CN107794596A - Double anisotropic conductive Janus structural membranes of red fluorescence and preparation method thereof - Google Patents

Double anisotropic conductive Janus structural membranes of red fluorescence and preparation method thereof Download PDF

Info

Publication number
CN107794596A
CN107794596A CN201711119678.1A CN201711119678A CN107794596A CN 107794596 A CN107794596 A CN 107794596A CN 201711119678 A CN201711119678 A CN 201711119678A CN 107794596 A CN107794596 A CN 107794596A
Authority
CN
China
Prior art keywords
janus
pmma
anisotropic conductive
red fluorescence
phen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201711119678.1A
Other languages
Chinese (zh)
Inventor
董相廷
李晓冰
马千里
田娇
李丹
奚雪
于文生
王昕璐
王进贤
刘桂霞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun University of Science and Technology
Original Assignee
Changchun University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun University of Science and Technology filed Critical Changchun University of Science and Technology
Priority to CN201711119678.1A priority Critical patent/CN107794596A/en
Publication of CN107794596A publication Critical patent/CN107794596A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • 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
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • 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
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds 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

Landscapes

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

Abstract

The present invention relates to double anisotropic conductive Janus structural membranes of red fluorescence and preparation method thereof, belong to technical field of nanometer material preparation.The present invention includes five steps：(1) precipitation method prepare Eu (BA)3(phen) complex；(2) polymetylmethacrylate is prepared；(3) spinning solution is prepared；(4) [Eu (BA) is prepared3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus nano-band array films, prepared using double-spinneret electrostatic spinning technique arranged side by side；(5) the double anisotropic conductive Janus structural membranes of red fluorescence are prepared.Prepared Janus structural membranes have good red fluorescence and double anisotropic conductive functions simultaneously.The method of the present invention is simple and easy, can produce in batches, this new nano structural material has broad application prospects.

