CN100344708C - Method for preparing carbon nanotube magnetic compositematerial modified by iron oxide red - Google Patents
Method for preparing carbon nanotube magnetic compositematerial modified by iron oxide red Download PDFInfo
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- CN100344708C CN100344708C CNB2005100249212A CN200510024921A CN100344708C CN 100344708 C CN100344708 C CN 100344708C CN B2005100249212 A CNB2005100249212 A CN B2005100249212A CN 200510024921 A CN200510024921 A CN 200510024921A CN 100344708 C CN100344708 C CN 100344708C
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Abstract
The present invention discloses a method for preparing ferric oxide modified carbon nano tube magnetic composite materials, which comprises the following steps: (1) at a room temperature, carbon nano tubes are dispersed in sodium dodecanesulphonate solution, washed, dried and added to soluble iron salt solution, washed and dried again to obtain ferric hydroxide modified carbon nano tubes before pH value is regulated with alkaline solution; (2) the obtained carbon nano tubes are placed in inert atmosphere; the room temperature is raised to 250 DEG C for heat preservation, and then is raised to 400 to 700 DEG C for heat preservation; the obtained carbon nano tubes are cooled to the room temperature under theinert atmosphere to obtain ferric oxide modified carbon nano tube magnetic composite materials. The present invention is simple and soft magnetic materials with good performance are prepared. The present invention has a good application foreground in the fields of high-density magnetic recording materials, wave absorbing materials, ink for electrostatic copying, broad-cellulae transformers, noise filters, transformers for communication, etc.
Description
Technical field
The present invention relates to a kind of preparation method of magnetic composite, particularly relate to a kind of preparation method of carbon nanotube novel magnetic matrix material of ferric oxide modification.
Background technology
Carbon nanotube since finding, has caused that scientist pays close attention to greatly with its unique physics and chemical property.Studies show that carbon nanotube is the best template of preparation one dimension matrix material, this one dimension matrix material shows excellent more physics and chemical property, as: better conductivity, mechanical property, optical property, absorption property and microwave absorbing property etc. have more wide application prospect.
At present the main method of the domestic and international report of the carbon nanotube of modifying about inorganic substance has hydro-thermal or solvent-thermal method, sol-gel processing, chemical precipitation method, electroless plating method, vapour deposition process etc.The hot method of solvent (water) can synthesize the crystal grain component and form is controlled, granularity is little and respectively evenly, the nano material of crystallization and excellent property.But experiment needs reactor, and the reaction times that needs sometimes is also longer.Yangqiao Liu etc. has reported that on Carbon 43 (2005) 47 solvent-thermal methods prepare CNT-NiFe
2O
4Structure has also been inquired into the variation of its electrical property.Experimental installation that sol-gel processing needs and experiment condition ratio are easier to realize, but adorned material is limited, and experimental period is also very long.K Hernadi etc. utilizes sol-gel processing to describe Al on Acta Mater51 (2003) 1447
2O
3The carbon nanotube of modifying.Advantages such as chemical precipitation method is because synthetic cost is low, and experiment condition realizes easily, and modifiable raw material range is wide are widely used in the carbon nanotube that inorganic substance are modified.QingHuang etc. have reported TiO on J.Mater.Chem
2The preparation of the composite structure of carbon nano tube of modifying.
The demand of nano-scale magnetic material in magnetic recording material is increasing, the nanometer ferric oxide is owing to have good physics and chemical stability, become a kind of application functional materials very widely, can be used to prepare materials such as magneticsubstance, gas sensitive, catalyzer, pigment.The nano-metal-oxide absorption agent has been carried out big quantity research abroad.The result shows that the metal oxide absorption agent with composite structure not only has good absorbing radar wave performance, suppresses the function of ir radiation simultaneously in addition.Carbon nanotube has caused the extensive concern of scientific circles with its excellent magnetic, electricity, mechanical properties, microwave absorbing property and unique vestibule structure, with ferric oxide fill or carbon nano-tube modified will show more excellent magnetism, electrically, microwave absorbing property, have more wide application prospect.Tsang etc. have described carbon nanotube and have mixed to reflux with the concentrated nitric acid solution that contains iron nitrate ferric oxide is inserted in the carbon nanotube on Nature 372 (1994) 159, use the ferric oxide filling carbon nano-pipe under the room temperature of delivering in the 25 the carbon meeting that Mittal etc. held in calendar year 2001.Pradhan etc. are reporting on the Chem Mater 10 (1998) 2510 that utilizing metal-organic to learn in the carbon nanotube of gas phase deposition technology at opening fills Fe
2O
3Above Fe
2O
3The research of filling carbon nano-pipe all concentrates on the sign of the method and structure of preparation, to Fe
2O
3The rare report of filling carbon nano-pipe performance of composites.Nearest Jiang etc. has reported that on Chem Mater15 (2003) 2848 with carbon nanotube, molysite and urea be raw material, has synthesized Fe by the solvent-thermal method original position
3O
4The carbon nano tube compound material of modifying, but the method complexity that is adopted, the reaction times that needs is longer, and the magnetic property of matrix material is not inquired into as yet yet.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of the carbon nanotube magnetic composite material that a kind of ferric oxide modifies, and to remedy the deficiencies in the prior art, satisfies and produces and relevant field is developed needs.
