0.9000g molecular weight is 86000, in
Stir 5h at 60 DEG C, dissolved and obtain uniform Colloidal fluid, add 0.6300g aniline ANI and 0.7856g camphorsulfonic acid
CSA, magnetic agitation 2h, 1.5437g Ammonium persulfate. APS is dissolved in 2.0000g DMF, magnetic agitation 2h, molten by these two parts
Liquid puts into cold preservation 1h in the refrigerator of 5 DEG C, mixes, these two parts of solution after magnetic agitation 3h, by mixed liquor afterwards in ice-water bath
Put into cold preservation 24h in the refrigerator of 5 DEG C, obtain spinning liquid II；
(4) [Tb (TTA) is prepared3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer composite Nano
Fibrous membrane
Spinning liquid I is injected in a 5mL syringe with 1mL plastic spray gun head, the positive pole of high-voltage DC power supply and injection
In device, copper wire electrode is connected, and negative pole is connected with receiving device wire gauze, uses perpendicular spray mode, and lance head with the distance of wire gauze is
10cm, spinning voltage is 13kV, and ambient temperature is 20-25 DEG C, and relative humidity is 20%-50%, carries out electrostatic spinning and obtains Tb
(TTA)3(TPPO)2/ PVP luminous nano fibre film, after spinning liquid I exhausts, is injected into spinning liquid II in syringe, continues
Carry out electrostatic spinning, at Tb (TTA)3(TPPO)2PANI/Fe is obtained on/PVP luminous nano fibre film3O4/ PAN electromagnetism Nanowire
Dimension film, along with the volatilization of solvent, finally gives [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism
Three function two-layer composite nano-fiber membranes, Tb (TTA)3(TPPO)2The average thickness of/PVP green emitting nanofiber layer is
122.59 μm, PANI/Fe3O4The average thickness of/PAN electromagnetism nanofiber layer is 300.63 μm；Ultraviolet excitation at 357nm
Under, [Tb (TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer composite nano-fiber membrane
Middle luminous side is launched main peak and is positioned at the bright green glow of 545nm；[Tb(TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/PAN]
The average conductivity of side of conducting electricity in green emitting electromagnetism three function two-layer composite nano-fiber membrane is 5.12 × 10-3S·cm-1；
[Tb(TTA)3(TPPO)2/PVP]/[PANI/Fe3O4/ PAN] green emitting electromagnetism three function two-layer composite nano-fiber membrane full
Being 3.785emu/g with the intensity of magnetization, prepared two-layer composite nano-fiber membrane has good green emitting electroconductive magnetic three
Function.
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