CN103806221B - A kind of preparation method of multicomponent mesh nano tunica fibrosa - Google Patents
A kind of preparation method of multicomponent mesh nano tunica fibrosa Download PDFInfo
- Publication number
- CN103806221B CN103806221B CN201410061970.2A CN201410061970A CN103806221B CN 103806221 B CN103806221 B CN 103806221B CN 201410061970 A CN201410061970 A CN 201410061970A CN 103806221 B CN103806221 B CN 103806221B
- Authority
- CN
- China
- Prior art keywords
- solution
- aramid
- meta
- tunica fibrosa
- nano
- 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.)
- Active
Links
Landscapes
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The present invention relates to a kind of preparation method of multicomponent mesh nano tunica fibrosa, concrete steps are: the first step: meta-aramid fibers, halogen are mixed and pulled an oar with mass ratio 1: 0.004-0.4: 2.996-18.6 with organic solvent, stir preparation meta-aramid solution; Second step: by functional high-polymer polymer and solvent with mass ratio 1: 5.4-98.99 mixes, and adds nano particle, adds thermal agitation function equipment Polymer Solution; Wherein, in solution, the mass fraction of nano particle is: 0.01%-5%; The 3rd step: the functional high-polymer solution that the meta-aramid solution that the first step is obtained obtains with second step in mass ratio 1: 0.05-0.5 drips and mixes, ultrasonic processing obtains spinning solution; The 4th step: under the condition of room temperature 20-30 DEG C and relative humidity 20%-70%, described spinning solution is carried out to electrostatic spinning, finally obtaining mesh nano fibre diameter is that 5-20nm, network structure coverage rate reach more than 95% multicomponent mesh nano tunica fibrosa. Preparation technology of the present invention is simple, cost is low, and tensile strength of material is remarkable up to 100-2000MPa and functional advantage.
Description
Technical field
The present invention relates to a kind of preparation method of multicomponent mesh nano tunica fibrosa, belong to nano material technology neckTerritory.
Background technology
Aramid fiber, carbon fiber and high-strength high-modulus polyethylene fiber are as current most important three kinds of high-performance fibresTie up, become gradually the focus in current fiber research field. Wherein meta-aramid with its excellent heat-resisting quantity,The characteristics such as dimensional stability, spinnability, fire line and corrosion resistance, have been successfully applied to high temperature filtration, individualIn the various fields such as body protection, battery isolating film, military project aerospace. Meta-aramid is not deposited by the restriction of body constructionAt fusing point, it just decomposed before melting, thereby its fiber preparation process is very limited, its preparation at presentTechnique mainly contains three kinds of dry spinning, wet spinning and dry-jet wet spinnings. The aramid fiber that these methods are preparedDiameter is micron number magnitude and fibre diameter deviation is larger, and this has limited its practical application greatly.
In recent years, electrostatic spinning technique is simple with its manufacturing installation, spinning is with low cost, it is numerous to spin substance classesThe advantages such as many, process controllability is strong, adjustability of structure is strong, become high-tech, high added value nanometer fibre graduallyOne of main stream approach prepared by dimension material. Researcher has prepared a series of positions by electrostatic spinning techniqueAramid nano-fiber, JournalofNanoscienceandNanotechnology11 (2011) 4004-4010 profitWith the article that electrostatic spinning technique is prepared meta-aramid nano-fiber be taking aramid fiber in-situ polymerization solution as spinning formerMaterial, through electrostatic spinning, has obtained the meta-aramid nano-fiber of diameter 150-200nm. Researcher's system subsequentlyDifferent ionic liquid dissolution system (FibersandPolymers11 (2010) 1032-1040, Journal are studiedOfTextileResearch32 (2011) 11-17), add CNT (Nanoscale5 (2013) 886-889),Aramid fiber nanometer fibre under the aftertreatment technologys such as hot-stretch (FibersandPolymers14 (2013) 405-408) conditionThe preparation of dimension. In addition, FibersandPolymers12 (2011) 197-206 has prepared meta-aramid/acetic acid fibreCellulose fiber and meta-aramid/cellulose fibre and investigated its heat resistance and mechanical performance. Chinese patentCN101838888A discloses preparation method, the CN101279204A public affairs of electrospun meta-aramid nano-fiberPreparation method, the CN102877152 that has opened high intensity nano fibre functional film discloses a kind of aramid fiber 1313/manyWall carbon nano tube nanofiber and preparation method thereof, it is abundant that above-mentioned research has obtained kind pattern to a certain extentVarious meta-aramid nano-fiber material, but prepared meta-aramid nano-fiber still exists fiber straightThe defects such as easy glide between the large and skewness in footpath, fiber, mechanical strength are poor, have seriously limited its practical applicationPerformance.
In the recent period, along with researcher is to the deepening continuously of electrostatic spinning technique research, it is found that this technology can lead toCross SOLUTION PROPERTIES and technological parameter obtain taking ultra-fine one dimension Electrospun Nanofibrous Materials: An as support, have and be similar toThe two-dimension netted fiber film material of spider net, soap bubble structure, reticular fibre diameter is than common electrostatic spinning nano fiberThe low order of magnitude of diameter, the current extensive concern that has caused academia and industrial quarters. PolymerIn International61 (2012) 1675-1682 article, successfully prepare novel meta-aramid mesh nano fiberFilm, the structure regulating of electrospun meta-aramid nano-fiber and performance study thereof (Master's thesis) have proposed utilizationElectrostatic spinning technique is prepared the method for meta-aramid mesh nano fiber, and Chinese patent CN102704028A is openA kind of preparation method of meta-aramid mesh nano tunica fibrosa, though that meta-aramid has been prepared in above-mentioned research is nettedNano-fiber material, has reduced fibre diameter, but it still exists, tunica fibrosa mechanical strength is poor, mesh nano is fineThe defects such as dimension structural constituent is single, functional deficiency, have seriously limited the practical application of this material.
Summary of the invention
The object of this invention is to provide a kind of preparation method of multicomponent mesh nano tunica fibrosa, particularly a kind of withMeta-aramid and functional high-polymer are the preparation side of the high strength multicomponent mesh nano tunica fibrosa of bulk materialMethod.