In order to solve the problems of the technologies described above the technical solution used in the present invention be: the preparation method of the carbon nanotube magnetic composite material that a kind of ferric oxide is modified comprises the steps:
(1) under the room temperature, carbon nanotube is dispersed in 0.2～2wt% sodium dodecyl sulfate solution, after washing, drying, join in the soluble iron salts solution, with concentration is that the pH value of the alkaline solution regulator solution of 15～70mol/l is 8～10, membrane filtration, drying is after leaching thing and repeatedly washing with deionized water, drying is 5～12 hours under 50～80 ℃, obtains the carbon nanotube that ironic hydroxide is modified;
The carbon nanotube of the ironic hydroxide modification that (2) step (1) is obtained is in inert atmosphere, rise to 250 ℃ from room temperature, 250 ℃ keep 1～2 hour after, be warming up to 400～700 ℃ again, and under this temperature, kept 0.5～3 hour, under inert atmosphere, be cooled to room temperature, be the carbon nanotube magnetic composite material that ferric oxide is modified.
Described molysite comprises one or more in iron(ic) chloride, iron nitrate or the ferric sulfate.
Described alkaline solution comprises one or more in ammoniacal liquor, sodium hydroxide, the potassium hydroxide.
Described alkaline solution is an ammonia soln.
Described molysite and 0.2～2wt% sodium dodecyl sulfate solution mix under 400～800 rev/mins rotating speed, add carbon nanotube, ultra-sonic dispersion then.
Described carbon nanotube is selected from the multi-walled carbon nano-tubes that average caliber is 20～40nm.
The volume of described sodium dodecyl sulfate solution and the mass ratio of carbon nanotube are: 50～100mL/g.
The volume of described iron salt solutions and the mass ratio of carbon nanotube are: 200～400ml/g.
The filter opening diameter range of described filter membrane is 0.4～1.2 μ m.
Described rare gas element is a nitrogen, one or more in argon gas or the neon, and 0.5～5 liter/minute of inert gas flow, heat-up rate are 3～10 ℃/minute.
Described sodium dodecyl sulfate solution is to mix a certain amount of sodium laurylsulfonate and deionized water formulated under 400～800 rev/mins rotating speed.
Ultimate principle of the present invention is such: carbon nanotube is in sodium dodecyl sulfate solution in the ultra-sonic dispersion process, sodium laurylsulfonate is adsorbed on the carbon nanotube wall, carbon nanotube is electronegative, positively charged ion directly is adsorbed in carbon nano tube surface, sulfate ion is adsorbed in the outside, the further metallic iron ion in the adsorbent solution, be attracted to the hydroxide ion reaction in the ammoniacal liquor of metallic iron ion on the carbon nanotube wall and adding, make that ironic hydroxide modifies on carbon nanotube, form the carbon nanotube that ferric oxide is modified through calcining.
The invention has the beneficial effects as follows: adopt simple method to prepare the carbon nano tube compound material that ferric oxide is modified first, it is the soft magnetic materials of excellent property, at the high density magnetic recording material, absorbing material, xerox ink, wide band transformer, the noise filter communication has a good application prospect with fields such as transformers.
Description of drawings
Fig. 1. the X-ray diffractogram before and after the carbon nano tube modified ferric oxide
Fig. 2. the carbon nanometer tube material transmission electron microscope photo of unmodified
Fig. 3. the transmission electron microscope photo of the carbon nanotube that ferric oxide is modified
Fig. 4. the magnetic hysteresis loop result before and after the carbon nanotube that ferric oxide is modified
Embodiment
Below in conjunction with specific embodiment the present invention is done further and to elaborate.
Embodiment 1
Under the room temperature, 0.5g sodium laurylsulfonate and 50ml deionized water are mixed the sodium dodecyl sulfate solution of preparing 1wt% under 400 rev/mins rotating speed, add the 1g carbon nanotube then and carried out ultra-sonic dispersion 3 hours, through washing, join after the drying in the solubility chlorination ferrous solution, ammonia soln with 2.5wt% carries out titration, pH value to solution is 10, titrated solution membrane filtration, after leaching thing and repeatedly washing with deionized water, in 80 ℃ of baking ovens dry 12 hours, after leaching the thing drying, obtain the carbon nanotube that ironic hydroxide is modified, put into quartz boat, the tubular type of packing into atmosphere furnace, feed nitrogen, 1 liter/minute of gas flow, heat-up rate are 5 ℃/minute, rise to 250 ℃ from room temperature, be incubated after 1 hour, with 10 ℃ of min
-1Be warming up to 650 ℃, calcined 2 hours down at 650 ℃, naturally cool to room temperature under nitrogen protection, obtaining black powder shape sample at last is the carbon nanotube that ferric oxide is modified.
