CN101041433A - Original position method for synthesizing magnetic alloy nano thread filled carbon nano-tube - Google Patents
Original position method for synthesizing magnetic alloy nano thread filled carbon nano-tube Download PDFInfo
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- CN101041433A CN101041433A CN 200710064169 CN200710064169A CN101041433A CN 101041433 A CN101041433 A CN 101041433A CN 200710064169 CN200710064169 CN 200710064169 CN 200710064169 A CN200710064169 A CN 200710064169A CN 101041433 A CN101041433 A CN 101041433A
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Abstract
The invention discloses a preparing method of iron magnetic properties alloy nanometer thread fill carbon nanometer pipe, which comprises the following steps: reacting in the pipe resistance furnace; combining organometal followed by weight ratio; dissolving in the chloric organic compound; allocating into reacting solution; leading the reacting solution into quartz tube; reacting proper time; halt-providing solution and hydrogen gas; cooling to room temperature naturally; accumulating black iron magnetic properties alloy nanometer thread fill carbon nanometer pipe in the middle of the quartz tube. The invention possesses simply craft, which can get iron magnetic properties alloy nanometer thread fill carbon nanometer pipe.
Description
Technical field
The invention belongs to the synthetic and applied technical field of carbon nanomaterial, particularly a kind of the magneticalloy nano-thread in-situ is filled in method in the carbon nanotube.
Background technology
Since carbon nanotube is found,, made them all have a wide range of applications in many aspects because it integrates excellent electric property and mechanical property.Carbon nanotube potential Application Areas comprises: [Liu C, et al.Science, 1999,286 (5442): 1127 such as storage of field emission source, nano-transistor, spin-polarized electron source, flat pannel display and hydrogen; Deheer WA, et al.Science, 1995,270 (5239): 1179].In addition, with the nano level container of carbon nanotube, especially, good application prospects is arranged also as the nano container of filler metal material as the second phase material.Ferromagnetic metal is (as Fe; Co; Ni or its alloy) nanoparticle and nano wire general than being easier to oxidation; if fill it in the carbon nanotube; because the provide protection of carbon nanotube can make its resistance of oxidation improve [Kang YJ, et al.PhysicalReview B greatly; 2005,71 (11): 115441].Has good physicochemical property owing to be filled with the carbon nanotube of ferromagnetic metal material simultaneously, they are at high density data storage [Grobert N, et al.AppliedPhysics Letters, 1999,75 (21): 3363], bio-medical field [Monch I, et al.Journal of Magnetism and Magnetic Materials, 2005,290:276] and absorption of electromagnetic wave and shielding [Che RC, et al.Advanced Materials, 2004,16 (5): 401] etc. all there is fabulous application prospect many aspects, thereby become a focus of current research.
Focus mostly on elemental metals (as Fe, Co and Ni etc.) filling carbon nano-pipe in the research aspect the preparation ferromagnetic metal filling carbon nano-pipe at present, the report of relevant magneticalloy filling carbon nano-pipe is considerably less.Compare with elemental metals, through the magnetic property of material after the alloying can improve a lot [Tian Minbo. magneticsubstance. press of Tsing-Hua University: Beijing, 2001].Therefore, if can prepare the carbon nanotube that magneticalloy is filled, for promoting of the practical application of this novel nano level composite material to have great importance in fields such as magnetic recording, Magnetic resonance imaging, radar wave absorptions.
