CN101819843A - Method for preparing multifunctional graphite vinyl composite material with magnetic conductivity - Google Patents
Method for preparing multifunctional graphite vinyl composite material with magnetic conductivity Download PDFInfo
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- CN101819843A CN101819843A CN 201010136802 CN201010136802A CN101819843A CN 101819843 A CN101819843 A CN 101819843A CN 201010136802 CN201010136802 CN 201010136802 CN 201010136802 A CN201010136802 A CN 201010136802A CN 101819843 A CN101819843 A CN 101819843A
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Abstract
The invention discloses a method for preparing a multifunctional graphite vinyl composite material with magnetic conductivity. The method comprises the following steps of: adding 1 part by weight of oxidizing graphite vinyl carbon and 100-2000 parts by weight of glycol into an reactor; treating for 0.1 minute-10 hours by ultrasonic waves; adding 0.1-10 parts of inorganic compound containing ferrum; in the hot bath with the temperature below 200-300 DEG C, adding 0.1-10 parts by weight of basic hydroxide, and reacting for 0.1-72 hours; filtering or centrifugating, washing and drying to obtain the multifunctional graphite vinyl composite material with magnetic conductivity. The invention has the advantages of simple method, simple process, strong controllability and scale production. The prepared multifunctional graphite vinyl composite material has superparamagnetism, conductivity and processability, and can be widely applied to fields of biological medicine, micro-nano electronics, high-property composite material and the like.
Description
Technical field
The present invention relates to the preparation method of multifunctional graphite vinyl composite material, relate in particular to a kind of preparation method of multifunctional graphite vinyl composite material of magnetic conductive.
Background technology
Graphene (graphene) is through sp by carbon atom
2The two dimensional surface monolayer carbon material that hybridized orbit forms.Graphene has character such as unique electricity, mechanics, calorifics, optics, and its carrier mobility is 200000cm
2V
-1s
-1, Young's modulus is 1100GPa, thermal conductivity is 5000Wm
-1K
-1, specific area is up to 2630m
2g
-1Because its excellent performance, Graphene has broad application prospects at aspects such as electronic device, reinforcer, composite materials.(Science 2004,306 for K.Novoselov, et al., and 666-669), Graphene has attracted to pay close attention to widely since the monolithic Graphene makes first.
Nano magnetic material is progressively to produce, develop afterwards the seventies in 20th century, becomes the new material that is full of vitality with broad application prospect.Magnetic nanoparticle can be metallic iron, cobalt, nickel or its alloy, oxide etc., owing to there are toxicity in cobalt, nickel etc., is restricted in application biological, medicine and other fields, and the oxide (γ-Fe of iron
2O
3, Fe
3O
4) because of its low toxicity, be easy to get, have good characteristics such as biocompatibility be with a wide range of applications (A.Lu, et al., Angew.Chem., Int.Ed.2007,46,1222-1244).The particle diameter of magnetic oxide is during less than 30 nanometers, and its coercive force reduces to zero, shows superparamagnetism.The surface that magnetic ferric oxide nano particles is coated on Graphene can make Graphene have superparamagnetism, gives its using value at aspects such as biological medicine, magnetic fluid, Magnetic Isolation.
In the process of preparation graphene composite material, Graphene is difficult to as direct initiation material, because the surface of Graphene does not have group, is difficult for disperseing in solvent.And a large amount of oxy radicals is contained on the graphene oxide surface, has strongly hydrophilic, can form stable dispersion liquid.And graphene oxide can make in a large number by the strong oxidizer graphite oxide, for easy, the large-scale production of graphene composite material provides may.
The preparation graphene composite material adopts graphene oxide as initiation material mostly now.But, graphene oxide be insulation with thermodynamic instability, directly use graphene oxide can limit its range of application.Therefore, it is very necessary to make graphene oxide be transformed into Graphene by the method for reducing.After yet in a single day graphene oxide joins in the composite material, again its reduction is difficult to avoid influence to other parts of composite material.So, if graphene oxide can will be made the preparation process of composite material simplify greatly by reduction simultaneously in the preparation process of composite material.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of multifunctional graphite vinyl composite material of easy, economic, efficient, the magnetic conductive that is produced on a large scale.