Description

Double anisotropic conductive Janus structural membranes of red fluorescence and preparation method thereof
Technical field
The present invention relates to technical field of nanometer material preparation, in particulars relate to the double anisotropic conductive Janus of red fluorescence Structural membrane and preparation method thereof.
Background technology
Anisotropic conductive film is a kind of new electronic component interconnecting material, it have electric conductivity in one direction and Insulating properties on other directions, be widely used in Electronic Packaging, chip is fixed and electrode bonding etc. field.Led by it Electric direction classification, can be divided into following two class：I type anisotropic conductive films：Thickness side of this anisotropic conductive film along film To conduction, and being insulated along film surface direction, the technology of preparing of this anisotropic conductive film is highly developed, and by widely Using in the electronic device；II type anisotropic conductive films：This anisotropic conductive film has not along the different directions of its film surface With electric conductivity, generally along in two vertical direction of film surface, a direction conduction, another direction insulation, have it is each to Different in nature electric conductivity.The research of II type anisotropic conductive films is still in the laboratory exploratory stage, be not implemented industrialized production and Using.
Janus materials refer to two kinds of chemical compositions or a kind of chemical composition but structure difference has clearly in same system Partitioned organization, thus there is double properties such as hydrophilic/hydrophobic, polar/non-polar, light/conductive, horizontal direction is conductive/vertical Direction conduction etc., it is one of forward position, hot research direction of materials science field.Janus nanobelts refer to two kinds of chemical compositions There is clear and definite partitioned organization in same nanobelt, there is two or more property, lighted as the side of nanobelt has Function, the opposite side of nanobelt have conducting function, if using special reception device, these Janus nanobelts can be determined To arrangement, Janus nano-band array films are formed, this array films have luminous and conduction difunctional.
Rare earth metal europium complex Eu (BA)3Phen, Eu3+For europium ion, BA is benzoic acid, and phen is phenanthroline, because The unique electron configuration of europium ion and as it is unique can red illuminating material, as luminous intensity is high, stability is good, glimmering The advantages that quantum yield is high, monochromaticjty is good, is a kind of wide variety of red fluorescence material.Polyaniline PANI is easy due to its The advantages that synthesis, good electrical conductivity height and environmental stability, have become one of focus of conducting polymer area research.People are Through the polyaniline PANI for having synthesized the one-dimensional nano structures such as nano wire, nanometer rods, nanotube and nanofiber.
Existing research is it has been proved that as dark colour electrically conductive polyaniline PANI and rare earth compounding Eu (BA)3Phen is straight Its illumination effect can be significantly reduced by connecing mixing, therefore obtain Eu (BA)3Illumination effect good phen, it is necessary to make Eu (BA)3Phen and PANI is realized and efficiently separated.If conductive polymer polyanilinc PANI is mixed with polymetylmethacrylate Nanobelt is prepared into, conductive PANI is continuous, ensure that its high conductivity, as the side of Janus nanobelts, then the side It is conductive, and by Eu (BA)3Phen, which is scattered in macromolecule PMMA, is prepared into nanobelt, as the another of Janus nanobelts Side, then the side there is the characteristics of luminescence, form [Eu (BA)3Phen/PMMA] // [PANI/PMMA] emitting red light conduction is difunctional Janus nanobelts, so as to so that electrically conductive polyaniline PANI and Eu (BA)3Phen, which is realized, to be efficiently separated, and obtains good hair Light effect.If using special device, Janus nano-band array films can also be obtained, are so led along nanobelt length direction It is electrically strong, and along on nanobelt direction, due to there is nonconducting Eu (BA)3Phen/PMMA construction units so that should Direction has insulating properties, so as to have anisotropic conductive, so can be obtained by [Eu (BA)3phen/PMMA]// [PANI/PMMA] anisotropic conductive red fluorescence Janus nano-band array films, recycle secondary electrospinning, construct same Janus nano-band array films, this two array films are firmly combined together to form tiled configuration, obtain Janus structural membranes, Among left and right one side of something of this Janus structural membrane, nanobelt length direction is vertical, namely conducting direction is vertical, therefore, this Janus structural membranes have double anisotropic conductive characteristics and emitting red light function.Such a special nano-structure film, will be in future There is important application prospect in nano structure device and medical diagnosis treatment.Have not yet to see the document report of correlation.