The method that is adopted in preparing the iron filling carbon nano-pipe mostly is ferrocene powder volatilization method [Rao CNR, et al.Chemical Communicatiohs, 1998,15:1525; Karmakar S, et al.Journalof Applied Physics, 2005,97 (5): 054306], promptly be carbon source and source of iron with the ferrocene, by heating it is decomposed and prepare the iron filling carbon nano-pipe.The shortcoming of this method is the extremely difficult control of ferrocene powder evaporable speed, and the tube wall of gained carbon nanotube is very thick, and the loading level of metallic iron is very low; In addition, also have more carbon iron clad granular disintegration to exist.Except that the powder volatilization method, another method that often adopts is a template when preparing the ferromagnetic metal filling carbon nano-pipe, this method generally need synthesize the template of suitable size and structure earlier (as porous anodic aluminium oxide [Bao JC, et al.Advanced Materials, 2002,14 (20): 1483], porous oxide carrier [Che RC, et al.Advanced Materials, 2004,16 (5): 401] etc.), utilize the method for physics or chemistry then to wherein filling ferromagnetic metal.The weak point of template is to synthesize template in advance, and reaction also will be managed template is removed after finishing, and technology is complicated, and efficient is very low; Simultaneously, also there is the low shortcoming of filling ratio.Aspect the choosing of carbon source, the work of the relevant ferromagnetic metal nano thread filled carbon nano-tube of having reported focuses mostly at organometallics [Rao CNR, et al.Chemical Communications, 1998,15:1525], methane [Che RC, et al.AdvancedMaterials, 2004,16 (5): 401], acetylene [Bao JC, et al.Advanced Materials, 2002,14 (20): 1483] etc. on the organism, use chlorine-containing organic compounds to come carbon nano-tube not appear in the newspapers as yet as carbon source.
Based on above-mentioned consideration, the present invention intends by selecting suitable reaction precursor body (to comprise the magneticmetal source, carbon source), it is simple to develop a kind of technology, the preparation method that controllability is good, realize the growth in situ of magneticalloy nano wire in thin wall carbon nano-tube, make magnetic alloy nano thread filled carbon nano-tube material with higher filling ratio and better magnetic properties.
Summary of the invention
The purpose of this invention is to provide and a kind of the magneticalloy nano-thread in-situ is filled in method in the carbon nanotube, it is characterized in that, comprise the steps:
(1) more than one organometallicss according to weight ratio 4～6: after 1～5: 1 combination, be dissolved in the chlorine-containing organic compounds, the reaction soln that is mixed with concentration and is 0.01～0.30g/mL is standby;
(2) substrate is placed on the quartz boat, put into the silica tube reaction chamber, again the silica tube reaction chamber is placed in the tube type resistance furnace;
(3) in the silica tube reaction chamber of the described good seal of step (2), feed argon gas, reaction chamber is heated to 700～900 ℃ simultaneously;
(4) temperature of silica tube inlet end is controlled between 200～400 ℃;
(5) argon flow amount to the 1000～3000mL/min of set-up procedure (3), and the hydrogen of feeding 300mL/min;
(6) by accurate flow pump the reaction soln for preparing is injected reaction chamber with the rate of feed of 0.1～0.6mL/min and begin reaction, after the time of reaction 25～40min, stop supplies solution and hydrogen, reduce argon flow amount to 100mL/min, silica tube is cooled to room temperature in argon gas atmosphere, stops the argon gas supply; All can collect black deposit at substrate and silica tube middle part, be the ferromagnetic alloy nano thread filled carbon nano-tube.
Described substrate is quartz or silicon chip.
Organometallics in the described step (1) is two or three in ferrocene, nickelocene and the dicyclopentadienylcobalt.
Chlorine-containing organic compounds in the described step (1) is chlorination aromatic hydrocarbon (as a dichlorobenzene, trichlorobenzene etc.).
The temperature of the control silica tube inlet end in the described step (4) is between 200～400 ℃.
Reaction soln in the described step (6) injects reaction chamber by accurate flow pump, and the rate of feed of solution is 0.14mL/min.
The prepared alloy nano-wire in described step (6) back is a ferrocobalt, or iron-nickel alloy, or the iron-cobalt-nickel ternary alloy.
Principal feature of the present invention: the one, adopting trichlorobenzene is carbon source and solvent, has realized the continuous controllable supply of reaction precursor body by accurate flow pump; Because the chlorine element can suppress the radially growth of carbon nanotube, can obtain the thin carbon nanotube of tube wall; The 2nd, can pass through control solution rate of feed, so that the axial growth speed of may command carbon nanotube, help a large amount of magneticmetal atoms and enter into carbon nanotubes lumen inside, finally can obtain the higher carbon nanotube of magneticmetal loading level; The 3rd, by adjusting the composition and the ratio of alloy compositions, can obtain the magnetic nanometer of different components alloy, to obtain required magnetostatic performance.