Technical scheme of the present invention is as follows:
The preparation method of the multifunctional graphite vinyl composite material of magnetic conductive is: add 1 weight portion graphite oxide olefinic carbon and 100～2000 weight portion glycol in reactor, with ultrasonic Treatment 0.1 minute～10 hours, the inorganic compound that adds 0.1～10 part of iron content, under 200～300 ℃ of heating baths, add 0.1～10 weight portion alkaline hydrated oxide, reacted 0.1～72 hour, and after suction filtration or centrifugal, washing, drying, obtained the multifunctional graphite vinyl composite material of magnetic conductive.
The raw material of described Graphene are selected from the Graphene through oxidation processes, and contain the Graphene of carboxyl functional group modification.Described glycol is selected from diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, five glycol or hexaethylene glycol.The inorganic compound of described iron content is selected from iron chloride, ferric nitrate, ferric sulfate, frerrous chloride, ferrous nitrate or ferrous sulfate.Described alkaline matter is selected from NaOH or potassium hydroxide.
The present invention utilizes the hydrolysis of iron ion under the high-temperature alkaline condition, generates ferroferric oxide nano granules on the Graphene surface, thereby makes the multifunctional graphite vinyl composite material of magnetic conductive.This preparation method and traditional Fe (acac)
3(ferric acetyl acetonade) or Fe (CO)
5(carbonyl iron) high-temperature decomposition relatively has tangible advantage, and lower as heating-up temperature, controllability is strong, and raw material is cheap and easy to get, economical and efficient, and agents useful for same and reprocessing environmental pollution are very little, and can scale produce in a large number.The dispersiveness of the multifunctional graphite vinyl composite material of the magnetic conductive of gained in solvent compared with Graphene and is significantly improved, and has a wide range of applications in fields such as biological medicine, micro-nano electronics, high-performance composite materials.
Description of drawings
Fig. 1 be the magnetic conductive multifunctional graphite vinyl composite material transmission electron microscope figure (figure a, b), scanning electron microscope diagram (figure c), atomic force microscope figure (figure d) has shown that the graphene nanometer sheet surface has evenly covered one deck nano particle;
Fig. 2 is the powder x-ray diffraction spectrogram of magnetic conductive multifunctional graphite vinyl composite material, the position of all diffraction maximums is corresponding well with the standard diagram of tri-iron tetroxide with intensity, has proved to have the ferroferric oxide nano crystal particle on the graphene nanometer sheet surface;
Fig. 3 is a magnetic conductive multifunctional graphite vinyl composite material magnetic hysteresis loop at room temperature, has shown that it has superparamagnetism, and saturation magnetization reaches 42.8emu/g;
Fig. 4 is that the magnetic conductive multifunctional graphite vinyl mixes the change curve of the conductivity of film forming with its weight content with polyurethane, has shown that it has conductivity.
Embodiment
Principle of the present invention is to utilize iron ion to be adsorbed in the graphene oxide surface, and alkaline liquid-phase hydrolysis at high temperature generates the magnetic Nano ferric oxide particles, and makes the graphene oxide reduction simultaneously, thereby makes the multifunctional graphite vinyl composite material of magnetic conductive.
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
Graphene oxide with the chemical oxidization method preparation is an initial raw material, reacts with compound that contains iron ion such as iron chloride, obtains the functionalization graphene of magnetic conductive.In the 100mL there-necked flask of agitating device is housed, add 30mg graphene oxide and 20g diethylene glycol (DEG), with the 40kHz ultrasonic Treatment after 1 hour, 60mg iron chloride is added in the reaction bulb, be heated to 220 ℃ under the nitrogen protection, stirred 30 minutes, the diethylene glycol solution that adds 50mg NaOH then, stir and to continue reaction 1 hour down,, obtain the functionalization graphene of magnetic conductive through suction filtration or centrifugation, washing, drying; The magnetic test analysis shows that its saturation magnetization is 30.7emu/g.
