CN101649501B - Magnetic composite nano fiber and preparation method thereof - Google Patents
Magnetic composite nano fiber and preparation method thereof Download PDFInfo
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- CN101649501B CN101649501B CN2009101873127A CN200910187312A CN101649501B CN 101649501 B CN101649501 B CN 101649501B CN 2009101873127 A CN2009101873127 A CN 2009101873127A CN 200910187312 A CN200910187312 A CN 200910187312A CN 101649501 B CN101649501 B CN 101649501B
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Abstract
The invention relates to a magnetic composite nano fiber and a preparation method thereof. The magnetic fluid comprising magnetic nanocrystalline and silicone oil in a heat resistant container (g) is arranged in the lower layer, a conductive polymer solution is arranged in the upper layer, and the vertical upper side and the lower side of the heat resistant container are provided with a high magnetic field (f); an electrode (d) is arranged at the bottom of the heat resistant container, a reverse electrode (c) is arranged above the heat resistant container, and the distance between the surface of the conductive solution and the reverse electrode is adjustable; and when the electrode voltage is 35-40 KV, and the distance between the reverse electrode and the surface of the solution is 10-15cm, the polymer solution realizes multistrand spray to the grounded reverse electrode to form a magnetic composite nano fiber. The fiber has the diameter of 80nm-4.0 microns, the length of 2-80 microns, the length-diameter ratio of 5-1,000 and the magnetic nanocrystalline mass percentage of 10-15 percent; in the frequency range of 2-18 GHz, the average attenuation is larger than -20dB, the peak absorption reaches -60dB, and the reflectivity is smaller than -10dB; and the strength can reach 2-8Mpa.
Description
Technical field
The present invention relates to the magnetic composite nano fiber technical field that magnetic nanometer particles and macromolecule are composited, be specifically related to the technical method that the auxiliary needleless electricity in magnetic field spins.
Background technology
Absorbing material is the electromagnetic a kind of functional material that can absorb, decay.Its basic principle is when electromagnetic wave acts on absorbing material, and material can produce electrical loss, magnetic loss etc. and convert electromagnetic energy to other forms of energy (mainly being heat energy) and dissipate, or electromagnetic wave is disappeared because of interference.Military stealth technology utilizes absorbing material to reduce or eliminate radar, the detection feature to target such as infrared to greatest extent; Now; The application of absorbing material has exceeded the military applications scope with research; More be widely used for microwave dark room, electromagnetic shielding, the reflection of reduction optics, avoid aspects such as communication apparatus disturbs, the anti-spoke of building, elimination ghost image of the tv; Therefore carrying out the preparation and the research of absorbing material, is that military affairs or civilian all have far reaching significance.
Good absorbing material should possess three conditions: when the absorbing material surface is propagated, incided in (1) when electromagnetic wave; Can make electromagnetic wave enter into absorbing material inside to greatest extent; To reduce electromagnetic direct reflection; This just requires when designing material, should take into full account its wave impedance matching properties.(2) in a single day get into material internal when electromagnetic wave, then require absorbing material can produce incident electromagnetic wave and effectively absorb or decay, promptly produce electromagnetic consumable, this will consider the electromagnetic consumable characteristic of material, i.e. attenuation characteristic.(3) satisfy the developing direction of " thin (thickness), light (weight), wide (frequency band), strong (absorption) ".Absorber to the single constituent element of tradition; It is impossible satisfying wave impedance matching properties and attenuation characteristic simultaneously; The material that real complex dielectric permittivity imaginary part ε " equals complex permeability imaginary part μ " also difficulty finds, and this is narrow owing to frequency band with regard to the application that makes traditional absorbing material, efficient is low, density is big is restricted.From development trend, novel wave-absorbing material should refinement compoundization again, promptly nano combinedization could be regulated electromagnetic parameter, makes it as far as possible under matching condition, to improve the absorption loss ability.
At present; When further improving and improving traditional absorbing material, just be devoted to the exploration of multiple new material both at home and abroad; Composite nano wave-absorbing material, cenosphere type absorbing material, conducting polymer absorbing material, CNT absorbing material and intelligent stealth technology etc. progressively are applied in the radar wave camouflage material because of controlling material dielectric constant and magnetic conductivity, thereby satisfy the requirement of absorbing material of new generation " thin, light, wide, strong ".Composite nano wave-absorbing material because of with different types of inorganic nano and organic polymer compound can process resistance loss type, dielectric loss type, the magnetic loss type of strong absorption and have electromagnetic consumable type absorbing material concurrently become focus.
The composite Nano wave absorbing agent mainly comprises composite nano powder, film and fiber wave absorbing agent
[1]Nanofiber has and powder, film different features, mainly shows as (1) dimensional effect, because specific area increases, volume reduces, reactivity and selectivity is obviously improved; (2) supermolecule is arranged effect, because the regular arrangement of molecule can realize selfization, thereby can manifest unified function; (3) hierarchical structure effect, the new effect that promptly occurs owing to the nanometer hierarchical structure of nano-high molecule chain level.These effects make the nanofiber absorbing material have in light weight, advantage such as surface density is little, intensity is high, modulus is high, bandwidth and ABRASION RESISTANCE are good; The electromagnetic parameter of the corresponding adjusting materials such as content of the length through regulating fiber, diameter, arrangement mode, dispersant is regulated the material absorbing property thereby reach.Research both at home and abroad shows
[2-4]The nanofiber wave absorbing agent particularly the nano-magnetic fibre absorbent because its magnetic anisotropy; Effective permeability can be greatly improved on the fibre length direction; Broken away from the restriction of spherical particle, therefore can under the low situation of volume content, obtain higher magnetic conductivity, helped weight reduction, broadening bandwidth Effective permeability
[5]Goldber etc.