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.Nearly more than ten years Since, occur preparing inorganic compound such as oxidate nano fibre using electrospinning process in inorfil preparing technical field The technical scheme of dimension, described oxide include TiO2、ZrO2、Y2O3、Y2O3:RE3+(RE3+=Eu3+、Tb3+、Er3+、Yb3+/Er3 +)、NiO、Co3O4、Mn2O3、Mn3O4、CuO、SiO2、Al2O3、V2O5、ZnO、Nb2O5、MoO3、CeO2、LaMO3(M=Fe, Cr, Mn, Co、Ni、Al)、Y3Al5O12、La2Zr2O7Deng metal oxide and composite oxide of metal.Q.Z.Yu, et al. use Static Spinning Silk technology is prepared for polyaniline PANI nanofibers [Mater.Sci.Eng.B, 2008,150,70-76].Someone utilizes electrostatic Spining technology be successfully prepared high molecular nanometer band [Materials Letters, 2007,61:2325–2328；Journal of Polymer Science:Part B:Polymer Physics,2001,39:2598–2606].Someone is organised using tin Compound, it is combined using electrostatic spinning technique with metallo-organic compound decomposition technique and is prepared for porous SnO2Nanobelt [Nanotechnology,2007,18:435704].Someone is prepared for PEO/ stannic hydroxides using electrostatic spinning technique and answered first Nanobelt is closed, is calcined to have obtained porous SnO2Nanobelt [J.Am.Ceram.Soc., 2008,91 (1):257-262].Dong Phase court of a feudal ruler etc. is prepared for trifluorides nanobelt [Chinese invention patent, application number using electrostatic spinning technique： 201010108039.7], titanium dioxide nano-belts [Chinese invention patent, grant number：ZL200810050948.2] and Gd3Ga5O12:Eu3+Porous nano-belt [SCI, 2010,31 (7), 1291-1296].Dong Xiangting etc. uses single Individual spinning head, PAN/Eu (BA) is prepared for using electrostatic spinning technique3Phen recombination luminescences nanofiber [New Chemical Materials, 2008,36(9),49-52].Dong Xiangting etc. is prepared for Eu (BA) using single spinning head, using electrostatic spinning technique3phen/ The difunctional composite nano fiber of PANI/PVP photoelectricity [SCI, 2012,33 (8), 1657-1662].Dong Xiangting Eu (BA) is prepared for Deng using electrostatic spinning technique3Phen/PVP//PANI/PVP photoelectricity double function two-stranded parallel nanometer fiber bundles [national inventing patent, application number：201210407369.5].Dong Xiangting etc. is prepared for single anisotropy using electrostatic spinning technique Conductive-magnetic-light three functions Janus nano-band arrays (national inventing patent, grant number：201410795673.0；Advanced Functional Materials,2015,25,2436-2443).At present, have no and prepare red fluorescence using electrostatic spinning technique The relevant report of double anisotropic conductive Janus structural membranes.
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 electrostatic spinning technique, spinning head be close together by the truncated diameter identical syringe needles of two 12# form it is arranged side by side double Spinning head, with Eu (BA)3Phen complexs, PMMA, N,N-dimethylformamide DMF and chloroform CHCl3Mixed liquor spun to be a kind of Silk liquid, by aniline, camphorsulfonic acid, ammonium persulfate, PMMA, DMF, CHCl3Mixing, it is another into forming after polyaniline after aniline polymerization Kind spinning solution, controls the viscosity of spinning solution most important, under optimal process conditions, obtains [Eu (BA)3phen/PMMA]// [PANI/PMMA] anisotropic conductive red fluorescence Janus nano-band array films, recycle secondary electrospinning, construct same Janus nano-band array films, this two array films are firmly combined together to form tiled configuration, obtain Janus structural membranes, Among left and right one side of something of this Janus structural membrane, nanobelt length direction is vertical, namely conducting direction is vertical, so as to obtain Janus structural membranes with double anisotropic conductive characteristics and emitting red light function.
The content of the invention
Macromolecule, metal oxide, metal fluoride and metal are prepared for using electrostatic spinning technique in the introduction Composite oxides nanofiber and nanobelt, PAN/Eu (BA)3Phen recombination luminescences nanofiber, polyaniline PANI Nanowires Dimension, Eu (BA)3The difunctional composite nano fiber of phen/PANI/PVP photoelectricity, Eu (BA)3Phen/PVP//PANI/PVP photoelectricity is double Two bursts of parallel bundles of nanofibers of function and single anisotropic conductive-magnetic-light three function Janus nano-band arrays.Used original Material, template, solvent and final target product and the method for the present invention are different.The present invention uses electrostatic spinning technique, [Eu (BA) is prepared for using double-spinneret arranged side by side3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus nano-band array films, recycle secondary electrospinning, construct same Janus nano-band array films, this two array films It is firmly combined together to form tiled configuration, obtains the double anisotropic conductive Janus structural membranes of red fluorescence, be anisotropy Conducting membrane material field adds a kind of conducting film of new structure.
