CN104388045B - A kind of single stage method prepares the method for CNTs/Fe nano composite material - Google Patents
A kind of single stage method prepares the method for CNTs/Fe nano composite material Download PDFInfo
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- CN104388045B CN104388045B CN201410502212.XA CN201410502212A CN104388045B CN 104388045 B CN104388045 B CN 104388045B CN 201410502212 A CN201410502212 A CN 201410502212A CN 104388045 B CN104388045 B CN 104388045B
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Abstract
Single stage method prepares the method for CNTs/Fe nano composite material, (1) weigh carbon nanotube and put into four-hole boiling flask, solvent is kerosene, controls the slow reacting by heating container of electric mantle to 160-220 DEG C, the condensing reflux 4-16h time, during heating, reaction vessel passes into shielding gas; Kerosene is greater than 5 times of carbon nanotube by volume; (2) under bath temperature 40-80 DEG C condition, pentacarbonyl iron steam imports in reaction vessel along with shielding gas, is dissolved in solvent kerosene the thermolysis of the line time 4-16h that goes forward side by side; The product of Fe nano load on the surface of carbon nanotube is obtained under mechanical agitation; Product is after dehydrated alcohol or acetone cleaning several times, and at 60 ± 10 DEG C, vacuum, drying can obtain CNTs/Fe nano composite material.The present invention can be uniformly distributed the Fe particle being of a size of about 20-30nm in the surface of carbon nanotube and part pipe.It is adjustable that the present invention can realize electromagnetic parameter, and technique is simply controlled, cheap, is conducive to industrial mass production.
Description
Technical field
The invention belongs to microwave absorbing material field, be specifically related to a kind of method preparing CNTs/Fe nano composite material.
Background technology
Carbon nanotube from 1991 by Japanese Electronic Speculum scholar lijima with electric arc legal system for the process of C60 in after Late Cambrian, the performances such as the structure of its uniqueness, excellent mechanics, electricity and chemistry, become rapidly the object competitively studied in the fields such as Materials science, physics, biology, chemistry, become study frontier and the focus of international novel material.
CNTs can regard the pipe curled into by individual layer or multi-layer graphene as, correspondingly be called Single Walled Carbon Nanotube (SWCNT) and multi-walled carbon nano-tubes (MWCNT), pipe diameter is between a few nanometer to tens nanometers, and length can reach several microns.The special construction of CNTs and dielectricity, it is made to show stronger wide-band microwave absorptive character in suction ripple field, have that quality is light, electroconductibility is adjustable, high-temperature oxidation resistance is strong concurrently and the series of advantages such as good stability simultaneously, be a kind of promising microwave absorption, can use as potential stealth material, electromagnetic shielding material or darkroom absorbing material.
In order to utilize the advantage of carbon nanotube, and expand its range of application, goal in research is turned to carbon nano tube compound material by various countries scientist one after another.Many kinds of substance is used to and its compound, comprises inorganic nano-particle, high molecular polymer, organic molecule and biomolecules etc.And as a class wherein, the compound of carbon nanotube and magnetic nanoparticle in recent years also pay close attention to by people, this matrix material has the excellent properties of carbon nanotube and magnetic nanoparticle concurrently simultaneously, and is further optimized under interaction, and has more wide application prospect.The people Ni/Al such as TianchunZou
2o
3make catalyzer, methane chemical vapour deposition, successfully prepare inner multi-walled carbon nano-tubes (MWCNTs) of filling Ni nano wire, this matrix material all exceedes-10dB in 6.4 ~ 11GHz frequency range internal reflection loss, and reaches-23.1dB at 8.0GHz.The people such as ByRenchaoChe also successfully prepare inner carbon nanotube of filling Fe nano particle, and near 11GHz, reach maximum loss-25dB.But these have certain deficiency, preparation method is very not easy, and absorbing property does not also improve a lot.
Summary of the invention
The technical problem solved: the invention provides a kind of method being prepared CNTs/Fe nano composite material by thermolysis pentacarbonyl iron, it is simple that the method has technique, and material subsequent disposal is simple, can realize the advantages such as scale operation; And in the CNTs/Fe nano composite material obtained, Nanoscale Iron iron granular size is homogeneous, does not occur agglomeration.Uniform one deck iron membrana granulosa can be formed in carbon nano tube surface.By the processing parameter of adjustment reaction, can control the clad ratio of matrix material, this structure of matrix material can also improve the oxidation-resistance of Fe nanometer particles.