Embodiment 2:
Adopt the reactions steps identical with embodiment 1, added the NaOH afterreaction 1 minute, reaction is after separate dry functionalization graphene that must magnetic conductive; The magnetic test analysis shows that its saturation magnetization is 14.0emu/g.
Embodiment 3:
Adopt the reactions steps identical with embodiment 1, added the NaOH afterreaction 24 hours, reaction is after separate dry functionalization graphene that must magnetic conductive; The magnetic test analysis shows that its saturation magnetization is 36.1emu/g.
Embodiment 4:
Adopt the reactions steps identical with embodiment 1, add 120mg iron chloride, reaction is after separate dry functionalization graphene that must magnetic conductive; The magnetic test analysis shows that its saturation magnetization is 42.8emu/g.
Embodiment 5:
Adopt the reactions steps identical with embodiment 1, add 15mg iron chloride, reaction is after separate dry functionalization graphene that must magnetic conductive; The magnetic test analysis shows that its saturation magnetization is 0.7emu/g.
Embodiment 6:
Adopt the reactions steps identical with embodiment 1, add 90mg NaOH, reaction is after separate dry functionalization graphene that must magnetic conductive; The magnetic test analysis shows that its saturation magnetization is 41.0emu/g.
Embodiment 7:
Adopt the reactions steps identical with embodiment 1, add 10mg NaOH, reaction is after separate dry functionalization graphene that must magnetic conductive; The magnetic test analysis shows that its saturation magnetization is 0.6emu/g.
Embodiment 8:
In reactor, add 1 part of graphene oxide material with carbon element and 100 portions of diethylene glycol (DEG)s, with ultrasonic Treatment 0.1 hour, the inorganic compound that adds 0.1 part of iron content, under 200 ℃ of heating baths, the diethylene glycol solution that adds 0.1 part of alkaline hydrated oxide, stir and to continue reaction 0.1 minute down,, obtain the functionalization graphene of magnetic conductive through suction filtration or centrifugation, washing, drying.
Embodiment 9:
In reactor, add 1 part of graphene oxide material with carbon element and 2000 portions of diethylene glycol (DEG)s, with ultrasonic Treatment 10 hours, the inorganic compound that adds 10 parts of iron content, under 300 ℃ of heating baths, the diethylene glycol solution that adds 10 parts of alkaline hydrated oxides, stir and to continue reaction 72 hours down,, obtain the functionalization graphene of magnetic conductive through suction filtration or centrifugation, washing, drying.
Embodiment 10:
In reactor, add 1 part of carboxyl-functional Graphene material with carbon element and 20g glycol; with ultrasonic Treatment after 1 hour; 60mg iron chloride is added in the reaction bulb; be heated to 220 ℃ under the nitrogen protection; stirred 30 minutes, and added the diethylene glycol solution of 50mg NaOH then, stir and continue reaction 1 hour down; through suction filtration or centrifugation, washing, drying, obtain the functionalization graphene of magnetic conductive.
Claims (5)
1. the preparation method of the multifunctional graphite vinyl composite material of a magnetic conductive, it is characterized in that: in reactor, add 1 weight portion graphite oxide olefinic carbon and 100～2000 weight portion glycol, with ultrasonic Treatment 0.1 minute～10 hours, the inorganic compound that adds 0.1～10 part of iron content, under 200～300 ℃ of heating baths, add 0.1～10 weight portion alkaline hydrated oxide, reacted 0.1～72 hour, after suction filtration or centrifugal, washing, drying, obtain the multifunctional graphite vinyl composite material of magnetic conductive.