The present invention is achieved in for preparing Eu (BA) using the precipitation method first3Phen complexs, with Eu (BA)3Phen, PMMA, DMF and CHCl3Mixed liquor as a kind of spinning solution, by aniline, camphorsulfonic acid, ammonium persulfate, PMMA, DMF And CHCl3Mixing, after aniline polymerization into another spinning solution is formed after polyaniline, control the viscosity of spinning solution most important.Adopt Electrostatic spinning is carried out with double-spinneret arranged side by side, using electrostatic spinning technique, under optimal process conditions, obtains [Eu (BA)3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus nano-band array films, recycle secondary electrospinning Technology, same Janus nano-band array films are constructed, this two array films are firmly combined together to form tiled configuration, obtain To the double anisotropic conductive Janus structural membranes of red fluorescence.Its step is：
(1) precipitation method prepare Eu (BA)3Phen complexs
By 1.7600g Eu2O3It is dissolved in 20mL concentrated nitric acids, heating is evaporated to obtain Eu (NO3)3Crystal, it is anhydrous to add 40mL Ethanol, it is configured to Eu (NO3)3Ethanol solution；It is anhydrous that 3.6640g benzoic acid and 1.8020g phenanthrolines are added to 100mL Mixed ligand solution is configured in ethanol, is heated to 50-60 DEG C, in the case where being stirred continuously by Eu (NO3)3Ethanol solution It is added dropwise in mixed ligand solution, adds dense NH3·H2O adjust pH for 6-6.5 between, continue react 3h, gained precipitate according to It is secondary to be washed 3 times with water and ethanol, 12h is finally dried at 60 DEG C in drying box, obtains Eu (BA)3Phen complexs；
(2) polymetylmethacrylate is prepared
100g methyl methacrylate MMA and 0.1g dibenzoyl peroxide BPO are weighed, are added to reflux In 250mL three-necked bottles and stir, being stirred vigorously and be back to solution above-mentioned solution at a temperature of 90-95 DEG C has necessarily Viscosity, after its viscosity is close with glycerine, stops heating while stirring is continued and naturally cool to room temperature, afterwards will be above-mentioned Infusion is into test tube, influx height 5-7cm, and 2h is stood after perfusion does not have bubble to invisible spectro solution, then Above-mentioned test tube is transferred in 50 DEG C of drying boxes and places 48h, invisible spectro liquid hardening is transparent solid, finally by drying box Temperature improves to 110 DEG C and is incubated 2h, terminates polymerisation, then naturally cools to room temperature, obtains poly-methyl methacrylate Ester PMMA；
(3) spinning solution is prepared
0.75g PMMA and 0.1125g Eu (BA) are added in 5.8259g chloroforms and 1.5066g DMF in the mixed solvent3Phen complexs simultaneously stir 24h, obtain a spinning solution, have emitting red light function；In 1.0125g chloroforms and 6.6282g DMF in the mixed solvent adds 0.6g PMMA, and stirring 2h obtains uniform colloidal fluid, by 0.1800g aniline and 0.2245g camphor trees After brain sulfonic acid is added in above-mentioned colloidal fluid and stirs 2h, 0.4411g ammonium persulfates stirring 30min is added, then puts solution Enter 24h in 5 DEG C of cold compartment of refrigerator, obtain another spinning solution, there is conducting function；
(4) [Eu (BA) is prepared3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus nanobelts Array films
The 5mL syringes of truncated 12# stainless steel syringe needles are all carried using two difference, two stainless pin heads are distinguished curved Bent 30 ° of angles, make two needle points closely parallel, and make using a 1mL plastic spray guns headgear on two parallel stainless steel syringe needles The tip of two stainless steel syringe needles is in the center section of plastic spray gun head, and 3ml two spinning solutions are injected separately into two In syringe, using perpendicular spray mode, reception device is a horizontal positioned long 20cm, and a diameter of 7cm cylindrical aluminum turns Cylinder, rotating speed 1500r/min, other spinning parameters are spinning voltage 6kV, and needle point and rotating cylinder spacing are 12cm, environment temperature For 20-28 DEG C, relative humidity 20%-30%, [Eu (BA) after spinning solution exhausts, is obtained3phen/PMMA]//[PANI/ PMMA] anisotropic conductive red fluorescence Janus nano-band array films；
(5) the double anisotropic conductive Janus structural membranes of red fluorescence are prepared
By described [Eu (BA)3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus nanometers Band array films are removed from aluminum rotating cylinder, cut out for be 2.2cm along Janus nanobelts direction, vertical nanowires with direction be 2cm's Rectangle, it is fixed on after being rotated by 90 ° on aluminum rotating cylinder, its 2 × 2cm is covered with aluminium foil2Area, remaining 2 × 0.2cm2 Joint face of the area as secondary electrospinning film, spinning solution dosage and spinning parameter are identical with first time electro-spinning process, carry out two Secondary electrospinning, film is removed from aluminum rotating cylinder after the completion of spinning and cut, obtains 2 × 4cm2The double anisotropy of red fluorescence Conductive Janus structural membranes.