Technical scheme
The method of CNTs/Fe nano composite material is prepared in a kind of pentacarbonyl iron thermolysis that the present invention proposes, and namely single stage method prepares the method for CNTs/Fe nano composite material, comprises the following steps:
(1) weigh carbon nanotube and put into four-hole boiling flask, solvent is kerosene, and control the slow reacting by heating container of electric mantle to 160-220 DEG C, the condensing reflux 4-16h time, during heating, reaction vessel passes into shielding gas; Kerosene is greater than 5 times of carbon nanotube by volume;
(2) under bath temperature 40-80 DEG C condition, pentacarbonyl iron steam imports in reaction vessel along with shielding gas, is dissolved in solvent kerosene the thermolysis of the line time 4-16h that goes forward side by side; The product of Fe nano load on the surface of carbon nanotube is obtained under mechanical agitation;
(3), after reaction terminates, under gas shield, room temperature is cooled to;
(4) product is after dehydrated alcohol or acetone cleaning several times, and at 60 ± 10 DEG C, vacuum, drying can obtain CNTs/Fe nano composite material.
Control to lead to air in for some time shielding gas emptying flask under mechanical stirring when electric mantle slowly heats, airshed is between 60-120ml/min.
Control electric mantle under mechanical stirring 300-400r/min condition slowly to heat.
Further, by changing the amount of the Nanoscale Iron in reaction times and temperature control CNTs area load.Illustrate in embodiment: under the identical reaction times, be more dispersed in carbon nano tube surface compared to the Nanoscale Iron at 180 DEG C of conditions, 200 DEG C of temperature.And can find out at the carbon nanotube of 200 DEG C of reaction 14h, nano iron particles distribution is more even, and carbon nanotube dispersed increases greatly, and the distribution of sizes of Nanoscale Iron is between 20-30nm.
The invention has the beneficial effects as follows, only need single stage method just can the method for loaded with nano-iron CNTs/Fe particulate composite and subsequent disposal is simple on the carbon nanotubes, the Fe particle being of a size of about 20-30nm can be uniformly distributed in the surface of carbon nanotube and part pipe.By changing the amount of the Nanoscale Iron in reaction times and temperature control CNTs area load, thus change Parameter Conditions according to the needs of oneself.Carbon nanotube (CNTs) especially loaded with nano-iron as potential absorbing material, simultaneously light with quality, electroconductibility is adjustable, high-temperature oxidation resistance is strong and the series of advantages such as good stability.
(1) pentacarbonyl iron liquid is volatile and can be dissolved in kerosene completely; under the condition of Control protection gas flow, steam is imported in kerosene uniformly; carry out thermolysis again after fully contacting with carbon nanotube, thus obtain Fe nanometer particles uniform loading in carbon nano tube surface.Fe nanometer particles can improve the dispersiveness of carbon nanotube in the load of carbon nano tube surface, and the structure of this matrix material can improve the dispersiveness, oxidation-resistance etc. of Fe nanometer particles simultaneously;
(2) simply, preparation technology is easy and simple to handle for CNTs/Fe Nano-composite materials method of the present invention and materials, and subsequent disposal is simple, and without the need to the synthesis device of complexity, preparation cost is lower, is applicable to industrial mass production;
(3) invent the CNTs/Fe nano composite material obtained, not only there is stronger magnetic property, and the light density of quality is low.CNTs/Fe nano composite material, combine the magnetic property of the excellent electrical property of carbon nanotube and Fe nanoparticle simultaneously, it is more extensive that its range of application becomes, such as can as lightweight electromagnetic shielding material, simultaneously first-class at microelectronic element, Biological imaging and target medicinal material is also that use scope strengthens.