[6]Report, draw ratio are that 50 ferrite fibre is compared with the non-fiber magnetic material of same amount, and its magnetic conductivity has increased by 50 times.Chen etc.
[7]Directly obtain the ZnO nanofiber at air evaporation with the metallic zinc powder, the result shows, the ZnO powder to the absorption of electromagnetic wave ability very a little less than, and the ZnO nanofiber is stronger to the absorption of electromagnetic wave ability.The composite nano fiber wave absorbing agent not only has the characteristic of magnetic fibre, also because of its distinctive nano effect, has excellent research and is worth.
At present, the preparation nanofiber has a lot of methods, wherein method of electrostatic spinning because can prepare that pattern is controlled, homogeneous, the very big material of draw ratio and become the main flow direction of research, receive much attention in the past several years always.Classical electrostatic spinning is to utilize high voltage to make the Polymer Solution surface have electric charge, and under the inducing of electric field, Polymer Solution stretches from the nozzle ejection and forms nanofiber.Its equipment is very simple: only need high voltage source, spinning heatproof container (normally syringe), shower nozzle (normally syringe needle), collecting board with holes, add some leads and get final product.The advantage of this method be cheap, convenient, simple to equipment requirements, preparation condition is gentle, process simply reaches environmentally safe etc., and can prepare that pattern is controlled, homogeneous, material that draw ratio is very big.Some research groups successively introduce the nanofiber research field with electrostatic spinning technique both at home and abroad in recent years, and have realized the morphology control to material to a certain extent, for example, and γ-Fe
2O
3, α-Fe
2O
3 [8,9], ZnO
[10], SiC
[11], BaTiO
3 [12,13]Fiber and MnFe
2O
4 [14], CoFe
2O
4 [15], CoFe
2O
4-Pb (Zr
0.52Ti
0.48)
O-3 [16], ZrO
2/ SiO
2 [17], PPV/PVA
[18]Prepared successively Deng composite nano fiber etc.
Recently; The composite magnetic nanofiber that magnetic nanometer particles and macromolecule is composited by method of electrostatic spinning is owing to have the characteristic of magnetic material, macromolecular material and nanofiber concurrently; Thereby favored; They had both had, and high molecular elasticity is high, process stability is strong, the characteristics of light weight, has the magnetic, high rigidity of magnetic inorganic material again concurrently, to characteristics such as heat and chemical attack are stable
[19]The research of relevant this respect is successively by bibliographical information; For example; The coaxial electrostatic spinning method obtains the FePt/PCL composite fibre, and particle diameter is that the FePt particle of 4nm is disperseed to be packaged in polycaprolactone (PCL) fiber, and shape is like composite nano fiber long Du Keda 3000nm the kidney bean; This nanofiber can be superparamagnetism usually, and its mechanical performance is better than magnetic particle itself
[20,21]Fe
3O
4/ PVP
[22]Fe in the composite nano fiber
3O
4Particle is evenly distributed in PVP (polyvinylpyrrolidone) fiber, Fe
3O
4Mass fraction be 36.18%, fiber demonstrates the characteristic of superparamagnetism; The CoFe that sol-gel process combines with method of electrostatic spinning and prepares
2O
4/ PVAc (polyvinyl acetate)
[23], have fine magnetic property; MnFe
2O
4/ PVAc
[24], Fe
2YF
5/ PVP
[25], NiFe
2O
4-Pb (Zr0
.52Ti
0.48)
O-3 [26]Inorganic nano-crystal in the composite nano fiber can both be distributed in the fiber parent uniformly, and these are nanocrystalline small-sized, and composite nano fiber has significant microwave absorbing property.
The problem that method of electrostatic spinning exists mainly contains: the firstth, and productivity ratio is extremely low.Its typical preparative capacibility is merely 0.001-1g/h, and a pin is realized one injection stream only, and the purposes of single nanofiber is extremely limited; If demanding productivity ratio or preparation composite fibre just need many pins, and so very easily cause obstruction.The secondth, the reappearance of spinning process is relatively poor.Because from the track of syringe needle ejection thread is very complicated 3d orbit, makes stability of technological process be affected, collected fiber alignment is disorderly and unsystematic mostly, and reappearance is relatively poor.Many seminars are all transforming method of electrostatic spinning both at home and abroad at present, in the hope of addressing the above problem.
List of references
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[2]Wang?D.J.，Tang?Y.，Dong?A.G.，et?al.，Acta?Chimica?Sinica，2003，61(9)：142.
[3] Mao Qianjin, in rosy clouds, Wang Qun, etc., Beijing University of Technology's journal, 2003,23 (3): 10.
[4]Kim?S.S.，Kim?E.T，Journal?of?Magnetism?and?Magnetic?Materials，2004，271：392.
[5] Wu Mingzhong, Zhao Zhensheng, what Hua Hui, functional material, 1999,30 (1): 91.
[6]Bordo?V.G.，Physical?Review，2008，8：101.
[7]Chen?Y.J.，Cao?M.S.，Wang?T.，Appl?Phys?Lett，2004，48(12)：3367.
[8]Zhan?S.H.，Chen?D.R.，Jiao?X.L.，et?al.，Journal?of?Colloid?and?InterfaceScience，2007，1：265.