Fig. 1 is the X-ray diffractogram of the carbon nanotube modified of the ferric oxide of embodiment 1 preparation, a is carbon nano tube modified preceding X-ray diffraction result among the figure, b is that X-ray diffraction result and the JCPDS card 39-1346 contrast after carbon nano tube modified shows: modifier is a ferric oxide, and characteristic diffraction peak is respectively the diffraction peak of ferric oxide (311) crystal face, (220) crystal face, (440) crystal face, (511) crystal face among the figure.
Fig. 2 is the transmission electron microscope photo of carbon nanometer tube material, and caliber is about 30nm.The carbon nanotube surfaces externally and internally is all very smooth, does not see what other materials were modified, and the shallow part of middle contrast is a sky nanotube tube chamber, and the dark part of contrast is the nanotube tube wall, and the thickness of tube wall is approximately 10nm (caliber 1/3rd).
Fig. 3 is the transmission electron microscope photo of the carbon nanotube of ferric oxide modification, and the carbon nanotube outside surface is no longer smooth.Indian red is nano-particle modified on the carbon nanotube outside surface, and the size of nano particle is 20-80nm.
Fig. 4. be the magnetic hysteresis loop result before and after the carbon nanotube of ferric oxide modification, the area of the magnetic hysteresis loop after modifying as can be seen significantly increases than modifying preceding area.A is the carbon nanometer tube material magnetic hysteresis loop among the figure, and b is the magnetic hysteresis loop of ferric oxide after carbon nano-tube modified.
Table 1 is the magnetic result before and after the carbon nano tube modified ferric oxide, and the coercive force of the carbon nanotube after the modification has improved 12% before modifying, and saturation magnetization and residual magnetic flux density have improved more than 100 times respectively.
Magnetic (saturation magnetization Ms, residual magnetic flux density Mr, coercivity H) result before and after table 1. carbon nanotube is modified by ferric oxide
| Sample | Ms(emu/g) | Mr(emu/g) | Hc(Oe) |
| Carbon nanometer tube material | 0.42 | 0.10 | 145.33 |
| The carbon nanotube that ferric oxide is modified | 50.18 | 10.23 | 163.44 |
Embodiment 2
Under the room temperature, 0.8g sodium laurylsulfonate and 50ml deionized water are mixed the sodium dodecyl sulfate solution of preparing 1.6wt% under 600 rev/mins rotating speed, add the 1g carbon nanotube then and carried out ultra-sonic dispersion 3 hours, after washing, drying, join in the solubility iron nitrate solution, ammoniacal liquor with 15mol/L carries out titration, pH value to solution is 10, below presses embodiment 1 described method preparation.X diffraction, TEM (transmission electron microscope) analysis show that ferric oxide modifies carbon nanotube, the magnetic property that the magnetic test shows is modified the back material obviously improves.
Embodiment 3
Under the room temperature, sodium laurylsulfonate and deionized water are mixed the sodium dodecyl sulfate solution of preparing 0.2wt% under 800 rev/mins rotating speed, add the 1.5g carbon nanotube then and carried out ultra-sonic dispersion 3 hours, after washing, drying, join in the solubility ferrum sulfuricum oxydatum solutum, sodium hydroxide with 15mol/L carries out titration, pH value to solution is 8, below presses embodiment 1 described method preparation.X diffraction, TEM (transmission electron microscope) analysis show that ferric oxide modifies carbon nanotube, the magnetic property that the magnetic test shows is modified the back matrix material obviously improves.
Embodiment 4
Under the room temperature, sodium laurylsulfonate and deionized water are mixed the sodium dodecyl sulfate solution of preparing 2wt% under 400 rev/mins rotating speed, add the 1.5g carbon nanotube then and carried out ultra-sonic dispersion 3 hours, after washing, drying, join in the solubility chlorination ferrous solution, ammonia soln with 40mol/L carries out titration, pH value to solution is 9, below presses embodiment 1 described method preparation.X diffraction, TEM (transmission electron microscope) analysis show that ferric oxide modifies carbon nanotube, the magnetic property that the magnetic test shows is modified the back matrix material obviously improves.