The present invention makes the excellent properties of carbon nanotube better be played, by preparing CNTs/Fe matrix material with Magnetic nano iron Particles dispersed, more can meet that present CNTs/Fe absorbing material electromagnetic wave absorption ability is strong, absorption band is wide, the free of contamination requirement of lightweight.It is adjustable that this invention can realize electromagnetic parameter, and technique is simply controlled, cheap, is conducive to industrial mass production, and method has an unexpected effect.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the CNTs/Fe nano composite material prepared under differing temps and time;
Fig. 2 is electron-microscope scanning (SEM) figure (embodiment 1 of the CNTs/Fe nano composite material prepared under differing temps and time, 2,3), embodiment 1, (a) in 2,3 difference corresponding diagram 2, (b), (c), and (d) is carbon nanometer tube material figure.As can be seen from the figure nano iron particles is evenly distributed in the surface of carbon nanotube, and too increases the dispersiveness of carbon nanotube without obvious agglomeration.Contrast (d), under the identical reaction times, is more dispersed in carbon nano tube surface compared to the Nanoscale Iron at 180 DEG C of conditions, 200 DEG C of temperature.And can find out at the carbon nanotube of 200 DEG C of reaction 14h, nano iron particles distribution is more even, the nano iron particles density of load is larger, carbon nanotube dispersed increases greatly, and the distribution of sizes of Nanoscale Iron is between 20-30nm, can find out the increasing along with the time, on carbon nanotube, the Nanoscale Iron of load increases, and under 200 DEG C of conditions, pentacarbonyl iron liquid decomposition speed strengthens.
Fig. 3 is transmission electron microscope (TEM) figure of multi-walled carbon nano-tubes raw material;
Fig. 4 is transmission electron microscope (TEM) figure of the CNTs/Fe nano composite material that at 200 DEG C prepared by reaction times 14h;
Fig. 5 is the CNTs/Fe nano composite material prepared under differing temps and time, reflection loss (RL) figure when figure layer thickness is 1mm;
Fig. 6 is the CNTs/Fe nano composite material that at 200 DEG C prepared by reaction times 14h, reflection loss (RL) figure under different layer thickness condition;
Embodiment:
Weigh multi-walled carbon nano-tubes 300 ~ 1000mg and put into 1000ml four-hole boiling flask, add solvent kerosene 300-800ml.Four-hole boiling flask is fixed and is placed in electric mantle and has connected condensation reflux unit.
Under speed is 300-400r/min in mechanical stirring and reflux course, first pass into shielding gas (N
2, Ar etc.) 20-70min discharges air in whole device, continue to adopt N
2, Ar etc. as guiding gas, flow control is at 60-120ml/min, and pentacarbonyl iron liquid is volatile, under bath temperature 40-80 DEG C condition, pentacarbonyl iron steam to be imported in four-hole boiling flask and to be dissolved in kerosene, and between 160-220 DEG C, carry out pyrolysis, the time is between 4-16h.
After completion of the reaction, continue to pass into shielding gas protection and be cooled to room temperature.
Product is after dehydrated alcohol, acetone cleaning several times, and at 60 DEG C, vacuum, drying can obtain CNTs/Fe nano composite material.
Below specific embodiment 1 of the present invention:
(1) weigh the multi-walled carbon nano-tubes of 600mg, put into 1000ml four-hole boiling flask, and add solvent kerosene 600ml.Four-hole boiling flask is fixed and is placed in electric mantle, connect spherical condensation tube, temperature controller, mechanical stirrer, inlet pipe respectively.The air in nitrogen 60min emptying device is passed under mechanical stirring speed 320r/min condition.
(2) pentacarbonyl iron liquid is volatile, and under bath temperature 60 DEG C of conditions, pentacarbonyl iron steam to be imported in four-hole boiling flask and to be dissolved in kerosene, is slowly heated to 180 DEG C to four-hole boiling flask subsequently, carries out condensing reflux with electric mantle.Continue to use N
2as guiding gas, guide pentacarbonyl iron steam to be dissolved in the kerosene of four-hole boiling flask and carry out thermolysis, N
2flow velocity keeps 100ml/min, and reaction continues 4h.
(3) after reaction terminates, at N
2be down to room temperature gradually under protection, the product obtained is CNTs/Fe nano composite material.
Embodiment 2:
(1) with (1) of embodiment 1.