In order to address the above problem, the invention provides a kind of preparation method of multicomponent mesh nano tunica fibrosa,It is characterized in that, concrete steps are:
The first step: by meta-aramid fibers, halogen and organic solvent with mass ratio 1: 0.004-0.4: 2.996-18.6Mix and pull an oar, stirring preparation meta-aramid solution;
Second step: by functional high-polymer polymer and solvent with mass ratio 1: 5.4-98.99 mixes, and addsEnter nano particle, add thermal agitation function equipment Polymer Solution; Nano particle in functional high-polymer solutionMass fraction is 0.01%-5%;
The 3rd step: the functional high-polymer solution that the meta-aramid solution that the first step is obtained and second step obtain byMass ratio 1: 0.05-0.5 drips mixing, and ultrasonic processing obtains spinning solution;
The 4th step: under the condition of room temperature 20-30 DEG C and relative humidity 20%-70%, by described spinning solutionCarry out electrostatic spinning, obtain the multicomponent mesh nano tunica fibrosa taking common nanofiber as support.
Preferably, organic solvent and halogen are mixed to form stable ionic liquid by being mixed into first in the described first stepBody dicyandiamide solution, then adds aramid fiber; Making beating in the first step refers to and at room temperature utilizes experiment point loose sandGrinding machine disperses 5-20min with the rotating speed of 3000-8000rpm; Stirring in the first step refers in temperatureAt 20-100 DEG C, stir 1-10h with magnetic stirring apparatus with the rotating speed of 20-200rpm. The present invention pulls an oar rotating speedHeight, can improve rate of dispersion and the degree of meta-aramid fibers, shortens dissolution time, reduces halogen aequum.
Preferably, in described second step add thermal agitation at 40-100 DEG C with magnetic stirring apparatus withThe rotating speed of 20-200rpm stirs 5-24h.
Preferably, the mixing of the dropping in described the 3rd step refers under the stirring of room temperature 20-200rpm rotating speed functionProperty Polymer Solution splash into meta-aramid solution with the speed of 1-5 second/drip; Surpassing of ultrasonic processing in the 3rd stepAcoustic frequency is 40-60kHz, and the ultrasonic processing time is 1-5h; The electrical conductivity of the spinning solution in the 3rd step is100-1500mS/m, viscosity is 300-10000cp.
Preferably, the electrostatic spinning in described the 4th step refers under electrospinning device auxiliary spinning solutionFlow velocity with 0.1-10mL/h pours into, and the high-tension electricity that applies 10-60kV simultaneously in spinning head place spinsSilk, the metallic plate that receiving system is ground connection, the distance between receiving system and spinning nozzle is 5-30cm, receives baseMaterial is aluminium foil, copper mesh, filter paper or nonwoven. Voltage that this patent applies is higher, has effectively promoted electrostatic spinningThe formation of small charged drop in process, increases cancellated coverage rate in tunica fibrosa.
Preferably, described halogen is in lithium chloride, calcium chloride, lithium bromide, sodium bromide, calcium bromide and KBrAny one or a few mixture. Organic solvent in the described first step be DMF,In 1-METHYLPYRROLIDONE, DMA, oxolane, dimethyl sulfoxide (DMSO) and acetone arbitrarilyThe mixture of one or more.
Preferably, described functional high-polymer polymer is Kynoar, polyurethane, polysulfones, poly-epoxy secondAlkene, PTT, nylon, polyacrylonitrile, polystyrene, polyvinyl chloride, polyvinyl alcohol,The mixture of any one or a few in polyacrylic acid and shitosan. Solvent in described second step is N,Dinethylformamide, formic acid, water, acetic acid, carrene, DMA, oxolane,Trifluoroacetic acid, chloroform, 1-METHYLPYRROLIDONE, ethanol, acetone, n-butanol, isobutanol, hexafluoro are differentPropyl alcohol, dimethylbenzene, carbon tetrachloride, dimethyl sulfoxide (DMSO), pyridine, bromobenzene, methyl phenyl ethers anisole, phthalic acid and differentThe mixture of any one or a few in propyl alcohol. Described nano particle be zirconia, silica, titanium oxide,The mixture of any one or a few in aluminium oxide, cupric oxide and silver nano-grain, the particle diameter of nano particle is5-50nm。
Preferably, described common nanofiber refers to meta-aramid nano-fiber, functional high-polymer nanofiberAnd the Hybrid nanofibers jointly being formed by meta-aramid and functional high-polymer, average fibre diameter is 100nm-1μm。
Preferably, in described multicomponent mesh nano tunica fibrosa, multicomponent reticular fibre has two-dimensional network structure,Comprise meta-aramid mesh nano fiber, functional high-polymer mesh nano fiber and by meta-aramid and functionProperty the macromolecule common hydridization mesh nano fiber forming, mesh nano average fibre diameter is 5-20nm, netThe coverage rate of shape structure in tunica fibrosa reaches more than 95%.
The hot strength of described high strength multicomponent mesh nano tunica fibrosa reaches 100-2000MPa; For heightThe thickness of intensity multicomponent mesh nano tunica fibrosa, can do any thickness, from 10 microns to tens centimetres veryTo thicker, relevant with the spinning time.
The present invention increases ionic liquid and aramid fiber interactive surfaces by introducing beating process amasss, and promotesCrack velocity and the degree of aramid fiber macromolecule interchain hydrogen bond, efficiently solve meta-aramid and be difficult to a difficult problem of dissolving,Can significantly reduce the quality of required halogen in aramid fiber course of dissolution, effectively improved the degree of purification of fiber simultaneously,Avoid halogen to destroy fiber bodies structure and reduced the problem of fibre strength; The introducing of nano particle significantly strengthensThe unstability of the most advanced and sophisticated charged fluid of taylor cone in follow-up electrostatic spinning process, promotes the shape of small charged dropBecome, promoted greatly cancellated coverage rate in tunica fibrosa; Taking meta-aramid and functional high-polymer as thisBody material, has successfully prepared high strength multicomponent mesh nano fiber film material, has greatly reduced the straight of fiberFootpath (mesh nano average fibre diameter is at 5-20nm), has promoted interfibrous adhesion, has successfully broken through fiberBetween easy glide and the bottleneck of poor mechanical property, netted receiving expanded in the formation of multicomponent mesh nano fiber greatlyRice fiber functional, the practical application performance of this new material has been played to vital effect.