[9]Zhu?Y.，Zhang?J.C.，Zhai?J.，et?al.，Thin?Solid?Films，2006，1：271.
[10]P.Viswanathamurthi，N.Bhattarai，H.Y.Kim，D.R.Lee，Nanotechnology，2004，15：320.
[11]Zhang?Z.M.，Wan?M.X.，Wei?Y，Nanotechnology，2005，12：2827.
[12]J.Yuh，J.C.Nino，W.M.Sigmund，Mater.Lett，2005，59：3645.
[13]J.T.Mcann，J.I.L.Chen，Dan?Li，Z.G.Ye，Y.Xia，Chem.Phys.Lett.，2006，424：162.
[14]B.Dong，H.Song，H.Yu，H.Zhang，R.Qin，J.Phys.Chem.C，2008，112，1435.
[15]Ju?Y.W.，Park?J.H.，Jung?H.R.，et?al.，Materials?Science?and?Engineering，2008，1：7.
[16]Xie?S.H.，Li?J.Y.，Qiao?Y.，et?al.，Applied?Physics?Letters，2008，6：35.
[17] Zhao Yiyang, Wang Haiying, Li Xiang, etc., SCI, 2007,28 (2): 382.
[18] Zhang Wen, Huang Zonghao, Wang becomes, etc., functional material, 2006,37 (4): 196.
[19]X.Sui，C.Shao，Y.Liu，Appl.Phys.Lett.2005，87：113.
[20]Song?T.，Zhang?Y.Z.，Zhou?T.J.，et?al.，Chemical?Physics?Letters，2005，4：317.
[21]Wang?A.，Singh?H.，Hatton?T.A.，et?al.，Polymer，16：550.
[22] Li Xiang, Wang Ce, SCI, 2006,10:2002.
[23]Zhao?Y.Y.，Martens?W.N.，Zhu?H.Y.，et?al.，International?Conference?onNanoscience?and?Nanotechnology，2006，1：242.
[24]Ju?Y.W.，Park?J.H.，Jung?H.R.，et?al.，Composites?Science?and?Technology，2008，7：1704.
[25]B.Dong，H.Song，H.Yu，H.Zhang，R.Qin，J.Phys.Chem.C，2008，112：1435
[26]Xie?S.H.，Li?J.Y.，Liu?Y.Y.，et?al.，Journal?of?Applied?Physics，2008，2：42.
[27]A.L.Yarin，E.Zussman，Polymer，2004，45：2977.
Summary of the invention
Defective to the prior art existence; The object of the present invention is to provide and having transformed classical electrospinning process is the method that the auxiliary needleless electricity in magnetic field spins; Make macromolecule surface realize the injection stream that multiply makes progress, form the composite magnetic nanofibrous structures, and boost productivity.
Principle of the present invention is: the auxiliary needleless electricity in magnetic field spins and utilizes vertical direction magnetic field, electric field to act on a stratified fluid system simultaneously, and lower floor's magnetic fluid impacts the upper strata conductive polymer solution and forms countless spicules, and electric spinning obtains nanofiber.Utilize the characteristics of ferromagnetic suspension, in magnetic field, realize the multiply injection stream without any need for pin.
Technological process of the present invention is as shown in Figure 1.The magnetic Nano that sol-gel process obtains brilliant (or cenosphere type magnetic Nano is brilliant) is processed magnetic fluid (magnetic Nano crystalline substance or cenosphere type magnetic Nano are brilliant to be mixed by 1: 2 weight ratio with silicone oil, and it is put into heatproof container).With polyacetylene class conductive polymer solution is the upper strata, and magnetic fluid is a lower floor, and gained composite electrospun solution spins legal system through the magnetic field auxiliary electrical and is equipped with composite nano fiber.Said polyacetylene class conducting polymer is two substituted polyacetylenes and block or graft copolymer, promptly gather sym-dibromoethylene, gather acetylene dichloride and gather dibenzenyl and block or graft copolymer in a kind of, W
MBe 3 * 10
4～1 * 10
7
Said polyacetylene class conducting polymer for the block copolymer in two substituted polyacetylenes and block or the graft copolymer is: 1. when polyacetylene segment content is 10%-25% (m) and the block copolymer that becomes of styrene (or isoprene); 2. polystyrene (or polyisoprene) is a main chain, and polyacetylene is the graft copolymer of side chain, and wherein polyacetylene segment content is the graft copolymer that 10%-40% becomes.Its block or graft copolymer are soluble conductive macromolecular.Said block copolymer, graft copolymer in synthetic, still done to mix with halogen or benzene, " polyacetylene segment " on the block copolymer is to gather acetylene dichloride, gather sym-dibromoethylene or gather tolans.
Said conductive polymer solution is: in two substituted polyacetylenes: 40% ethanol water that the two substituted polyacetylene ethanol solutions of 2%wt chlorine or bromine add equivalent mixes, or the 40% toluene aqueous solution that 2%wt diphenyl substituted polyacetylene toluene solution adds equivalent forms; Block copolymer is that the 40% chloroform water solution that the chloroformic solution of 2%wt polyacetylene block copolymer adds equivalent mixes; Graft copolymer is that 40% tetrahydrofuran aqueous solution of the tetrahydrofuran solution equivalent of 2%wt graft copolymer mixes;
It is as shown in Figure 3 that the magnetic field auxiliary electrical is spun subtraction unit.For the auxiliary needleless electricity in magnetic field spins method experimental provision sketch.A is a magnetic fluid layer among the figure, and b is the conductive polymer solution layer, and c counterelectrode, d are that electrode inserts in the magnetic fluid, and e is a high voltage source, and f is permanent magnet or the coil that high-intensity magnetic field is provided.It is to carry out among the heatproof container g in vertically strong magnetic field that the magnetic field auxiliary electrical is spun method.An electrode d inserts the bottom among the heatproof container g, and another counterelectrode c places the heatproof container top, and conductive polymer solution b surface is adjustable with the distance between the counterelectrode.During operation; After conductive polymer solution b adds; Be immersed in voltage on the bottom electrode among the heatproof container g and constantly increase to 35～40KV, top counterelectrode and liquid level polymer solution when 10～15cm and begin to realize that to the counterelectrode of ground connection multiply sprays (as shown in Figure 4), lower floor's magnetic fluid impacts that the upper strata conductive polymer solution forms countless spicules and electric spinning obtains nanofiber.