(2) pentacarbonyl iron liquid is volatile, and under bath temperature 60 DEG C of conditions, pentacarbonyl iron steam to be imported in four-hole boiling flask and to be dissolved in kerosene, is slowly heated to 200 DEG C to four-hole boiling flask subsequently, carries out condensing reflux with electric mantle.Continue to use N
2as guiding gas, guide pentacarbonyl iron liquid vapour to be dissolved in the kerosene of four-hole boiling flask and carry out thermolysis, N
2flow velocity keeps 100ml/min, and reaction continues 4h.
(3) with (3) of embodiment 1.
Embodiment 3:
(1) with (1) of embodiment 1.
(2) pentacarbonyl iron liquid is volatile, and under bath temperature 60 DEG C of conditions, pentacarbonyl iron steam to be imported in four-hole boiling flask and to be dissolved in kerosene, is slowly heated to 200 DEG C to four-hole boiling flask subsequently, carries out condensing reflux with electric mantle.Continue to use N
2as guiding gas, guide pentacarbonyl iron liquid vapour to be dissolved in the kerosene of four-hole boiling flask and carry out thermolysis, N
2flow velocity keeps 100ml/min, and reaction continues 14h.
(3) with (3) of embodiment 1.
Fig. 1 is the X-ray diffractogram (embodiment 1 of the CNTs/Fe nano composite material prepared under differing temps and time, 2,3), as can be seen from the XRD figure of matrix material we, the diffraction peak of Fe (110) crystal face clearly, there is no the peak of other impurity and oxide compound, determine that the product prepared is very pure.
Fig. 3 is transmission electron microscope (TEM) figure of multi-walled carbon nano-tubes raw material, and from figure, we can find out carbon nanometer tube material smooth surface and be hollow structure.
Fig. 4 is transmission electron microscope (TEM) figure (embodiment 3) of the CNTs/Fe nano composite material that at 200 DEG C prepared by reaction times 14h, nano iron particles on the area load that comparison diagram 3 can find out carbon nanotube, and dispersion is more even.The distribution of sizes of Nanoscale Iron is between 20-30nm.
Fig. 5 is the CNTs/Fe nano composite material prepared under differing temps and time, reflection loss (RL) figure (embodiment 1 when figure layer thickness is 1mm, 2,3), as can be seen from the figure, when coat-thickness is 1mm along with temperature and the increase of time, the resonant frequency of sample is all to high-frequency mobile.During reaction times 14h, maximum reflection loss can close-10dB.
Fig. 6 is the CNTs/Fe nano composite material that at 200 DEG C prepared by reaction times 14h, reflection loss (RL) figure (embodiment 3) under different layer thickness condition.Can find out the increase along with coat-thickness, the resonant frequency of sample moves to low frequency.And when coat-thickness is 4mm, the maximum reflection loss of sample reaches maximum-44dB, shows superior absorbing property.
Claims (4)
1. single stage method prepares the method for CNTs/Fe nano composite material, it is characterized in that comprising the following steps:
(1) weigh carbon nanotube and put into four-hole boiling flask, solvent is kerosene, and control the slow reacting by heating container of electric mantle to 160-220 DEG C, the condensing reflux 4-16h time, during heating, reaction vessel passes into shielding gas; Kerosene is greater than 5 times of carbon nanotube by volume;
(2) under bath temperature 40-80 DEG C condition, pentacarbonyl iron steam imports in reaction vessel along with shielding gas, is dissolved in solvent kerosene the thermolysis of the line time 4-16h that goes forward side by side; The product of Fe nano load on the surface of carbon nanotube is obtained under mechanical agitation;
(3), after reaction terminates, under gas shield, room temperature is cooled to;
(4) product is after dehydrated alcohol or acetone cleaning several times, and at 60 ± 10 DEG C, vacuum, drying can obtain CNTs/Fe nano composite material.
2. single stage method according to claim 1 prepares the method for CNTs/Fe nano composite material, it is characterized in that controlling to lead to air in for some time shielding gas emptying flask under mechanical stirring when electric mantle slowly heats, and airshed is between 60-120ml/min.
3. single stage method according to claim 1 prepares the method for CNTs/Fe nano composite material, controls electric mantle and slowly heat under it is characterized in that mechanical stirring 300-400r/min condition.
4. single stage method according to claim 1 prepares the method for CNTs/Fe nano composite material, it is characterized in that the amount of the Nanoscale Iron by changing reaction times and temperature control CNTs area load.
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