Compared with prior art, the invention has the beneficial effects as follows:
1, the preparation method of high strength multicomponent mesh nano tunica fibrosa of the present invention, effectively reduce fibre diameter,When promoting mesh nano fiber-covered rate, fortifying fibre mechanical property, expand greatly mesh nano fibreTie up the functional of material, and this novel high-performance nano material preparation process technique is simple, with low cost. SimultaneouslyThis tunica fibrosa has the excellent performance such as heatproof fire prevention, acid-alkali-corrosive-resisting, filtration, sensing, battery isolating film,The fields such as individual protection have broad application prospects.
2, the beating process in the first step of the present invention can utilize mechanical force effectively to reduce the length of aramid fiber, increasesThe interactive surfaces that adds solion and aramid fiber is long-pending, promotes the crack velocity of aramid fiber macromolecule interchain hydrogen bondWith degree, thereby realize the rapid dispersion of aramid fiber macromolecule in ion liquid dissolving system, finally realized allOne stablizes the rapidly and efficiently preparation of meta-aramid solution, efficiently solve meta-aramid because of bulk properties be difficult to dissolveBottleneck problem. Meanwhile, the introducing of beating process can significantly reduce the quality of required halogen in aramid fiber course of dissolution,Effectively improve the degree of purification of fiber, avoided halogen to destroy fiber bodies structure and reduced asking of fibre strengthTopic.
3, in second step of the present invention nano particle add the Effective Regulation that can realize solution bulk properties, fromAnd strengthen the unstability of the most advanced and sophisticated charged fluid of taylor cone in follow-up electrostatic spinning process, promote small charged dropFormation, fine droplet is further through the formation network structure that is separated fast, final effectively improve obtain highCancellated coverage rate in intensity multicomponent mesh nano tunica fibrosa;
4, the dropping in the present invention's the 3rd step mixes effectively expanding function Polymer Solution drop and a position virtueThe contact area of synthetic fibre solution, the mixing velocity of raising solution; Ultrasonic processing can ensure that nano particle is at mixed solutionIn effective dispersion, strengthen the stable homogeneous of solution, prevent from being separated between solution. Functional high-polymerIntroducing not only can expand the kind of mesh nano fiber in tunica fibrosa, strengthen the merit of mesh nano fiber film materialEnergy property, meanwhile, it can promote interfibrous adhesion in film, suppresses interfibrous slippage under effect of stress, effectivelyPromote the bulk strength of tunica fibrosa.
Brief description of the drawings
Fig. 1 is the field emission scan electronic display of high strength multicomponent (meta-aramid/polyurethane) mesh nano tunica fibrosaMicro mirror photo
Detailed description of the invention
Below in conjunction with detailed description of the invention, further set forth the present invention. Should be understood that these embodiment are only for sayingBright the present invention and being not used in limits the scope of the invention. In addition should be understood that and reading the content that the present invention lecturesAfterwards, those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within equallyThe application's appended claims limited range.
Embodiment 1
A preparation method for high strength multicomponent mesh nano tunica fibrosa, concrete steps are:
The first step: 0.4g lithium chloride is joined to 14.6gN, in N-dimethylacetylamide magnetic agitation preparation fromSub-liquid dissolution system, then adds the mixed experiment that is incorporated in 5000rpm rotating speed of 5g meta-aramid fibers to disperseIn sand mill, disperse making beating 20min, stir 1h with magnetic stirring apparatus with the rotating speed of 100rpm at 20 DEG C, obtainMeta-aramid and lithium chloride mass fraction are respectively 25%, 2% stable homogeneous solution (A solution);
Second step: 1g polyurethane is joined to 8.9gN, mix in N-dimethylacetylamide, then addEnter the monox nanometer particle that 0.1g particle diameter is distributed in 5-30nm and mix, under 50 DEG C of heating conditions, useMagnetic stirring apparatus stirs 5h with the rotating speed of 50rpm, obtains polyurethane and nano particle mass fraction and is respectively10%, 1% stable homogeneous solution (B solution);
The 3rd step: under the magnetic agitation of 20rpm rotating speed, the polyurethane high molecule solution that second step is obtained byMass ratio with the speed of 2 second/droplet splashes into meta-aramid solution and drips mixing at 1: 10, under 30kHz frequencyUltrasonic processing 5h obtains electrostatic spinning solution (C solution), and gained electrical conductivity of solution is 120mS/m, and viscosity is500cp；
The 4th step: under the condition of 25 DEG C of room temperatures and relative humidity 70%, under electrospinning device auxiliaryDescribed spinning solution is carried out to electrostatic spinning, and wherein solution pours into the flow velocity of 1mL/h, simultaneously in spraySilk head place applies the high direct voltage of 30kV, and the metallic plate that receiving system is ground connection, between receiving system and spinning nozzleDistance be 15cm, reception base material is aluminium foil; Obtain the high strength multicomponent taking common nanofiber as supportMesh nano tunica fibrosa; Described common nanofiber average diameter is 300nm, and reticular fibre average diameter is17nm, the hot strength of high strength multicomponent mesh nano fiber film material reaches 500MPa, mesh nano fibreDimension coverage rate is 98%, and its field emission scanning electron microscope photo is as shown in description Fig. 1.
Embodiment 2
A preparation method for high strength multicomponent mesh nano tunica fibrosa, concrete steps are:
The first step: 0.2g calcium bromide and 0.2g lithium chloride are joined to magnetic force in 15.6gN-methyl pyrrolidoneIon liquid dissolving system is prepared in stirring, then adds the mixed 5000rpm rotating speed that is incorporated in of 4g meta-aramid fibersExperiment disperse to disperse in sand mill making beating 5min, stir with the rotating speed of 100rpm with magnetic stirring apparatus at 80 DEG C10h, obtains meta-aramid and calcium bromide mass fraction and is respectively 20%, 2% stable homogeneous solution (A solution);
Second step: 1g polysulfones is joined in 8.95gN-methyl pyrrolidone and mixed, then add 0.05gThe aluminum oxide nanoparticle that particle diameter is distributed in 8-30nm mixes, and under 100 DEG C of oil bath heating, stirs with magnetic forceMix device and stir 10h with the rotating speed of 80rpm, obtain polysulfones and nano particle mass fraction and be respectively 10%, 0.5%Stable homogeneous solution (B solution);
The 3rd step: under the magnetic agitation of 200rpm rotating speed, the polysulfones Polymer Solution that second step is obtained byMass ratio with the speed of 3 second/droplet splashes into meta-aramid solution and drips mixing at 1: 5, under 55kHz frequencyUltrasonic processing 1h obtains electrostatic spinning solution (C solution), and gained electrical conductivity of solution is 1500mS/m, viscosityFor 10000cp;
The 4th step: under the condition of 25 DEG C of room temperatures and relative humidity 25%, under electrospinning device auxiliaryDescribed spinning solution is carried out to electrostatic spinning, and wherein solution pours into the flow velocity of 0.1mL/h, simultaneously in spraySilk head place applies the high direct voltage of 40kV, and the metallic plate that receiving system is ground connection, between receiving system and spinning nozzleDistance be 20cm, reception base material is nonwoven; Many groups of the high strength of acquisition taking common nanofiber as supportDivide netted nano fibrous membrane; Described common nanofiber average diameter is 500nm, and reticular fibre average diameter is5nm, the hot strength of high strength multicomponent mesh nano fiber film material reaches 1200MPa, mesh nano fibreDimension coverage rate is 95%.