Description of drawings
Fig. 1 is an experimental installation synoptic diagram of the present invention (1): silica tube (2): tube type resistance furnace (3): accurate flow (4): reaction soln (5): heating zone (6): temperature controller (7): be equipped on the substrate (8) on the quartz boat: the tail gas outlet.
Fig. 2 is pattern and the composition (a) that utilizes the FeCo nano thread filled carbon nano-tube of present method preparation: transmission electron microscope (TEM) photo (b): energy dispersion (EDS) spectrogram.
Fig. 3 is pattern and the composition (a) that utilizes the FeNi nano thread filled carbon nano-tube of present method preparation: TEM photo (b): EDS spectrogram.
Fig. 4 is pattern and the composition (a) that utilizes the FeCoNi nano thread filled carbon nano-tube of present method preparation: TEM photo (b): EDS spectrogram.
Fig. 5 is a magnetostatic performance of utilizing the alloy nano-wire filling carbon nano-pipe of present method preparation.
Embodiment
The invention provides and a kind of the magneticalloy nano-thread in-situ is filled in method in the carbon nanotube, in experimental installation shown in Figure 1, carry out, the structure of experimental installation is that silica tube 1 is placed in the tube type resistance furnace 2, substrate 7 is equipped on and puts into silica tube 1 on the quartz boat, reaction soln bottle 4 is fixed on the reaction soln entrance of silica tube 1 inlet end by accurate flow 3 and the connection of silica tube 1 inlet end, heating zone 5 and temperature controller 6, another temperature controller 6 is fixed on the tube type resistance furnace 2, measure the temperature at silica tube 1 middle part, tail gas outlet 8 exit end at silica tube 1.Below in conjunction with drawings and Examples the present invention is further specified.
0.33g ferrocene and 0.06g dicyclopentadienylcobalt be dissolved in to form a brown solution in the 6.5mL trichlorobenzene behind sonic oscillation standby; Quartz substrate 7 is placed in the quartz boat 1, slowly pushes silica tube 1 reaction chamber middle part then; Silica tube 1 inlet end temperature T 1 is set in 220 ℃, and furnace temperature T2 is set in 800 ℃ to begin to heat up, and is the argon gas of 100mL/min toward silica tube 1 interior feeding flow simultaneously, to discharge air wherein; After treating that T1 and T2 all reach set(ting)value, the flow of argon gas and hydrogen is set in 3000mL/min and 300mL/min respectively, solution is fed into the flow of 0.14mL/min by accurate flow pump 3 and begins reaction in the silica tube 1, the reaction times is 30min; Reaction finishes, and stops hydrogen, and argon flow amount is transferred to 100mL/min, makes product be cooled to room temperature in argon gas atmosphere, collects the product on the quartz substrate, is FeCo alloy nano-wire filling carbon nano-pipe.
Fig. 2 (a) is the TEM photo of sample, and Fig. 2 (b) is accordingly can spectrogram.All filled the FeCo alloy nano-wire in about as shown in Figure 2 70% the carbon nanotubes lumen, the diameter of nano wire is comparatively even, is about 10～20nm, and its length can reach 2 μ m.
0.30g ferrocene and 0.24g nickelocene are dissolved in the 10mL dichlorobenzene, and it is standby to form a dark green solution behind sonic oscillation; Quartz substrate 7 is placed in the quartz boat, slowly pushes silica tube 1 reaction chamber middle part then; Silica tube 1 inlet end temperature T 1 is set in 250 ℃, and furnace temperature T2 is set in 860 ℃ to begin to heat up, and is the argon gas of 100mL/min toward the interior feeding of silica tube flow simultaneously, to discharge air wherein; After treating that T1 and T2 all reach set(ting)value, the flow of argon gas and hydrogen is set in 3000mL/min and 300mL/min respectively, solution is fed into the flow of 0.14mL/min by accurate flow pump 3 and begins reaction in the silica tube 1, the reaction times is 30min; Reaction finishes, and stops hydrogen, and argon flow amount is transferred to 100mL/min, makes product be cooled to room temperature in argon gas atmosphere, collects the product on the quartz substrate, is FeNi alloy nano-wire filling carbon nano-pipe.