2. the preparation method of the multifunctional graphite vinyl composite material of a kind of magnetic conductive according to claim 1 is characterized in that the raw material of described Graphene are selected from the Graphene of process oxidation processes, and contains the Graphene of carboxyl functional group modification.
3. the preparation method of the multifunctional graphite vinyl composite material of a kind of magnetic conductive according to claim 1 is characterized in that described glycol is selected from diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, five glycol or hexaethylene glycol.
4. the preparation method of the multifunctional graphite vinyl composite material of a kind of magnetic conductive according to claim 1 is characterized in that the inorganic compound of described iron content is selected from iron chloride, ferric nitrate, ferric sulfate, frerrous chloride, ferrous nitrate or ferrous sulfate.
5. the preparation method of the multifunctional graphite vinyl composite material of a kind of magnetic conductive according to claim 1 is characterized in that described alkaline matter is selected from NaOH or potassium hydroxide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103638894A (en) * | 2013-12-11 | 2014-03-19 | 江苏大学 | Preparation method of modified graphene-based iron oxide nano-composite material |
| CN105510416A (en) * | 2016-01-07 | 2016-04-20 | 上海第二工业大学 | Preparation method of electrochemical sensor based on magnetic nanocomposite |
| CN105513740A (en) * | 2015-12-07 | 2016-04-20 | 上海第二工业大学 | Spinel type ferromagnet/graphene nanometer composite material, preparing method and application thereof |
| CN106206064A (en) * | 2016-08-24 | 2016-12-07 | 张伟 | Ultracapacitor High-performance graphene electrode material and preparation method thereof |
| CN110745813A (en) * | 2019-10-21 | 2020-02-04 | 上海船舶工程质量检测有限公司 | Graphene-loaded ferroferric oxide magnetic powder particle and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550003A (en) * | 2009-04-22 | 2009-10-07 | 湖南大学 | Nano-graphite alkenyl composite wave-absorbing material and method of preparing the same |
| WO2009158117A2 (en) * | 2008-05-30 | 2009-12-30 | The Regents Of The University Of California | Chemical modulation of electronic and magnetic properties of graphene |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009158117A2 (en) * | 2008-05-30 | 2009-12-30 | The Regents Of The University Of California | Chemical modulation of electronic and magnetic properties of graphene |
| CN101550003A (en) * | 2009-04-22 | 2009-10-07 | 湖南大学 | Nano-graphite alkenyl composite wave-absorbing material and method of preparing the same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103638894A (en) * | 2013-12-11 | 2014-03-19 | 江苏大学 | Preparation method of modified graphene-based iron oxide nano-composite material |
| CN105513740A (en) * | 2015-12-07 | 2016-04-20 | 上海第二工业大学 | Spinel type ferromagnet/graphene nanometer composite material, preparing method and application thereof |
| CN105510416A (en) * | 2016-01-07 | 2016-04-20 | 上海第二工业大学 | Preparation method of electrochemical sensor based on magnetic nanocomposite |
| CN106206064A (en) * | 2016-08-24 | 2016-12-07 | 张伟 | Ultracapacitor High-performance graphene electrode material and preparation method thereof |
| CN106206064B (en) * | 2016-08-24 | 2019-02-12 | 苏州欢颜电气有限公司 | Supercapacitor High-performance graphene electrode material and preparation method thereof |
| CN110745813A (en) * | 2019-10-21 | 2020-02-04 | 上海船舶工程质量检测有限公司 | Graphene-loaded ferroferric oxide magnetic powder particle and preparation method thereof |
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| CN101819843B (en) | 2013-05-22 |
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Effective date of registration: 20190904 Address after: 313199 Room 830, 8th Floor, Changxing World Trade Building, 1278 Mingzhu Road, Changxing Economic Development Zone, Huzhou City, Zhejiang Province Patentee after: Changxin de Technology Co., Ltd. Address before: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Patentee before: Zhejiang University |