Embodiment 3
A preparation method for high strength multicomponent mesh nano tunica fibrosa, concrete steps are:
The first step: 0.005g lithium bromide is joined to magnetic agitation in 3.795g dimethyl sulfoxide (DMSO) and prepare ionic liquidBody dissolution system, then adds the mixed experiment that is incorporated in 8000rpm rotating speed of 0.2g meta-aramid fibers to divide loose sandIn grinding machine, disperse making beating 10min, stir 5h with magnetic stirring apparatus with the rotating speed of 100rpm at 80 DEG C, between obtainingPosition aramid fiber and calcium bromide mass fraction are respectively 5%, 0.1% stable homogeneous solution (A solution);
Second step: will add 1.2g Pluronic F-127 to mix in 8.65g dimethyl sulfoxide solvent, thenAdd 0.1g particle diameter to be distributed in the silver nano-grain of 30-50nm and 0.05g particle diameter to be distributed in the oxygen of 40-50nmSiClx nano particle mixes, and under 100 DEG C of oil bath heating, stirs with the rotating speed of 120rpm with magnetic stirring apparatusMix 20h, acquisition Pluronic F-127 and nano particle mass fraction are respectively 12%, 1.5% stable homogeneous solution(B solution);
The 3rd step: under the magnetic agitation of 30rpm rotating speed, the Pluronic F-127 macromolecule that second step is obtained is moltenLiquid with the speed of 3 second/droplet splashes into meta-aramid solution in mass ratio and drips mixing at 1: 3, at 40kHz frequentlyUnder rate, ultrasonic processing 1h obtains electrostatic spinning solution (C solution), and gained electrical conductivity of solution is 500mS/m, stickyDegree is 300cp;
The 4th step: under the condition of 30 DEG C of room temperatures and relative humidity 20%, under electrospinning device auxiliaryDescribed spinning solution is carried out to electrostatic spinning, and wherein solution pours into the flow velocity of 1mL/h, simultaneously in spraySilk head place applies the high direct voltage of 30kV, and the metallic plate that receiving system is ground connection, between receiving system and spinning nozzleDistance be 18cm, reception base material is filter paper. Obtain the high strength multicomponent taking common nanofiber as supportMesh nano tunica fibrosa; Described common nanofiber average diameter is 100nm, and reticular fibre average diameter is5nm, the hot strength of high strength multicomponent mesh nano fiber film material reaches 100MPa, mesh nano fibreDimension coverage rate is 96%.
Embodiment 4
A preparation method for high strength multicomponent mesh nano tunica fibrosa, concrete steps are:
The first step: 0.05g KBr is joined to 3.95gN, magnetic agitation preparation in N-dimethylacetylamideIon liquid dissolving system, then adds the mixed experiment that is incorporated in 6000rpm rotating speed of 1g meta-aramid fibers to divideIn loose sand grinding machine, disperse making beating 10min, stir 5h with magnetic stirring apparatus with the rotating speed of 150rpm at 35 DEG C,Be respectively 20%, 1% stable homogeneous solution (A solution) to meta-aramid and calcium bromide mass fraction;
Second step: will add 0.6g polysulfones and 0.6g polyurethane to 8.65gN, dinethylformamide is organic moltenIn agent, mix, the monox nanometer particle that then adds 0.15g particle diameter to be distributed in 5-20nm mixes,Under 80 DEG C of oil bath heating, stir 15h with magnetic stirring apparatus with the rotating speed of 150rpm, obtain polysulfones and nanometerGrain mass fraction is respectively 12%, 1.5% stable homogeneous solution (B solution);
The 3rd step: under the magnetic agitation of 200rpm rotating speed, the polysulfones Polymer Solution that second step is obtained byMass ratio with the speed of 5 second/droplet splashes into meta-aramid solution and drips mixing at 1: 5, under 55kHz frequencyUltrasonic processing 2h obtains electrostatic spinning solution (C solution), and gained electrical conductivity of solution is 100mS/m, and viscosity is2500cp；
The 4th step: under the condition of 28 DEG C of room temperatures and relative humidity 25%, under electrospinning device auxiliaryDescribed spinning solution is carried out to electrostatic spinning, and wherein solution pours into the flow velocity of 1mL/h, simultaneously in spraySilk head place applies the high direct voltage of 45kV, and the metallic plate that receiving system is ground connection, between receiving system and spinning nozzleDistance be 20cm, reception base material is filter paper. Obtain the high strength multicomponent taking common nanofiber as supportMesh nano tunica fibrosa; Described common nanofiber average diameter is 800nm, and reticular fibre average diameter is15nm, the hot strength of high strength multicomponent mesh nano fiber film material reaches 1100MPa, mesh nanoFiber-covered rate is 96%.