Fig. 3 (a) is the TEM photo of sample, and Fig. 3 (b) is accordingly can spectrogram.Evenly filled the FeNi alloy nano-wire as shown in Figure 3 in the carbon nanotubes lumen, the diameter of nano wire is about 30nm, and its length can reach 2 μ m.
With the 0.16g ferrocene, 0.20g dicyclopentadienylcobalt and 0.04g nickelocene are dissolved in the 10mL trichlorobenzene, and it is standby to form a brown solution behind sonic oscillation; Quartz substrate 7 is placed in the quartz boat, slowly pushes silica tube 1 reaction chamber middle part then; Silica tube inlet end temperature T 1 is set in 300 ℃, and furnace temperature T2 is set in 900 ℃ to begin to heat up, and is the argon gas of 100mL/min toward silica tube 1 interior feeding flow simultaneously, to discharge air wherein; After treating that T1 and T2 all reach set(ting)value, the flow of argon gas and hydrogen is set in 3000mL/min and 300mL/min respectively, solution is fed into the flow of 0.14mL/min by accurate flow pump 3 and begins reaction in the silica tube 1, the reaction times is 30min; Reaction finishes, and stops hydrogen, and argon flow amount is transferred to 100mL/min, makes product be cooled to room temperature in argon gas atmosphere, collects the product on the quartz substrate, is FeCoNi alloy nano-wire filling carbon nano-pipe.
Fig. 4 (a) is the TEM photo of sample, and Fig. 4 (b) is accordingly can spectrogram.All filled the FeCoNi alloy nano-wire in about as shown in Figure 4 80% the carbon nanotubes lumen, the diameter of nano wire is about 20nm, and its length can reach 1 μ m.
The magnetostatic performance of sample is tested with vibration magnetometer (VSM, Lake shore 7307), and the result all shows good ferromagnetic property as shown in Figure 5.The specific saturation magnetization of gained alloy nano-wire filling carbon nano-pipe is respectively: 33.2emu/g (FeCo alloy sample among the embodiment 1), (28.1emu/g FeNi alloy sample among the embodiment 2) and 27.6emu/g (FeCoNi alloy sample among the embodiment 3), improving a lot than the pure metal filling carbon nano-pipe, (for example the specific saturation magnetization of Ni filling carbon nano-pipe is only for 12.0emu/g[Junfeng Geng, et al.Journal of Materials Chemistry, 2005,15:844]).
Claims (8)
1. one kind is filled in method in the carbon nanotube with the magneticalloy nano-thread in-situ, it is characterized in that, comprises the steps:
(1) more than one organometallicss according to weight ratio 4～6: after 1～5: 1 combination, be dissolved in the chlorine-containing organic compounds, the reaction soln that is mixed with concentration and is 0.01～0.30g/mL is standby;
(2) substrate is placed on the quartz boat, put into the silica tube reaction chamber, again the silica tube reaction chamber is placed in the tube type resistance furnace;
(3) in the silica tube reaction chamber of the described good seal of step (2), feed argon gas, reaction chamber is heated to 700～900 ℃ simultaneously;
(4) temperature of silica tube inlet end is controlled between 200～400 ℃;
(5) argon flow amount to the 1000～3000mL/min of set-up procedure (3), and the hydrogen of feeding 300mL/min;
(6) by accurate flow pump the reaction soln for preparing is injected reaction chamber with the rate of feed of 0.1～0.6mL/min and begin reaction, after the time of reaction 25～40min, stop supplies solution and hydrogen, reduce argon flow amount to 100mL/min, silica tube is cooled to room temperature in argon gas atmosphere, stops the argon gas supply; All can collect black deposit at substrate and silica tube middle part, be the ferromagnetic alloy nano thread filled carbon nano-tube.