" black hole " effect that obtains electrical loss, magnetic loss and cenosphere is inhaled the ripple nanofiber in the MULTILAYER COMPOSITE of the impedance transition mechanism structure of one.Can cover wave bands such as centimeter wave, millimeter wave, infrared, visible light by the nano combined absorbing material of its preparation; In the 2-18GHz frequency range, average attenuation is greater than-20dB, and peak absorbance reaches-60dB, and reflectivity is all less than-10dB; Density is d=0.2-0.6g/cm3, and intensity can reach 2-4Mpa, and dispersive property is good, can be evenly dispersed in the base-material.
The circular cross section of above-described magnetic composite nano fiber is the outer conducting polymer that is, its nexine is the magnetic Nano nucleus.Fibre diameter is 80nm～4.0 μ m, and magnetic Nano crystalloid amount mark is 10～15%, and fibre length is in that 2 μ m～80 mu m ranges are adjustable, and the fiber draw ratio is 5～1000.Magnetic composite nano fiber again with following two kinds for well, be the composite nano fiber of nuclear promptly and be the composite nano fiber of nuclear that it characterizes and performance is with cenosphere type magnetic Nano crystalline substance with the magnetic Nano crystalline substance:
(1) with the magnetic Nano crystalline substance be the composite magnetic nanofiber of nuclear: its cross section is shown in accompanying drawing 2-a, and the skin of circular cross section is conducting polymer a, and internal layer is nanometer ferrite nuclear b.Fibre diameter is between 85～165nm, and average diameter is the soft magnetism γ-Fe about 10nm
2O
3Nano particle or Hard Magnetic Fe
3O
4Nano particles etc. are evenly distributed in the conducting polymer fibres, and magnetic Nano crystalloid amount mark is between 10～15%, and fibre length is in that 2 μ m～80 mu m ranges are adjustable, and the fiber draw ratio is 5～1000.
In 2～18GHz frequency range, on average greater than-15dB, peak absorbance reaches-40dB magnetic composite nano fiber wave absorbing agent of the present invention to attenuation of Electromagnetic, and reflectivity is all less than-10dB; Density is d=0.6g/cm
3, intensity can reach 2.6Mpa, and dispersive property is good, can be evenly distributed in the base-material.
(2) the brilliant composite magnetic nanofiber for nuclear of cenosphere type magnetic Nano: its cross section is shown in accompanying drawing 2-b; The skin of circular cross section is conducting polymer a; Its internal layer be nanometer ferrite with rich iron cenosphere in the two spin-exchange-coupled inclusion enclave c mutually that form of iron phase, the bosom is the cavity d of cenosphere.Fibre diameter is about (diameter of cenosphere own is between 1-3 μ m) between the 2-3.5 μ m, and average diameter is 1.5-3 μ m left and right sides SmFeO
3/ Fe
2O
3Nanocrystalline parcel cenosphere is evenly distributed in the conducting polymer fibres, and magnetic Nano crystalloid amount mark is between 10-15%, and fibre length is in that 2 μ m～80 mu m ranges are adjustable, and the fiber draw ratio is 5～1000.
In 2～18GHz frequency range, on average greater than-20dB, peak absorbance reaches-60dB magnetic composite nano fiber wave absorbing agent of the present invention to attenuation of Electromagnetic, and reflectivity is all less than-10dB; Density is d=0.2g/cm
3, intensity can reach 4Mpa, and dispersive property is good, can be evenly distributed in the base-material.
Described magnetic Nano crystalline substance is γ-Fe
2O
3, cenosphere type magnetic Nano crystalline substance is SmFeO
3/ Fe
2O
3Nanocrystalline+cenosphere.
Sol-gel process is clad nano ferrite (crystallite dimension is less than 10nm) thin layer SmFeO on rich iron cenosphere surface
3, coating form is stratiform or network-like distribution.According to spin-exchange-coupled flexible magnets model, if two arbitrary phase is arranged in mutually crystallite dimension less than critical dimension (10nm), clad ferrite SmFeO
3With the iron phase Fe on the rich iron cenosphere
2O
3Spin-exchange-coupled will take place, and two exchange coupling body SmFeO mutually
3/ Fe
2O
3Can significantly improve anisotropy energy, strengthen wave-sucking performance.
The particle diameter of cenosphere is 1-3 μ m (a 7000-5000 order), and the mass fraction in the magnetic Nano crystalline substance is 60-75%.The ratio of adjustment base-material, magnetic composite nano fiber wave absorbing agent, additive (can add as required) after process high-speed mixer or low speed mixer are even, can be used.Mixing process is simple, and the user can allocate as required.