Embodiment 5
A preparation method for high strength multicomponent mesh nano tunica fibrosa, concrete steps are:
The first step: 0.02g lithium bromide is joined to 1.8g dimethyl sulfoxide (DMSO) and 2.18gN, N--methyl formylIn the mixed solvent of amine, magnetic agitation is prepared ion liquid dissolving system, then adds 1g meta-aramid fibers mixedThe experiment that is incorporated in 5000rpm rotating speed disperses to disperse in sand mill making beating 12min, uses magnetic stirring apparatus at 80 DEG CStir 5h with the rotating speed of 100rpm, obtain meta-aramid and calcium bromide mass fraction and be respectively 20%, 0.4%Stable homogeneous solution (A solution);
Second step: 1.2g Pluronic F-127 is joined to 8.65gN, in the mixed solvent of N-dimethylacetylamideMix, then add 0.1g particle diameter to be distributed in Zirconium oxide nano grain and the 0.05g particle diameter of 10-25nmThe monox nanometer particle that is distributed in 8-45nm mixes, and under 100 DEG C of oil bath heating, uses magnetic stirring apparatusRotating speed with 100rpm stirs 15h, and obtain Pluronic F-127 and nano particle mass fraction and be respectively 12%,1.5% stable homogeneous solution (B solution);
The 3rd step: under the magnetic agitation of 200rpm rotating speed, the Pluronic F-127 macromolecule that second step is obtainedSolution with the speed of 3 second/droplet splashes into meta-aramid solution in mass ratio and drips mixing at 1: 3, at 40kHzUnder frequency, ultrasonic processing 1h obtains electrostatic spinning solution (C solution), and gained electrical conductivity of solution is 1500mS/m,Viscosity is 7500cp;
The 4th step: under the condition of 30 DEG C of room temperatures and relative humidity 20%, under electrospinning device auxiliaryDescribed spinning solution is carried out to electrostatic spinning, and wherein solution pours into the flow velocity of 3mL/h, simultaneously in spraySilk head place applies the high direct voltage of 50kV, and the metallic plate that receiving system is ground connection, between receiving system and spinning nozzleDistance be 28cm, reception base material is filter paper. Obtain the high strength multicomponent taking common nanofiber as supportMesh nano tunica fibrosa; Described common nanofiber average diameter is 1 μ m, and reticular fibre average diameter is17nm, the hot strength of high strength multicomponent mesh nano fiber film material reaches 1300MPa, mesh nanoFiber-covered rate is 100%.
Embodiment 6
A preparation method for high strength multicomponent mesh nano tunica fibrosa, concrete steps are:
The first step: 0.05g lithium bromide is joined to 4.45gN, magnetic in the mixed solvent of dinethylformamidePower stirs prepares ion liquid dissolving system, then adds the mixed 3000rpm that is incorporated in of 0.5g meta-aramid fibersThe experiment of rotating speed disperses to disperse in sand mill making beating 15min, at 80 DEG C with magnetic stirring apparatus turning with 150rpmSpeed stirs 3h, obtains meta-aramid and calcium bromide mass fraction and is respectively 10%, 1% stable homogeneous solution (ASolution);
Second step: will add 1.2g Pluronic F-127 to 4.3gN, N-dimethylacetylamide and 4g oxolaneMixed solvent in mix, then add 0.5g particle diameter to be distributed in the monox nanometer particle of 10-25nmMix, under 80 DEG C of oil bath heating, stir 20h with magnetic stirring apparatus with the rotating speed of 70rpm, obtain poly-ringOxygen ethene and nano particle mass fraction are respectively 12%, 1.5% stable homogeneous solution (B solution);
The 3rd step: under the magnetic agitation of 100rpm rotating speed, by the Pluronic F-127 high score obtaining with second stepSub-solution with the speed of 3 second/droplet splashes into meta-aramid solution in mass ratio and drips mixing at 1: 3, at 50kHzUnder frequency, ultrasonic processing 1h obtains electrostatic spinning solution (C solution), and gained electrical conductivity of solution is 800mS/m,Viscosity is 5500cp;
The 4th step: under the condition of 27 DEG C of room temperatures and relative humidity 23%, under electrospinning device auxiliaryDescribed spinning solution is carried out to electrostatic spinning, and wherein solution pours into the flow velocity of 0.8mL/h, simultaneously in spraySilk head place applies the high direct voltage of 35kV, and the metallic plate that receiving system is ground connection, between receiving system and spinning nozzleDistance be 25cm, reception base material is nonwoven. Many groups of the high strength of acquisition taking common nanofiber as supportDivide netted nano fibrous membrane; Described common nanofiber average diameter is 400nm, and reticular fibre average diameter is8nm, the hot strength of high strength multicomponent mesh nano fiber film material reaches 100MPa, mesh nano fibreDimension coverage rate is 97%.
Embodiment 7
A preparation method for high strength multicomponent mesh nano tunica fibrosa, concrete steps are:
The first step: 0.1g lithium bromide is joined to 10gN, dinethylformamide and 8.9gN, N-dimethylIn acetamide solvent, magnetic agitation is prepared ion liquid dissolving system, then adds 1g meta-aramid fibers to mixAnd disperse to disperse in sand mill making beating 5min in the experiment of 3000rpm rotating speed, at 100 DEG C with magnetic stirring apparatus withThe rotating speed of 200rpm stirs 4h, obtain meta-aramid and lithium chloride mass fraction be respectively 5%, 0.5% allOne stabilizing solution (A solution);
Second step: 1g Kynoar is joined to 5.4gN, mix in N--NMF, soAfter add 0.2g particle diameter to be distributed in 5-30nm Zirconium oxide nano grain and 0.1g particle diameter be distributed in 15-30nmTitanium dioxide nanoparticle mix, under 40 DEG C of oil baths heating with magnetic stirring apparatus the rotating speed with 20rpmStir 24h, obtaining Kynoar and nano particle mass fraction, to be respectively 15%, 4.5% stable homogeneous moltenLiquid (B solution);
The 3rd step: under the magnetic agitation of 20rpm rotating speed, the Kynoar macromolecule that second step is obtained is moltenLiquid with the speed of 1 second/droplet splashes into meta-aramid solution in mass ratio and drips mixing at 1: 2, at 60kHz frequentlyUnder rate, ultrasonic processing 3h obtains electrostatic spinning solution (C solution), and gained electrical conductivity of solution is 1500mS/m,Viscosity is 5800cp;
The 4th step: under the condition of 22 DEG C of room temperatures and relative humidity 20%, under electrospinning device auxiliaryDescribed spinning solution is carried out to electrostatic spinning, and wherein solution pours into the flow velocity of 10mL/h, simultaneously in spraySilk head place applies the high direct voltage of 60kV, and the metallic plate that receiving system is ground connection, between receiving system and spinning nozzleDistance be 30cm, reception base material is copper mesh. Obtain the high strength multicomponent taking common nanofiber as supportMesh nano tunica fibrosa; Described common nanofiber average diameter is 550nm, and reticular fibre average diameter is13nm, the hot strength of high strength multicomponent mesh nano fiber film material reaches 700MPa, mesh nano fibreDimension coverage rate is 99%.