The area of the double anisotropic conductive Janus structural membranes of prepared red fluorescence is 2 × 4cm in said process2, by [Eu(BA)3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus nano-band array films or so are compound Form, left and right one side of something is by [the Eu (BA) aligned3Phen/PMMA] // [PANI/PMMA] Janus nanobelts composition, often The width of bar Janus nanobelts is 8.99 μm, thickness 816nm, among left and right one side of something of Janus structural membranes, nanometer belt length It is vertical to spend direction, namely conducting direction is vertical, strong along nanobelt length direction electric conductivity, average conductance is 9.90 × 10-6S, And along weak perpendicular to nanobelt length direction electric conductivity, average conductance is 2.73 × 10-10S, there are double anisotropic conductives； Under 289nm ultraviolet excitation, launch the bright red that main peak is located at 615nm；Prepared Janus structural membranes have good Good red fluorescence and double anisotropic conductive functions, realize goal of the invention.
Brief description of the drawings
Fig. 1 is the SEM photograph of the double anisotropic conductive Janus structural membranes of red fluorescence, and the figure also serves as Figure of abstract；
Fig. 2 is the SEM photograph of Janus nano-band array films in the double anisotropic conductive Janus structural membranes of red fluorescence；
Fig. 3 is the width distribution histogram of Janus nanobelts in the double anisotropic conductive Janus structural membranes of red fluorescence；
Fig. 4 is the line analysis energy dispersive spectrum of Janus nanobelts in the double anisotropic conductive Janus structural membranes of red fluorescence Figure；
Fig. 5 is that the light microscope of wall scroll Janus nanobelts in the double anisotropic conductive Janus structural membranes of red fluorescence shines Piece；
Fig. 6 is the SEM photograph of Janus nanobelts in the double anisotropic conductive Janus structural membranes of red fluorescence；
Fig. 7 is the exciting light spectrogram of the double anisotropic conductive Janus structural membranes of red fluorescence；
Fig. 8 is the launching light spectrogram of the double anisotropic conductive Janus structural membranes of red fluorescence.
Embodiment
Europium oxide Eu selected by the present invention2O3Purity be 99.99%, DMF, chloroform, nitric acid, benzene Formic acid, phenanthroline, absolute ethyl alcohol, ammoniacal liquor, aniline, camphorsulfonic acid, dibenzoyl peroxide, methyl methacrylate, over cure Sour ammonium, it is commercially available analysis net product；Make by oneself in deionized water laboratory；Glass apparatus and equipment used is commonly used in laboratory Instrument and equipment.
Embodiment：By 1.7600g Eu2O3It is dissolved in 20mL concentrated nitric acids, heating is evaporated to obtain Eu (NO3)3Crystal, add 40mL absolute ethyl alcohols, it is configured to Eu (NO3)3Ethanol solution；3.6640g benzoic acid and 1.8020g phenanthrolines are added to Mixed ligand solution is configured in 100mL absolute ethyl alcohols, is heated to 50-60 DEG C, in the case where being stirred continuously by Eu (NO3)3's Ethanol solution is added dropwise in mixed ligand solution, adds dense NH3·H2O adjusts pH between 6-6.5, continues to react 3h, institute It must precipitate and be washed 3 times with water and ethanol successively, finally dry 12h at 60 DEG C in drying box, obtain Eu (BA)3Phen coordinates Thing；100g methyl methacrylate MMA and 0.1g dibenzoyl peroxide BPO are weighed, are added to the 250mL with reflux In three-necked bottle and stir, being stirred vigorously and be back to solution above-mentioned solution at a temperature of 90-95 DEG C has certain viscosity, After its viscosity is close with glycerine, stops heating while stirring is continued and naturally cool to room temperature, afterwards by above-mentioned solution It is filled into test tube, influx height 5-7cm, 2h is stood after perfusion does not have bubble to invisible spectro solution, then will be upper State test tube and be transferred in 50 DEG C of drying boxes and place 48h, invisible spectro liquid hardening is transparent solid, finally by drying box temperature Improve to 110 DEG C and be incubated 2h, terminate polymerisation, then naturally cool to room temperature, obtain polymethyl methacrylate PMMA；0.75g PMMA and 0.1125g Eu (BA) are added in 5.8259g chloroforms and 1.5066g DMF in the mixed solvent3Phen complexs simultaneously stir 24h, obtain a spinning solution, have emitting red light function；In 1.0125g chloroforms and 6.6282g DMF in the mixed solvent adds 0.6g PMMA, and stirring 2h obtains uniform colloidal fluid, by 0.1800g aniline and 0.2245g camphor trees After brain sulfonic acid is added in above-mentioned colloidal fluid and stirs 2h, 0.4411g ammonium persulfates stirring 30min is added, then puts solution Enter 24h in 5 DEG C of cold compartment of refrigerator, obtain another spinning solution, there is conducting function；Using two difference all with truncated The 5mL syringes of 12# stainless steel syringe needles, two stainless pin heads are bent into 30 ° of angles respectively, make two needle points closely parallel, and adopt With a 1mL plastic spray guns headgear on two parallel stainless steel syringe needles, the tip of two stainless steel syringe needles is set to be in plastics spray The center section