The magnetic composite nano fiber of the present invention's preparation is mainly used in the wave absorbing agent in stealth technology and the electromagnetic shielding; Conducting polymer and magnetic Nano crystalline substance is compound, improve magnetic conductivity with the sacrificial section electrical loss, can make electromagnetic parameter convergence optimum Match; Reduce reflection, increase absorption.The electromagnetic parameter of corresponding adjusting materials such as the length through regulating brilliant structure, granularity, dispersiveness and composite fibre of magnetic Nano, diameter, arrangement mode, thus reach the purpose of regulating the material absorbing property, obtain efficient composite nano fiber wave absorbing agent.
Compared with prior art religion, the characteristics that the present invention gives prominence to are: (1) proposes a high production rate ground preparation functional multi layer composite nano fiber new way-magnetic field auxiliary electrical and spins method.The 10-100 that can boost productivity doubly.(2) composite magnetic nanofiber wave absorbing agent is to be that shell, magnetic nano-particle are nuclear with the conducting polymer, and " black hole " effect of current collection loss, magnetic loss and cenosphere is in the wave absorbing agent of one.To absorb favourable conducting polymer and magnetic nano-particle combines to different frequency bands with composite methods, can reach the purpose of widening frequency band.The electromagnetic parameter of corresponding adjusting materials such as the content of the length through regulating fiber, diameter, arrangement mode, magnetic Nano nucleus and distribution mode, thus reach the purpose of regulating the material absorbing property, broken away from the restriction of spherical particle to Effective permeability.(3), when the size of magnetic is suitable with the characteristic physical length, will present the magnetic property of abnormality owing to be in nanometer scale just with the characteristic physical length of magnetic dependence.The nanofiber that magnetic nanometer particles and macromolecule are composited has the characteristic of nano magnetic material and macromolecular material concurrently; Demonstrate unique character at aspects such as light, electricity, sound, magnetic, therefore have potential application prospect at aspects such as chemical industry, information material, medical science and bioengineering.
Below with specific embodiment the present invention is described further.
Description of drawings
Fig. 1: be technology path process block diagram.
Fig. 2: multi-layered magnetic composite nano fiber cross sectional representation.Wherein A figure is the brilliant composite nano fiber cross sectional representation for nuclear of magnetic Nano, and the skin of circular cross section is conducting polymer a, and internal layer is nanometer ferrite nuclear b; B figure is the composite nano fiber cross sectional representation of cenosphere type magnetic Nano nucleus; The skin of circular cross section is conducting polymer a; Its internal layer be nanometer ferrite with rich iron cenosphere in the two spin-exchange-coupled inclusion enclave c mutually that form of iron phase, the bosom is the cavity d of cenosphere.
Fig. 3: for the auxiliary needleless electricity in magnetic field spins method experimental provision sketch.A is a magnetic fluid layer among the figure, and b is the conductive polymer solution layer, and c counterelectrode, d are that electrode inserts in the magnetic fluid, and e is a high voltage source, and f is strong permanent magnet or coil, and g is a heatproof container.
Fig. 4: spin the variation of liquid for the auxiliary electricity down in magnetic field.(a) do not have the magnetic fluid when adding auxiliary magnetic field among the figure; (b) the auxiliary magnetic fluid of externally-applied magnetic field is arranged; (c) add auxiliary magnetic field and increase, lower floor's magnetic fluid impacts the upper strata Polymer Solution and forms nadel, (d) adds auxiliary magnetic field and continues to increase; Realize the injection stream that multiply makes progress from macromolecule surface, electric spinning obtains nanofiber.
The specific embodiment
Embodiment 1: be the preparation of the magnetic nano composite fibre of nuclear with the magnetic Nano crystalline substance.
Preparation facilities is as shown in Figure 3.With γ-Fe
2O
3Nanocrystalline and silicone oil is mixed and made into magnetic fluid a by 1: 2 mass ratio, and 20 gram magnetic fluid a are put into heatproof container g.(2%wt bromination polyacetylene ethanol solution 10mL+10mL40% ethanol water mixes to gather sym-dibromoethylene conducting polymer b20mL; Form bromination polyacetylene, water, alcohol mixed solution) be the upper strata; Magnetic fluid a is a lower floor, and gained composite electrospun solution spins legal system through the magnetic field auxiliary electrical and is equipped with magnetic nano composite fibre.
It is to be to carry out among the heatproof container g in the magnetic field that provided by magnet f of 70mT at a device at vertical magnetic field magnetic flux that the magnetic field auxiliary electrical is spun.The voltage 35KV of electrode d among the heatproof container g, counterelectrode and liquid level polymer solution when 10cm begins to spray to the counterelectrode multiply of ground connection.
Fibre diameter 80nm～165nm, length 2 μ m～80 μ m, the fiber draw ratio is 12～1000, magnetic Nano crystalloid amount mark is 10～15%.
In the 2-18GHz frequency range, on average greater than-15dB, peak absorbance reaches-40dB magnetic composite nano fiber wave absorbing agent of the present invention to attenuation of Electromagnetic, and reflectivity is all less than-10dB; Density is d=0.6g/cm
3, intensity can reach 2.6Mpa, and dispersive property is good, can be evenly dispersed in the base-material.
Embodiment 2: be the preparation of the magnetic nano composite fibre of nuclear with the magnetic Nano crystalline substance.
It is to be conducting polymer, magnetic fluid in (as shown in Figure 3) other heatproof container that carries out in the heatproof container in the magnetic field that provided by coil f of 50mT at a device at vertical magnetic field magnetic flux that the magnetic field auxiliary electrical is spun, and operation is all with embodiment 3.
The physical data of magnetic nano composite fibre and performance are with embodiment 1.
Embodiment 3: with cenosphere type magnetic Nano crystalline substance is the preparation of the magnetic nano composite fibre of nuclear
With SmFeO
3/ Fe
2O
3Nanocrystalline+cenosphere and silicone oil are mixed and made into magnetic fluid a by 1: 2 mass ratio, and 20 gram magnetic fluid a are put into heatproof container g.(2%wt bromination polyacetylene ethanol solution 10mL+10mL40% ethanol water mixes to gather sym-dibromoethylene conducting polymer b20mL; Form bromination polyacetylene, water, alcohol mixed solution) be upper strata b; Magnetic fluid is a of lower floor, and gained composite electrospun solution spins legal system through the magnetic field auxiliary electrical and is equipped with magnetic nano composite fibre.
It is that at vertical magnetic field magnetic flux to be provided by magnet at a device be to carry out in the heatproof container in the magnetic field of 80mT that the magnetic field auxiliary electrical is spun method experiment.The voltage 40KV of electrode d among the heatproof container g, counterelectrode c and liquid level polymer solution when 12cm begins to spray to the counterelectrode multiply of ground connection.
Fibre diameter 2～3.5 μ m, length 21 μ m～80 μ m, the fiber draw ratio is 6～40, magnetic Nano crystalloid amount mark is 10～15%.
In the 2-18GHz frequency range, on average greater than-20dB, peak absorbance reaches-60dB magnetic composite nano fiber wave absorbing agent of the present invention to attenuation of Electromagnetic, and reflectivity is all less than-10dB; Density is d=0.2g/cm
3, intensity can reach 4Mpa, and dispersive property is good, can be evenly dispersed in the base-material.
Embodiment 4: with cenosphere type magnetic Nano crystalline substance is the preparation of the magnetic nano composite fibre of nuclear
The magnetic field auxiliary electrical spins that vertical magnetic field is provided by coil f in the device of method, and magnetic flux is 60mT, conducting polymer, magnetic fluid among other heatproof container g, and operation is all with embodiment 3.
The physical data of magnetic nano composite fibre and performance are with embodiment 3.
Embodiment 5: be the preparation of the magnetic nano composite fibre of nuclear with the magnetic Nano crystalline substance
With γ-Fe
2O
3Nanocrystalline and silicone oil is mixed and made into magnetic fluid a by 1: 2 mass ratio, and 20 gram magnetic fluid a are put into heatproof container g.(2%wt gathers dibenzenyl ethanol solution 10mL+10mL40% ethanol water and mixes to gather dibenzenyl conducting polymer b20mL; Formation gathers dibenzenyl, water, alcohol mixed solution) put it into and be upper strata b in the heatproof container g; Magnetic fluid is a of lower floor, and gained composite electrospun solution spins legal system through the magnetic field auxiliary electrical and is equipped with magnetic nano composite fibre.
It is to be to carry out among the heatproof container g in the vertical magnetic field that provides of the magnet of 70mT by magnetic flux at one that the magnetic field auxiliary electrical is spun method experiment.The voltage 35KV of electrode d among the heatproof container g, counterelectrode c and liquid level polymer solution when 10cm begins to spray to the counterelectrode multiply of ground connection.
Fibre diameter 80nm～165nm, length 2 μ m～80 μ m, the fiber draw ratio is 12～1000, magnetic Nano crystalloid amount mark is 10～15%.
In the 2-18GHz frequency range, on average greater than-15dB, peak absorbance reaches-40dB this patent magnetic composite nano fiber wave absorbing agent to attenuation of Electromagnetic, and reflectivity is all less than-10dB; Density is d=0.6g/cm
3, intensity can reach 2.6Mpa, and dispersive property is good, can be evenly dispersed in the base-material.
Embodiment 6: be the preparation of the magnetic nano composite fibre of nuclear with the magnetic Nano crystalline substance
The magnetic field auxiliary electrical spins that vertical magnetic field is provided by coil in the device of method, and magnetic flux is 50mT, conducting polymer, magnetic fluid in other heatproof container, and operation is all with embodiment 5.
The physical data of magnetic nano composite fibre and performance are with embodiment 5.
Embodiment 7: with cenosphere type magnetic Nano crystalline substance is the preparation of the magnetic nano composite fibre of nuclear
With SmFeO
3/ Fe
2O
3Nanocrystalline+cenosphere and silicone oil are mixed and made into magnetic fluid a by 1: 2 mass ratio, and a puts into heatproof container g with the 20g magnetic fluid.With styrene and acetylene block copolymer, wherein polyacetylene segment content is 25%, and the MW of polymer is 3 * 10
6～1 * 10
7Conductive polymer solution b is: get the chloroformic solution+10mL40% chloroform aqueous solution of 10mL2%wt polyacetylene block copolymer, form polyacetylene block copolymer, water, chloroform mixed solution.Get conductive polymer solution b20mL solution carefully add to be equipped with among the heatproof container g 20 gram magnetic fluid a above.Spinning gained composite electrospun solution through electricity spins legal system through the magnetic field auxiliary electrical and is equipped with magnetic nano composite fibre.
It is to be to carry out among the heatproof container g in the vertical magnetic field that provides of the magnet of 80mT by magnetic flux at one that the magnetic field auxiliary electrical is spun method experiment.Voltage 40KV, counterelectrode and the liquid level of electrode d polymer solution when 12cm begins to spray to the counterelectrode multiply of ground connection among the heatproof container g.
In the 2-18GHz frequency range, on average greater than-20dB, peak absorbance reaches-60dB this patent magnetic composite nano fiber wave absorbing agent to attenuation of Electromagnetic, and reflectivity is all less than-10dB; Density is d=0.2g/cm
3, intensity can reach 4Mpa, and dispersive property is good, can be evenly dispersed in the base-material.
Embodiment 8: be the preparation of the magnetic nano composite fibre of nuclear with the magnetic Nano crystalline substance
The magnetic field auxiliary electrical spins that vertical magnetic field is provided by coil in the device of method, and magnetic flux is 60mT, and conducting polymer is the block copolymer of isoprene and acetylene, and polyacetylene segment content is 10% (mol), and its MW is 3 * 10
4～1 * 10
5The preparation of conductive polymer solution, magnetic fluid in other heatproof container, and operation is all with embodiment 7.
The physical data of magnetic nano composite fibre and performance are with embodiment 7.
Embodiment 9: be the preparation of the magnetic nano composite fibre of nuclear with the magnetic Nano crystalline substance
With γ-Fe
2O
3Nanocrystalline and silicone oil is mixed and made into magnetic fluid by 1: 2 mass ratio, 20g magnetic fluid a is put into heatproof container g be lower floor.With the polystyrene is that main chain and polyacetylene are that the block copolymer that grafted chain is processed is a conducting polymer, and wherein polyacetylene segment content is 40%, and the MW of polymer is 3 * 10
6～1 * 10
7Conductive polymer solution b is: tetrahydrofuran solution+10mL40% tetrahydrofuran aqueous solution of getting 10mL2%wt polystyrene-poly acetylene graft copolymer mixes, and forms polystyrene-poly acetylene block copolymer, water, chloroform mixed solution.Getting conductive polymer solution b20mL solution carefully adds 20 gram magnetic fluid a are housed among the heatproof container g top to and is the upper strata.Spinning gained composite electrospun solution through electricity spins legal system through the magnetic field auxiliary electrical and is equipped with magnetic nano composite fibre.
It is to be to carry out among the heatproof container g in the vertical magnetic field that provides of the magnet of 70mT by magnetic flux at one that the magnetic field auxiliary electrical is spun method experiment.Voltage 35KV, counterelectrode and the liquid level of electrode d polymer solution when 10cm begins to spray to the counterelectrode multiply of ground connection among the heatproof container g.
In the 2-18GHz frequency range, on average greater than-15dB, peak absorbance reaches-40dB this patent magnetic composite nano fiber wave absorbing agent to attenuation of Electromagnetic, and reflectivity is all less than-10dB; Density is d=0.6g/cm
3, intensity can reach 2.6Mpa, and dispersive property is good, can be evenly dispersed in the base-material.
Embodiment 10
The magnetic field auxiliary electrical spins that vertical magnetic field is provided by coil in the device of method, and magnetic flux is 50mT, and conductive compound is for being that main chain, polyacetylene are the graft copolymer of side chain with the polyisoprene, and polyacetylene segment content is 10%, and MW is 3 * 10
4～1 * 10
5Prepare conductive polymer solution with embodiment 9, other heatproof container magnetic fluid, and operation is all with embodiment 9.
The physical data of magnetic nano composite fibre and performance are with embodiment 9.
Claims (7)
1. magnetic composite nano fiber; It is characterized in that being used for the MULTILAYER COMPOSITE nanofiber of stealth technology and electromagnetic shielding wave absorbing agent; Be made up of outer conducting polymer materials, nexine magnetic Nano nucleus, fibre diameter is 80nm～4.0 μ m, and magnetic Nano crystalloid amount mark is 10～15%; Fibre length is in that 2 μ m～80 mu m ranges are adjustable, and the fiber draw ratio is 5～1000;
Nano combined absorbing material by its preparation can cover centimeter wave, millimeter wave, infrared, visible light wave range; In the 2-18GHz frequency range, average attenuation is greater than-20dB, and peak absorbance reaches-60dB, and reflectivity is all less than-10dB; Density is d=0.2-0.6g/cm3, and intensity can reach 2-4Mpa, and dispersive property is good, can be evenly dispersed in the base-material;
Wherein: said conducting polymer be gather sym-dibromoethylene, gather acetylene dichloride and gather dibenzenyl and block or graft copolymer in a kind of: when polyacetylene segment content is 10%-25% and the block copolymer that becomes of styrene or isoprene; When polystyrene or polyisoprene are main chain, polyacetylene is the graft copolymer of side chain; Wherein polyacetylene segment content is 10%-40%; Its block or graft copolymer are soluble conductive macromolecular, W
MBe 3 * 10
4～1 * 10
7
Said magnetic Nano nucleus is that nanometer ferrite or cenosphere type magnetic Nano are brilliant; Wherein said nanometer ferrite is selected from soft magnetism γ-Fe
2O
3Material or hard magnetic material BaFe
12O
19Cenosphere type magnetic Nano crystalline substance is SmFeO
3/ Fe
2O
3Nanocrystalline+cenosphere, cenosphere diameter 1-3 μ m;
Make with following step:
(a) being magnetic fluid layer, (b) is the conductive polymer solution layer, and (c) counterelectrode (d) for electrode inserts in the magnetic fluid, (e) is high voltage source, (f) for the permanent magnet or the coil of high-intensity magnetic field are provided; It is to carry out in the heatproof container (g) in vertically strong magnetic field that the magnetic field auxiliary electrical is spun method: an electrode (d) inserts the bottom in the heatproof container (g); Another counterelectrode (c) places the heatproof container top, and conductive polymer solution (b) surface is adjustable with the distance between the counterelectrode; During operation; After conductive polymer solution (b) adds; Be immersed in voltage on the bottom electrode in the heatproof container (g) and constantly increase to 35～40KV, top counterelectrode and liquid level polymer solution when 10～15cm and begin to realize that to the counterelectrode of ground connection multiply sprays, lower floor's magnetic fluid impacts that the upper strata conductive polymer solution forms countless spicules and electric spinning obtains nanofiber;
The magnetic flux of the magnet of said high-intensity magnetic field is 80mT; The magnetic flux of the coil of high-intensity magnetic field is 50mT.
2. according to the said magnetic composite nano fiber of claim 1, it is characterized in that with the magnetic Nano crystalline substance being the composite magnetic nanofiber of nuclear: the skin of its circular cross section is conducting polymer (a), and internal layer is a nanometer ferrite nuclear (b);
Fibre diameter is 85～165nm, and average diameter is soft magnetism γ-Fe of 10nm
2O
3Nano particle or Hard Magnetic Fe
3O
4Nano particle is evenly distributed in the conducting polymer fibres;
In 2～18GHz frequency range, on average greater than-15dB, peak absorbance reaches-40dB the magnetic composite nano fiber wave absorbing agent to attenuation of Electromagnetic, and reflectivity is all less than-10dB; Density is d=0.6g/cm
3, intensity can reach 2.6Mpa.
3. based on the said magnetic composite nano fiber of claim 1; It is characterized in that with cenosphere type magnetic Nano crystalline substance be the composite magnetic nanofiber of nuclear: the skin of its circular cross section is conducting polymer (a); Its internal layer be nanometer ferrite with rich iron cenosphere in the two spin-exchange-coupled inclusion enclaves (c) mutually that form of iron phase, the bosom is the cavity (d) of cenosphere;
Fibre diameter is about 2-3.5 μ m, and average diameter is 1.5-3.0 μ m, SmFeO
3/ Fe
2O
3Nanocrystalline parcel cenosphere is evenly distributed in the conducting polymer fibres;
In 2～18GHz frequency range, on average greater than-20dB, peak absorbance reaches-60dB the magnetic composite nano fiber wave absorbing agent to attenuation of Electromagnetic, and reflectivity is all less than-10dB; Density is d=0.2g/cm
3, intensity can reach 4Mpa.
4. the preparation method of magnetic composite nano fiber according to claim 1 is characterized in that method of operating is:
(a) being magnetic fluid layer, (b) is the conductive polymer solution layer, and (c) counterelectrode (d) for electrode inserts in the magnetic fluid, (e) is high voltage source, (f) for the permanent magnet or the coil of high-intensity magnetic field are provided; It is to carry out in the heatproof container (g) in vertically strong magnetic field that the magnetic field auxiliary electrical is spun method: an electrode (d) inserts the bottom in the heatproof container (g); Another counterelectrode (c) places the heatproof container top, and conductive polymer solution (b) surface is adjustable with the distance between the counterelectrode; During operation; After conductive polymer solution (b) adds; Be immersed in voltage on the bottom electrode in the heatproof container (g) and constantly increase to 35～40KV, top counterelectrode and liquid level polymer solution when 10～15cm and begin to realize that to the counterelectrode of ground connection multiply sprays, lower floor's magnetic fluid impacts that the upper strata conductive polymer solution forms countless spicules and electric spinning obtains nanofiber;
The magnetic flux of the magnet of said high-intensity magnetic field is 80mT; The magnetic flux of the coil of high-intensity magnetic field is 50mT.
5. according to the preparation method of the said magnetic composite nano fiber of claim 5, it is characterized in that said magnetic fluid (a) mixes by 1: 2 weight ratio with silicone oil for magnetic Nano is brilliant.
6. according to the preparation method of the said magnetic composite nano fiber of claim 5, it is characterized in that said magnetic fluid (a) is SmFeO
3/ Fe
2O
3Nanocrystalline+cenosphere and silicone oil are mixed and made into by 1: 2 mass ratio.
7. according to the preparation method of the said magnetic composite nano fiber of claim 5; It is characterized in that said conductive polymer solution is that the aqueous solution of 40%wt solvent of conducting polymer solvent solution and the equivalent volume of 2%wt forms: in two substituted polyacetylenes: 40% ethanol water that the two substituted polyacetylene ethanol solutions of 2%wt chlorine or bromine add equivalent mixes, or the 40% toluene aqueous solution that 2%wt diphenyl substituted polyacetylene toluene solution adds equivalent forms; Block copolymer is that the 40% chloroform water solution that the chloroformic solution of 2%wt polyacetylene block copolymer adds equivalent mixes; Graft copolymer is the 40% tetrahydrofuran aqueous solution mixing that the tetrahydrofuran solution of 2%wt graft copolymer adds equivalent.
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| CN103243407A (en) * | 2013-05-16 | 2013-08-14 | 东华大学 | Method for preparing skin-core structured drug-loading nanofiber through needleless electrostatic spinning technology |
| CN104911719B (en) * | 2015-05-26 | 2017-07-07 | 青岛大学 | A kind of method of the standby conductive polymer micro-nano rice fiber of magnetic spinning |
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| CN110331468B (en) * | 2019-06-28 | 2022-04-22 | 无锡燊旺和电子科技有限公司 | Ultra-long continuous ferrite fiber and preparation method thereof |
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