Embodiment 8
A preparation method for high strength multicomponent mesh nano tunica fibrosa, concrete steps are:
The first step: 0.04g calcium chloride is joined to 1.96gN, middle magnetic in N-dimethylacetylamide and 1g acetonePower stirs prepares ion liquid dissolving system, then adds that 1g meta-aramid fibers is mixed to be incorporated in 3000rpm and to turnThe experiment of speed disperses to disperse in sand mill making beating 20min, stirs at 70 DEG C with magnetic stirring apparatus with the rotating speed of 20rpmMix 5h, obtain meta-aramid and lithium chloride mass fraction and be respectively 25%, 1% stable homogeneous solution (A is moltenLiquid);
Second step: 0.5g polyurethane and 0.5 Kynoar are joined to 94gN, in dinethylformamideMix, the copper oxide nanometer particle and the 2.5g particle diameter that then add 2.5g particle diameter to be distributed in 7-20nm divideThe silver nano-grain of cloth 5-20nm is mixing, under 100 DEG C of oil baths heating with magnetic stirring apparatus withThe rotating speed of 200rpm stirs 10h, and acquisition polyurethane and nano particle mass fraction are respectively 1%, 5% homogeneousStabilizing solution (B solution);
The 3rd step: under the magnetic agitation of 80rpm rotating speed, polyurethane, Kynoar that second step is obtainedPolymer Solution with the speed of 5 second/droplet splashes into meta-aramid solution in mass ratio and drips mixing at 1: 20, complies withInferior under 45kHz frequency ultrasonic processing 5h obtain electrostatic spinning solution (C solution), gained electrical conductivity of solution is600mS/m, viscosity is 10000cp;
The 4th step: under the condition of 20 DEG C of room temperatures and relative humidity 30%, under electrospinning device auxiliaryDescribed spinning solution is carried out to electrostatic spinning, and wherein solution pours into the flow velocity of 0.1mL/h, simultaneously in spraySilk head place applies the high direct voltage of 10kV, and the metallic plate that receiving system is ground connection, between receiving system and spinning nozzleDistance be 5cm, reception base material is copper mesh. Obtain the high strength multicomponent net taking common nanofiber as supportShape nano fibrous membrane; Described common nanofiber average diameter is 750nm, and reticular fibre average diameter is15nm, the hot strength of high strength multicomponent mesh nano fiber film material reaches 2000MPa, mesh nanoFiber-covered rate is 95%.
Embodiment 9-12 preparation process is with embodiment 1, wherein solution parameter, technological parameter and film properties parameter asShown in table 1:
Table 1
Embodiment 15-20 preparation process is with embodiment 2, wherein solution parameter, technological parameter and film properties parameterAs shown in table 2:
Table 2
Embodiment 21-26 preparation process is with embodiment 3, wherein solution parameter, technological parameter and film properties parameterAs shown in table 3:
Table 3
Embodiment 27-32 preparation process is with embodiment 4, wherein solution parameter, technological parameter and film properties parameterAs shown in table 4:
Table 4
Embodiment 33-38 preparation process is with embodiment 5, wherein solution parameter, technological parameter and film properties parameterAs shown in table 5:
Table 5
Embodiment 39-44 preparation process is with embodiment 6, wherein solution parameter, technological parameter and film properties parameterAs shown in table 6:
Table 6
Embodiment 45-50 preparation process is with embodiment 7, wherein solution parameter, technological parameter and film properties parameterAs shown in table 7:
Table 7
Embodiment 51-56 preparation process is with embodiment 8, wherein solution parameter, technological parameter and film properties parameterAs shown in table 8:
Table 8
Note: A solution is meta-aramid solution, B solution is functional high-polymer solution, C solution be by A andThe mixed electrostatic spinning solution of B.
Fig. 1 is the field emission scanning electron microscope of high strength multicomponent (PMIA/PU) mesh nano tunica fibrosa, in photo display fibers film, obviously there is multiple mesh nano fibre structure and the network structure coverage rate utmost point in photoHeight, in net, distribution of fiber diameters, in 17nm left and right, has obvious adhesion structure between fiber.
Claims (9)
1. a preparation method for multicomponent mesh nano tunica fibrosa, is characterized in that, concrete steps are:
The first step: meta-aramid fibers, halogen are mixed and pulled an oar with mass ratio 1:0.004 0.4:2.996 18.6 with organic solvent, stir preparation meta-aramid solution; Organic solvent and halogen are mixed to form stable ion liquid solvent system by described being mixed into first, then adds aramid fiber; Described making beating refers to and at room temperature utilizes experiment to disperse sand mill to disperse 5 20min with the rotating speed of 3000 8000rpm; It is to stir 1 10h with magnetic stirring apparatus with the rotating speed of 20 200rpm at 20 100 DEG C that described stirring refers in temperature;
Second step: functional high-polymer polymer is mixed with mass ratio 1:5.4 98.99 with solvent, add nano particle, add thermal agitation function equipment Polymer Solution; In functional high-polymer solution, the mass fraction of nano particle is 0.01% 5%;
The 3rd step: the functional high-polymer solution that the meta-aramid solution that the first step is obtained obtains with second step in mass ratio 1:0.05 0.5 drips and mixes, ultrasonic processing obtains spinning solution;
The 4th step: under the condition of 20 30 DEG C of room temperatures and relative humidity 20% 70%, described spinning solution is carried out to electrostatic spinning, obtain the multicomponent mesh nano tunica fibrosa taking common nanofiber as support.
2. the preparation method of multicomponent mesh nano tunica fibrosa as claimed in claim 1, is characterized in that, the thermal agitation that adds in described second step is to stir 5 24h with magnetic stirring apparatus with the rotating speed of 20 200rpm at 40 100 DEG C.
3. the preparation method of multicomponent mesh nano tunica fibrosa as claimed in claim 1, it is characterized in that, the dropping mixing in described the 3rd step refers to that room temperature 20 200rpm rotating speeds splash into meta-aramid solution by functional high-polymer solution with the speed of 15 seconds/under stirring; The supersonic frequency of the ultrasonic processing in the 3rd step is 40 60kHz, and the ultrasonic processing time is 1 5h; The electrical conductivity of the spinning solution in the 3rd step is 100 1500mS/m, and viscosity is 300 10000cp.