of pipette tips, 3ml two spinning solutions are injected separately into two syringes, using perpendicular spray mode, reception device For a horizontal positioned long 20cm, a diameter of 7cm cylindrical aluminum rotating cylinder, rotating speed 1500r/min, other spinning parameters For, spinning voltage 6kV, needle point is 12cm with rotating cylinder spacing, and environment temperature is 20-28 DEG C, relative humidity 20%-30%, After spinning solution exhausts, [Eu (BA) is obtained3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus receives Rice band array films；By described [Eu (BA)3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus receives Rice band array films removed from aluminum rotating cylinder, cut out for be 2.2cm along Janus nanobelts direction, vertical nanowires band direction be 2cm Rectangle, be fixed on after being rotated by 90 ° on aluminum rotating cylinder, its 2 × 2cm covered with aluminium foil2Area, remaining 2 × 0.2cm2Joint face of the area as secondary electrospinning film, spinning solution dosage and spinning parameter are identical with first time electro-spinning process, Secondary electrospinning is carried out, film is removed from aluminum rotating cylinder after the completion of spinning and cut, obtains 2 × 4cm2Red fluorescence is double each Anisotropy conduction Janus structural membranes.The double anisotropic conductive Janus structural membranes of red fluorescence have left and right Half-edge Structure, on a left side In right Half-edge Structure, nanobelt length direction is vertical, and nanobelt is in aligning, as shown in Figure 1；Prepared red fluorescence is double Janus nanobelts align to form array films in anisotropic conductive Janus structural membranes, as shown in Figure 2；Prepared red In the double anisotropic conductive Janus structural membranes of fluorescence the width of Janus nanobelts for 8.99 μm as shown in Figure 3；S and Eu elements Distribution can reflect polyaniline and Eu (BA) respectively3Phen distribution, S elements are distributed only over the side of Janus nanobelts, Eu members Element is distributed in the opposite side of Janus nanobelts, and this is consistent with the structure of Janus nanobelts, as shown in Figure 4；Wall scroll Janus receives The side of rice band includes dark colour polyaniline, and opposite side includes the Eu (BA) of water white transparency3Phen complexs, as shown in Figure 5； The thickness of wall scroll Janus nanobelts is 816nm, as shown in Figure 6；Monitoring wavelength, double anisotropic conductives are used as using 615nm Janus structural membranes have a wide excitation band at 200-360nm, and its peak value can be classified as π → π * jumps of part at 289nm Move, as shown in Figure 7；Under 289nm ultraviolet excitation, double anisotropic conductive Janus structural membranes are launched main peak and are located at 615nm bright red, it corresponds to Eu ions5D0→7F2Transition, as shown in Figure 8；Prepared red fluorescence it is double respectively to Among left and right one side of something of the conductive Janus structural membranes of the opposite sex, nanobelt length direction is vertical, namely conducting direction is vertical, along receiving Rice strip length direction electric conductivity is strong, and average conductance is 9.90 × 10-6S, and along weak perpendicular to nanobelt length direction electric conductivity, Average conductance is 2.73 × 10-10S, has double anisotropic conductives, and prepared Janus structural membranes have well red glimmering Light and double anisotropic conductive functions.
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. the double anisotropic conductive Janus structural membranes of red fluorescence, it is characterised in that by [Eu (BA)3phen/PMMA]// [PANI/PMMA] anisotropic conductive red fluorescence Janus nano-band array films or so are combined, and left and right one side of something is by orientation [the Eu (BA) of arrangement3Phen/PMMA] // [PANI/PMMA] Janus nanobelts composition, and nanobelt length direction is vertical, I.e. conducting direction is vertical, strong along nanobelt length direction electric conductivity, and along weak perpendicular to nanobelt length direction electric conductivity, With double anisotropic conductives, prepared Janus structural membranes have good red fluorescence and double anisotropic conductive functions, Membrane area is 2 × 4cm2。
2. a kind of preparation method of the double anisotropic conductive Janus structural membranes of red fluorescence as claimed in claim 1, its feature It is, using double-spinneret electrostatic spinning technique arranged side by side, prepares product as the double anisotropic conductive Janus structures of red fluorescence Film, its step are：
(1) precipitation method prepare Eu (BA)3Phen complexs
By 1.7600g Eu2O3It is dissolved in 20mL concentrated nitric acids, heating is evaporated to obtain Eu (NO3)3Crystal, 40mL absolute ethyl alcohols are added, It is configured to Eu (NO3)3Ethanol solution；3.6640g benzoic acid and 1.8020g phenanthrolines are added in 100mL absolute ethyl alcohols Mixed ligand solution is configured to, is heated to 50-60 DEG C, in the case where being stirred continuously by Eu (NO3)3Ethanol solution add dropwise Into mixed ligand solution, dense NH is added3·H2O adjusts pH between 6-6.5, continues to react 3h, gained precipitation uses water successively Washed 3 times with ethanol, finally dry 12h at 60 DEG C in drying box, obtain Eu (BA)3Phen complexs；
(2) polymetylmethacrylate is prepared
100g methyl methacrylate MMA and 0.1g dibenzoyl peroxide BPO are weighed, are added to reflux In 250mL three-necked bottles and stir, being stirred vigorously and be back to solution above-mentioned solution at a temperature of 90-95 DEG C has necessarily Viscosity, after its viscosity is close with glycerine, stops heating while stirring is continued and naturally cool to room temperature, afterwards will be above-mentioned Infusion is into test tube, influx height 5-7cm, and 2h is stood after perfusion does not have bubble to invisible spectro solution, then Above-mentioned test tube is transferred in 50 DEG C of drying boxes and places 48h, invisible spectro liquid hardening is transparent solid, finally by drying box Temperature improves to 110 DEG C and is incubated 2h, terminates polymerisation, then naturally cools to room temperature, obtains poly-methyl methacrylate Ester PMMA；
(3) spinning solution is prepared
0.75g PMMA and 0.1125g Eu (BA) are added in 5.8259g chloroforms and 1.5066g DMF in the mixed solvent3phen Complex simultaneously stirs 24h, obtains a spinning solution, has emitting red light function；In 1.0125g chloroforms and 6.6282g DMF In the mixed solvent adds 0.6g PMMA, and stirring 2h obtains uniform colloidal fluid, by 0.1800g aniline and 0.2245g camphorsulfonic acids After being added in above-mentioned colloidal fluid and stirring 2h, 0.4411g ammonium persulfates stirring 30min is added, solution is then put into 5 DEG C 24h in cold compartment of refrigerator, another spinning solution is obtained, there is conducting function；
(4) [Eu (BA) is prepared3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus nano-band arrays Film
The 5mL syringes of truncated 12# stainless steel syringe needles are all carried using two difference, two stainless pin heads are bent respectively 30 ° of angles, make two needle points closely parallel, and make two on two parallel stainless steel syringe needles using a 1mL plastic spray guns headgear The tip of root stainless steel syringe needle is in the center section of plastic spray gun head, and 3ml two spinning solutions are injected separately into two notes In emitter, using perpendicular spray mode, reception device is a horizontal positioned long 20cm, a diameter of 7cm cylindrical aluminum rotating cylinder, Rotating speed is 1500r/min, and other spinning parameters are spinning voltage 6kV, and needle point and rotating cylinder spacing are 12cm, and environment temperature is 20-28 DEG C, relative humidity 20%-30%, after spinning solution exhausts, obtain [Eu (BA)3phen/PMMA]//[PANI/ PMMA] anisotropic conductive red fluorescence Janus nano-band array films；
(5) the double anisotropic conductive Janus structural membranes of red fluorescence are prepared
By described [Eu (BA)3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus nano-band arrays Film is removed from aluminum rotating cylinder, cut out for be 2.2cm along Janus nanobelts direction, vertical nanowires with direction be the rectangular of 2cm Shape, it is fixed on after being rotated by 90 ° on aluminum rotating cylinder, its 2 × 2cm is covered with aluminium foil2Area, remaining 2 × 0.2cm2Face Joint face of the product as secondary electrospinning film, spinning solution dosage and spinning parameter are identical with first time electro-spinning process, carry out secondary electricity Spin, film is removed from aluminum rotating cylinder after the completion of spinning and cut, obtains 2 × 4cm2The double anisotropic conductives of red fluorescence Janus structural membranes, by [Eu (BA)3Phen/PMMA] // [PANI/PMMA] anisotropic conductive red fluorescence Janus nanobelts Array films or so are combined, and left and right one side of something is by [the Eu (BA) aligned3phen/PMMA]//[PANI/PMMA]Janus Nanobelt forms, and the width of every Janus nanobelt is 8.99 μm, thickness 816nm, half of in the left and right of Janus structural membranes Central, nanobelt length direction is vertical, namely conducting direction is vertical, strong along nanobelt length direction electric conductivity, average conductance For 9.90 × 10-6S, and along weak perpendicular to nanobelt length direction electric conductivity, average conductance is 2.73 × 10-10S, have double Anisotropic conductive, under 289nm ultraviolet excitation, Janus structural membranes launch the bright red that main peak is located at 615nm, Prepared Janus structural membranes have good red fluorescence and double anisotropic conductive functions.
CN201711119678.1A 2017-11-14 2017-11-14 Double anisotropic conductive Janus structural membranes of red fluorescence and preparation method thereof Withdrawn CN107794596A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711119678.1A CN107794596A (en) 2017-11-14 2017-11-14 Double anisotropic conductive Janus structural membranes of red fluorescence and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711119678.1A CN107794596A (en) 2017-11-14 2017-11-14 Double anisotropic conductive Janus structural membranes of red fluorescence and preparation method thereof