2. the method for original position synthesizing magnetic alloy nano-wire filling carbon nano-pipe according to claim 1 is characterized in that described substrate is quartz or silicon chip.
3. the method for original position synthesizing magnetic alloy nano-wire filling carbon nano-pipe according to claim 1 is characterized in that the organometallics in the described step (1) is two or three in ferrocene, nickelocene and the dicyclopentadienylcobalt.
4. the method for original position synthesizing magnetic alloy nano-wire filling carbon nano-pipe according to claim 1 is characterized in that the chlorine-containing organic compounds in the described step (1) is a chlorination aromatic hydrocarbon.
5. the method for original position synthesizing magnetic alloy nano-wire filling carbon nano-pipe according to claim 1, the temperature that it is characterized in that the control silica tube inlet end in the described step (4) is between 200～400 ℃.
6. the method for original position synthesizing magnetic alloy nano-wire filling carbon nano-pipe according to claim 1 is characterized in that the reaction soln in the described step (6) injects reaction chamber by accurate flow pump, and the rate of feed of solution is 0.14mL/min.
7. the method for original position synthesizing magnetic alloy nano-wire filling carbon nano-pipe according to claim 1 is characterized in that the prepared alloy nano-wire in described step (6) back is a ferrocobalt, or iron-nickel alloy, or the iron-cobalt-nickel ternary alloy.
8. according to the method for claim 1 or 4 described original position synthesizing magnetic alloy nano-wire filling carbon nano-pipes, it is characterized in that described chlorination aromatic hydrocarbon is dichlorobenzene or trichlorobenzene.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880040A (en) * | 2010-06-24 | 2010-11-10 | 吉林大学 | Method for preparing gamma-Fe2O3 nanometer wire filling carbon nitrogen multi-wall nanometer tubes through one-step reaction |
| CN101607704B (en) * | 2009-07-14 | 2011-06-29 | 清华大学 | Carbon nanotube cotton and preparation method thereof |
| CN104874351A (en) * | 2015-05-15 | 2015-09-02 | 广西师范大学 | Semi-capsule-shaped magnetic carbon nano-tube as well as preparation method thereof and application |
| CN106319488A (en) * | 2016-09-08 | 2017-01-11 | 天津大学 | CNTs/PDMS flexible composite film coated with moniliform FeNi alloy and preparing method |
| CN112941680A (en) * | 2021-01-28 | 2021-06-11 | 华侨大学 | Preparation method of carbon nanotube fiber-loaded nano iron oxide composite material |
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2007
- 2007-03-05 CN CN 200710064169 patent/CN101041433A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101607704B (en) * | 2009-07-14 | 2011-06-29 | 清华大学 | Carbon nanotube cotton and preparation method thereof |
| CN101880040A (en) * | 2010-06-24 | 2010-11-10 | 吉林大学 | Method for preparing gamma-Fe2O3 nanometer wire filling carbon nitrogen multi-wall nanometer tubes through one-step reaction |
| CN101880040B (en) * | 2010-06-24 | 2012-02-08 | 吉林大学 | Method for preparing gamma-Fe2O3 nanometer wire filling carbon nitrogen multi-wall nanometer tubes through one-step reaction |
| CN104874351A (en) * | 2015-05-15 | 2015-09-02 | 广西师范大学 | Semi-capsule-shaped magnetic carbon nano-tube as well as preparation method thereof and application |
| CN106319488A (en) * | 2016-09-08 | 2017-01-11 | 天津大学 | CNTs/PDMS flexible composite film coated with moniliform FeNi alloy and preparing method |
| CN112941680A (en) * | 2021-01-28 | 2021-06-11 | 华侨大学 | Preparation method of carbon nanotube fiber-loaded nano iron oxide composite material |
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