4. the preparation method of multicomponent mesh nano tunica fibrosa as claimed in claim 1, it is characterized in that, electrostatic spinning in described the 4th step refers under electrospinning device auxiliary spinning solution is poured into the flow velocity of 0.1 10mL/h, the high-tension electricity that applies 10 60kV in spinning head place carries out spinning simultaneously, receiving system is the metallic plate of ground connection, distance between receiving system and spinning nozzle is 5 30cm, and reception base material is aluminium foil, copper mesh, filter paper or nonwoven.
5. the preparation method of multicomponent mesh nano tunica fibrosa as claimed in claim 1, is characterized in that, described halogen is any one or a few the mixture in lithium chloride, calcium chloride, lithium bromide, sodium bromide, calcium bromide and KBr; Organic solvent in the described first step is any one or a few the mixture in DMF, 1-METHYLPYRROLIDONE, DMA, oxolane, dimethyl sulfoxide (DMSO) and acetone.
6. the preparation method of multicomponent mesh nano tunica fibrosa as claimed in claim 1, it is characterized in that, described functional high-polymer polymer is any one or a few the mixture in Kynoar, polyurethane, polysulfones, Pluronic F-127, PTT, nylon, polyacrylonitrile, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyacrylic acid and shitosan; Solvent in described second step is N, the mixture of any one or a few in dinethylformamide, formic acid, water, acetic acid, carrene, DMA, oxolane, trifluoroacetic acid, chloroform, 1-METHYLPYRROLIDONE, ethanol, acetone, n-butanol, isobutanol, hexafluoroisopropanol, dimethylbenzene, carbon tetrachloride, dimethyl sulfoxide (DMSO), pyridine, bromobenzene, methyl phenyl ethers anisole, phthalic acid and isopropyl alcohol; Nano particle is any one or a few the mixture in zirconia, silica, titanium oxide, aluminium oxide, cupric oxide and silver nano-grain, and the particle diameter of nano particle is 5 50nm.
7. as the preparation method of any one multicomponent mesh nano tunica fibrosa in claim 1 ~ 6, it is characterized in that, described common nanofiber refers to meta-aramid nano-fiber, functional high-polymer nanofiber and the Hybrid nanofibers jointly being formed by meta-aramid and functional high-polymer, and average fibre diameter is 100nm 1 μ m.
8. as the preparation method of any one multicomponent mesh nano tunica fibrosa in claim 1 ~ 6, it is characterized in that, in described multicomponent mesh nano tunica fibrosa, multicomponent reticular fibre has two-dimensional network structure, the hydridization mesh nano fiber that comprises meta-aramid mesh nano fiber, functional high-polymer mesh nano fiber and jointly formed by meta-aramid and functional high-polymer, mesh nano average fibre diameter is 5 20nm, and the coverage rate of network structure in tunica fibrosa reaches more than 95%.
9. as the preparation method of any one multicomponent mesh nano tunica fibrosa in claim 1 ~ 6, it is characterized in that, the hot strength of described multicomponent mesh nano tunica fibrosa reaches 100 2000MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410061970.2A CN103806221B (en) | 2014-02-24 | 2014-02-24 | A kind of preparation method of multicomponent mesh nano tunica fibrosa |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410061970.2A CN103806221B (en) | 2014-02-24 | 2014-02-24 | A kind of preparation method of multicomponent mesh nano tunica fibrosa |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103806221A CN103806221A (en) | 2014-05-21 |
| CN103806221B true CN103806221B (en) | 2016-05-04 |
Family
ID=50703581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410061970.2A Active CN103806221B (en) | 2014-02-24 | 2014-02-24 | A kind of preparation method of multicomponent mesh nano tunica fibrosa |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103806221B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104294479B (en) * | 2014-09-05 | 2018-03-30 | 上海工程技术大学 | A kind of native cellulose/polyacrylonitrile nano anti-bacterial fibre film and preparation method thereof |
| CN104480702B (en) * | 2014-12-29 | 2016-08-24 | 中科院广州化学有限公司 | A kind of preparation method and applications of oil dispersion aramid nano-fiber |
| CN104437140B (en) * | 2014-12-29 | 2017-02-22 | 中科院广州化学有限公司 | Nano aramid fiber reinforced polysulfone membrane and preparation method and application thereof |
| JP2016164319A (en) * | 2015-03-06 | 2016-09-08 | パナソニックＩｐマネジメント株式会社 | Non-woven cloth and inspection tool |
| CN105063808B (en) * | 2015-07-29 | 2017-06-30 | 浙江理工大学 | A kind of preparation method of the hollow type meta-aramid nano-fiber of lamellar structure stacking |
| CN105113045B (en) * | 2015-09-28 | 2017-05-10 | 倪士勇 | Fiber, method for manufacturing same and fabric with fiber |
| CN105113051A (en) * | 2015-09-28 | 2015-12-02 | 倪士勇 | Fiber, method for manufacturing same and fabric with fiber |
| CN106087411B (en) * | 2016-06-06 | 2018-06-12 | 深圳市新纶科技股份有限公司 | A kind of modifying aramid fiber pulp and preparation method thereof and the brake block manufactured with it |
| CN107354532A (en) * | 2017-06-28 | 2017-11-17 | 滁州市三和纤维制造有限公司 | A kind of preparation method of polyurethane-modified Fanglun slurry cake |
| CN107297103B (en) * | 2017-07-28 | 2020-05-15 | 中材科技膜材料（山东）有限公司 | Dust filtering base material, preparation method and application thereof |
| CN107354587B (en) * | 2017-08-01 | 2019-12-31 | 东华大学 | Two-dimensional net-shaped superfine nanofiber material for air filtration and preparation method thereof |
| CN107675361B (en) * | 2017-10-12 | 2019-05-10 | 上海工程技术大学 | A kind of Static Spinning nano-composite fiber felt and its preparation method and application |
| CN109355803B (en) * | 2018-11-30 | 2020-08-07 | 中科院广州化学有限公司 | Preparation method of coated polysulfide electrostatic spinning nanofiber membrane and application of coated polysulfide electrostatic spinning nanofiber membrane in metal ion adsorption under oxidative stimulus response |
| CN111020882A (en) * | 2019-12-13 | 2020-04-17 | 中国科学院深圳先进技术研究院 | Flexible conductive fiber membrane material and preparation method thereof |