Publications (1)

Publication Number Publication Date
CN107794596A true CN107794596A (en) 2018-03-13

Family

ID=61536025

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711119678.1A Withdrawn CN107794596A (en) 2017-11-14 2017-11-14 Double anisotropic conductive Janus structural membranes of red fluorescence and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107794596A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109252292A (en) * 2018-04-08 2019-01-22 长春理工大学 Double anisotropic conductive flexible compound films of green emitting and preparation method thereof
CN109252290A (en) * 2018-08-29 2019-01-22 长春理工大学 Magneto-optic anisotropic conductive special construction Janus nano-band array film
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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109252292A (en) * 2018-04-08 2019-01-22 长春理工大学 Double anisotropic conductive flexible compound films of green emitting and preparation method thereof
CN109252290A (en) * 2018-08-29 2019-01-22 长春理工大学 Magneto-optic anisotropic conductive special construction Janus nano-band array film
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

Similar Documents

Publication Publication Date Title
CN104532393B (en) Anisotropic conductive magneto-optic three function trichroism flag form nano-band array and preparation method thereof
CN104532394B (en) Anisotropic conductive magneto-optic three function Janus nano-band array and preparation method thereof
CN107794596A (en) Double anisotropic conductive Janus structural membranes of red fluorescence and preparation method thereof
CN107881593A (en) Double anisotropic conductive green fluorescence Janus structural membranes and preparation method thereof
CN104538121B (en) Photo-electro-magnetic three-function banded coaxial nano cable array and preparation method thereof
CN102874861B (en) Electrostatic spinning method of red fluorescent nanosheet Y2O2SO4: Eu3+
CN102943317A (en) Method for constructing photoelectricity double function two-stranded parallel nanometer fiber bundle
CN102504805B (en) Magneto-optic dual-function composite nanobelt and its preparation method
CN103225129A (en) Photo-electromagnetic three-functional three-strands-paralleled nanometer fiber bundle and its preparation method
CN106391129B (en) Luminous four two layers of nano-fiber composite films of function of photocatalysis of electromagnetism and preparation method thereof
CN109252290B (en) Janus nano-belt array film with magneto-optical anisotropic conductive special structure
CN103225120A (en) Magneto-optical bifunctional double-strand parallel nanoribbon bundle and preparation method thereof
CN103225127A (en) Photo-electromagnetic three-functional two-strands-paralleled nanometer fiber bundle
CN108374209A (en) Three function Janus nanofiber array films of anisotropic conductive magneto-optic
CN109537164A (en) Three function sandwich structure composite membrane of anisotropic conductive magneto-optic and preparation method thereof
CN103225128A (en) Photo-electromagnetic three-functional two-strands-paralleled nanometer fiber bundle and its preparation method
CN109266327A (en) Double anisotropic conductive flexible compound films of magnetic green fluorescence and preparation method thereof
CN102618966B (en) Method for preparing europium-doped sodium tetrafluoro gadolinium red luminescent nanofiber
CN109252292A (en) Double anisotropic conductive flexible compound films of green emitting and preparation method thereof
CN109082773A (en) The conductive special Janus nano-band array film of magneto-optic functionalization high anisotropy
CN108978047B (en) High-concentration co-doped nanofiber membrane for single-drop trace fluorescence detection and preparation method and application thereof
CN109097909A (en) Double anisotropic conductive flexible compound films of red and green color fluorescence and preparation method thereof
CN108360077A (en) Three function special construction Janus nanofibers of photoelectromagnetic and preparation method thereof
CN102817108B (en) Preparation method for terbium doped yttrium trifluoride green luminescence hollow nano-fibers
CN109706621B (en) Anisotropic conductive magnetic red-green double-color fluorescent sandwich structure multifunctional composite film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20180313

WW01 Invention patent application withdrawn after publication