Claims (10)
1. the preparation method of the carbon nanotube magnetic composite material of a ferric oxide modification is characterized in that, comprises the steps:
(1) under the room temperature, carbon nanotube is dispersed in 0.2～2wt% sodium dodecyl sulfate solution, after washing, drying, join in the soluble iron salts solution, with concentration is that the pH value of the alkaline solution regulator solution of 15～70mol/l is 8～10, membrane filtration, drying is after leaching thing and repeatedly washing with deionized water, drying is 5～12 hours under 50～80 ℃, obtains the carbon nanotube that ironic hydroxide is modified;
The carbon nanotube of the ironic hydroxide modification that (2) step (1) is obtained is in inert atmosphere, rise to 250 ℃ from room temperature, 250 ℃ keep 1～2 hour after, be warming up to 400～700 ℃ again, and under this temperature, kept 0.5～3 hour, under inert atmosphere, be cooled to room temperature, be the carbon nanotube magnetic composite material that ferric oxide is modified.
2. the preparation method of the carbon nanotube magnetic composite material that a kind of ferric oxide according to claim 1 is modified, it is characterized in that: described molysite is selected from one or more in iron(ic) chloride, iron nitrate or the ferric sulfate.
3. the preparation method of the carbon nanotube magnetic composite material that a kind of ferric oxide according to claim 1 is modified, it is characterized in that: described alkaline solution is selected from one or more in ammoniacal liquor, sodium hydroxide, the potassium hydroxide.
4. the preparation method of the carbon nanotube magnetic composite material that a kind of ferric oxide according to claim 3 is modified, it is characterized in that: described alkaline solution is an ammonia soln.
5. the preparation method of the carbon nanotube magnetic composite material that a kind of ferric oxide according to claim 1 is modified, it is characterized in that: described carbon nanotube is selected from the multi-walled carbon nano-tubes that average caliber is 20～40nm.
6. the preparation method of the carbon nanotube magnetic composite material that a kind of ferric oxide according to claim 1 is modified, it is characterized in that: the volume of sodium dodecyl sulfate solution and the mass ratio of carbon nanotube are: 50～100mL/g.
7. method according to claim 1 is characterized in that: the volume of iron salt solutions and the mass ratio of carbon nanotube are: 200～400ml/g.
8. the preparation method of the carbon nanotube magnetic composite material that a kind of ferric oxide according to claim 1 is modified is characterized in that the filter opening diameter range of described filter membrane is 0.4～1.2 μ m.
9. the preparation method of the carbon nanotube magnetic composite material that a kind of ferric oxide according to claim 1 is modified, it is characterized in that: described inert atmosphere is a nitrogen, in argon gas or the neon one or more, 0.5～5 liter/minute of inert atmosphere flow, heat-up rate are 3～10 ℃/minute.
10. the preparation method of the carbon nanotube magnetic composite material that a kind of ferric oxide according to claim 1 is modified, it is characterized in that: described sodium dodecyl sulfate solution is to mix a certain amount of sodium laurylsulfonate and deionized water formulated under 400～800 rev/mins rotating speed.
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| CN101745434B (en) * | 2008-12-19 | 2011-08-10 | 中国科学院金属研究所 | Method for selectively filling ferric oxide particles in hollow cavity of carbon nanotube |
| CN101962169A (en) * | 2010-09-14 | 2011-02-02 | 东莞市迈科新能源有限公司 | Method for preparing carbon nanotubes filled with metallic oxide |
| US8652386B2 (en) | 2010-09-16 | 2014-02-18 | Georgia Tech Research Corporation | Alignment of carbon nanotubes comprising magnetically sensitive metal oxides in nanofluids |
| CN102151575B (en) * | 2011-01-29 | 2013-04-17 | 浙江师范大学 | Method for preparing carbon nanometer tube loaded type catalyst |
| CN103529080B (en) * | 2013-10-17 | 2015-07-01 | 山东理工大学 | Preparation method of film-type gas sensor |
| US9312046B2 (en) | 2014-02-12 | 2016-04-12 | South Dakota Board Of Regents | Composite materials with magnetically aligned carbon nanoparticles having enhanced electrical properties and methods of preparation |
| PL3134932T3 (en) | 2014-04-25 | 2022-01-17 | South Dakota Board Of Regents | High capacity electrodes |
| US10468674B2 (en) | 2018-01-09 | 2019-11-05 | South Dakota Board Of Regents | Layered high capacity electrodes |
| CN111606325A (en) * | 2020-06-12 | 2020-09-01 | 东华大学 | Preparation method of graphene-ferrite-based nano functional particles with wave absorbing function |
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| CN1401562A (en) * | 2002-10-14 | 2003-03-12 | 北京大学 | Carbon nano-tube/ferromagnetism metal nanowire composite material, mfg. method and use thereof |
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