| CN111013272A (en) * | 2020-01-13 | 2020-04-17 | 中原工学院 | PVDF (polyvinylidene fluoride) dendritic structure nanofiber air filtering material and preparation method thereof |
| CN111013256A (en) * | 2020-01-15 | 2020-04-17 | 中原工学院 | High-efficiency low-resistance multi-component air filtering material with three-dimensional cavity structure and preparation method thereof |
| CN111411450B (en) * | 2020-02-17 | 2022-06-21 | 五邑大学 | Preparation method and application of flexible nano-cobweb-structured conductive polyurethane film |
| CN111249926A (en) * | 2020-02-24 | 2020-06-09 | 上海工程技术大学 | Meta-aramid/polysulfonamide nano composite air filter membrane and preparation method thereof |
| CN112962216B (en) * | 2021-02-07 | 2022-02-01 | 宁波工程学院 | Preparation method of nylon 6/chitosan/precious metal nano-fiber |
| CN113794034A (en) * | 2021-08-03 | 2021-12-14 | 惠州锂威新能源科技有限公司 | Self-supporting diaphragm and preparation method thereof, composite pole piece and secondary battery |
| CN113842498B (en) * | 2021-08-31 | 2023-01-17 | 上海市第六人民医院 | Electrospun membrane scaffold for promoting healing of rotator cuff tendon and bone and inhibiting muscle fat infiltration and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003917A (en) * | 2007-01-19 | 2007-07-25 | 中国民航大学 | Complex type electrostatic spinning method with positive and negative electrodes in same electric field, and application |
| CN101279204A (en) * | 2008-01-15 | 2008-10-08 | 沈阳航空工业学院 | Preparation of high intensity nano fibre functional film |
| CN101838888A (en) * | 2010-05-10 | 2010-09-22 | 张家港耐尔纳米科技有限公司 | Method for preparing electrospun meta-aramid nano-fiber |
| CN101928996A (en) * | 2010-07-20 | 2010-12-29 | 东华大学 | Preparation method of fibrous membrane with super hydrophobic multi-stage nanometer structure |
| CN102247027A (en) * | 2011-06-20 | 2011-11-23 | 东华大学 | Protective material capable of efficiently decomposing biochemical reagent and preparation method thereof |
| CN102704028A (en) * | 2012-05-26 | 2012-10-03 | 东华大学 | Preparation method of meta-aramid nano-nets fiber membrane |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101275058B1 (en) * | 2011-08-17 | 2013-06-17 | 웅진케미칼 주식회사 | Electro spinning method of Meta Aramid and Meta Aramid fiber manufactured therefrom |
| KR101273898B1 (en) * | 2011-08-17 | 2013-06-17 | 웅진케미칼 주식회사 | Manufacturing method of Meta Aramid nonwoven fabric and Meta Aramid nonwoven fabric manufactured thereby |
-
2014
- 2014-02-24 CN CN201410061970.2A patent/CN103806221B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003917A (en) * | 2007-01-19 | 2007-07-25 | 中国民航大学 | Complex type electrostatic spinning method with positive and negative electrodes in same electric field, and application |
| CN101279204A (en) * | 2008-01-15 | 2008-10-08 | 沈阳航空工业学院 | Preparation of high intensity nano fibre functional film |
| CN101838888A (en) * | 2010-05-10 | 2010-09-22 | 张家港耐尔纳米科技有限公司 | Method for preparing electrospun meta-aramid nano-fiber |
| CN101928996A (en) * | 2010-07-20 | 2010-12-29 | 东华大学 | Preparation method of fibrous membrane with super hydrophobic multi-stage nanometer structure |
| CN102247027A (en) * | 2011-06-20 | 2011-11-23 | 东华大学 | Protective material capable of efficiently decomposing biochemical reagent and preparation method thereof |
| CN102704028A (en) * | 2012-05-26 | 2012-10-03 | 东华大学 | Preparation method of meta-aramid nano-nets fiber membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103806221A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103806221B (en) | A kind of preparation method of multicomponent mesh nano tunica fibrosa | |
| CN106567274B (en) | A method of preparing aramid paper with p-aramid fiber nanofiber | |
| Zhang et al. | Spraying functional fibres by electrospinning | |
| Gonçalves et al. | Morphology and thermal properties of core-shell PVA/PLA ultrafine fibers produced by coaxial electrospinning | |
| CN101709534A (en) | Device and method for manufacturing airflow melting electrostatic spinning nano-fiber non-woven fabric | |
| Jiang et al. | An improved free surface electrospinning for high throughput manufacturing of core–shell nanofibers | |
| CN106835304B (en) | A kind of electrostatic spinning-electrical painting device and its application | |
| Qian et al. | Electrospinning of polymethyl methacrylate nanofibres in different solvents | |
| CN103752848B (en) | A kind of preparation method of nano-silver thread | |
| CN106238726B (en) | A kind of flexible compound nano-silver thread and preparation method thereof | |
| CN103061038A (en) | Tourmaline electret polylactic acid melt-blown non-woven cloth and manufacture method | |
| CN102534869A (en) | Method for preparing high-strength conductive graphene fiber by large-size graphene oxide sheet | |
| CN106229446A (en) | The one-body molded preparation method of lithium battery multiple elements design barrier film and diaphragm material | |
| Wang et al. | Preparation of flexible phenolic resin-based porous carbon fabrics by electrospinning | |
| CN102733000A (en) | Preparation method for hollow polymer nanofibers | |
| Wei et al. | Nanofibers: principles and manufacture | |
| Xie et al. | Highly stable coated polyvinylpyrrolidone nanofibers prepared using modified coaxial electrospinning | |
| Kang et al. | Electrospun poly (tetrafluoroethylene) nanofiber membranes from PTFE-PVA-BA-H 2 O gel-spinning solutions | |
| Im et al. | Preparation of poly (vinyl alcohol)/zro 2 composite nanofibers via co-axial electrospinning with higher zro 2 particle content | |
| Zhang et al. | Stable multi-jet electrospinning with high throughput using the bead structure nozzle | |
| Raghavan et al. | Control of Inter-fiber Fusing for nanofiber Webs via Electrospinning | |
| CN106048749B (en) | A kind of linear channel-shaped needle-free electrostatic spinning apparatus and spinning process | |
| CN108998841A (en) | A kind of preparation method of porous polypropylene nitrile nanofibre | |
| CN113046925B (en) | Polyvinylidene fluoride superfine nanofiber membrane and preparation method thereof | |
| Cheng et al. | Effect of surface active agent on bubble-electrospun polyacrylonitrile nanofibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |