CN1254306C - Manufacturing method of packed magnetic metal nanometer carbon ball - Google Patents
Manufacturing method of packed magnetic metal nanometer carbon ball Download PDFInfo
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- CN1254306C CN1254306C CN02141949.3A CN02141949A CN1254306C CN 1254306 C CN1254306 C CN 1254306C CN 02141949 A CN02141949 A CN 02141949A CN 1254306 C CN1254306 C CN 1254306C
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- magnetic metal
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- carbon microsphere
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Abstract
The present invention relates to a method for manufacturing a nanometer carbon ball filled with magnetic metals, which comprises the following steps: (a) providing an electric arc reaction chamber with a graphite cathode and a composite graphite anode, and filling a noble gas into the electric arc reaction chamber, wherein the composite graphite anode comprises at least one magnetic metal or a derivative thereof; (b) applying a pulse current between the cathode and the anode to generate electric arc discharge reaction; (c) collecting a product deposited at the graphite cathode. The present invention can obtain a high-purity nanometer carbon ball filled with magnetic metals (the nanometer carbon ball filled with the magnetic metals is a main product), and moreover, the present invention has the advantages of low cost, easy purification, etc.
Description
Technical field
The present invention relates to the manufacture method of a kind of filling magnetic metal nano carbon microsphere (magnetic metal filled carbonnanocapsules), particularly a kind of high-purity is filled the manufacture method of magnetic metal nano carbon microsphere.
Background technology
The polyhedron carbon that the skin of filling the magnetic metal nano carbon microsphere is made up of with the structure of ball in the ball the multilayer graphite linings bunch, its core is by being made up of metal, metallic compound, metal carbides or the alloy material of magnetic.The about 3-100nm of formed its diameter of filling magnetic metal nano carbon microsphere; have special fullerene (fullerene) structure and light, electricity, magnetic property; and because the encirclement of peripheral graphite linings can protect the internal magnetization metal nanoparticle to avoid oxidation and acid etching.Fill the magnetic metal nano carbon microsphere and can be applicable to many fields, for example: medicine (pharmaceutical grade activated carbon); Light, heat absorption and magnetic recording; Magnetic fluid; Catalyst, sensor; The tool thermal conductance, special electrically, the fields such as nano composite material of magnetic.
Yet the method gained head product for preparing filling magnetic metal nano carbon microsphere on the document only has a small amount of nano carbon microsphere based on the individual layer CNT.Owing between nano carbon microsphere and CNT strong Fan Dewali is arranged, under the few situation of amount, be difficult for its separation and purification, because of individual layer CNT one end is coated with the metal solvent particle, have magnetic equally with filling magnetic metal nano carbon microsphere, also can't utilize magnetic force to be separated.So conventional method is difficult for the highly purified filling magnetic metal nano carbon microsphere of preparation, product not only purity is low, and contains a large amount of carbon ash impurity and individual layer CNT etc.And because conventional method cost height, the related application that causes filling the magnetic metal nano carbon microsphere is limited to standstill state always.
Summary of the invention
Main purpose of the present invention is to provide a kind of manufacture method (is primary product to fill the magnetic metal nano carbon microsphere) of filling the magnetic metal nano carbon microsphere, can obtain high-purity and fill the magnetic metal nano carbon microsphere.
For reaching above-mentioned purpose, method of the present invention comprises following key step: an electric arc reaction chamber (a) is provided, contain graphite cathode and composite graphite anode, this composite graphite anode contains at least a magnetic metal or derivatives thereof, and feeds an inert gas in this electric arc reaction chamber; (b) apply a voltage between above-mentioned negative electrode and the anode with a pulse current, thereby produce the arc discharge reaction; And the deposit that (c) is collected in graphite cathode.
In addition, comprise a purification procedures (d) afterwards in addition in step (c), to go out to fill the magnetic metal nano carbon microsphere from above-mentioned product separation and purification, it can comprise: (d1) with an interfacial agent above-mentioned product is scattered in the solution; (d2) separate the principal product and the CNT of the filling magnetic metal nano carbon microsphere in the above-mentioned solution with tubing string chromatography or filter membrane; And (d3) utilize magnetic attraction to isolate and fill the magnetic metal nano carbon microsphere, and utilize acidity or basic solvent to clean and remove kish particulate and interfacial agent.
Description of drawings
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, and conjunction with figs. is described in detail below:
Fig. 1 shows that one is used to implement the schematic diagram of electric arc reaction of the present invention chamber.
Fig. 2 is electron microscope (TEM) photo that nano carbon microsphere is bored in the filling behind the purifying.
Fig. 3 bores electron microscope (TEM) photo of nano carbon microsphere for the filling of amplifying.
Description of symbols
1--electric arc reaction chamber; The 2--power supply; The 10--graphite cathode;
12--composite graphite anode; The 14--inert gas entrance;
The outlet of 16--inert gas; The 18--cooling water inlet;
The 20--coolant outlet.
The specific embodiment
Technology of the present invention mainly is under the inert gas of high pressure (greater than 1 atmospheric pressure), utilize pulse current (pulse current) to carry out the arc discharge reaction, density of electrode surface temperature, magnetic metal vapour density and carbon vapor is improved the productive rate of carbon ball when changing arc discharge by this, and is used for making filling magnetic metal nano carbon microsphere.
Please refer to Fig. 1, Fig. 1 shows that one is used to implement the schematic diagram of electric arc reaction of the present invention chamber.In electric arc reaction chamber 1, comprise a pair of electrode 10,12 at least as arc discharge.Inert gas is entered in the electric arc reaction chamber 1 by introducing port 12, is discharged by outlet 16.The periphery of electric arc reaction chamber 1 surrounds with the cooling water that flows, and 16 is the cooling water inlet among the figure, and 18 is coolant outlet.
In the present invention, electric arc reaction carries out under the inert gas that flows, and the flow velocity of inert gas can be controlled in 10-200mm
3/ min preferably is controlled at 30-120mm
3/ min.Be applicable to that inert gas of the present invention includes but not limited to: helium, argon gas, nitrogen etc.For preparing filling magnetic metal nano carbon microsphere of the present invention, the pressure of electric arc reaction chamber can be controlled in the 0.1-5 atmospheric pressure, preferably can be controlled between the 1--2 atmospheric pressure.
In electric arc reaction chamber 1, be provided with two mutual right electrodes 10,12.Electrode 10 used herein is a graphite material, generally is as graphite cathode with graphite rod; Electrode 12 used herein is for containing the composite graphite anode of at least a magnetic metal or derivatives thereof, generally be to suppress the composite stone inker that forms for being mixed with the powder of at least a magnetic metal or derivatives thereof by carbon dust, the mole mixture ratio example of the powder of carbon dust and magnetic metal or derivatives thereof is between 100: 1 to 100: 20.The composite graphite anode can further comprise resin, mixing compacting opens tempering under high temperature (400～1500 ℃) anaerobic, the resin graphitization is shaped, the ratio that resin adds is when the summation of the powder of this carbon dust and magnetic metal or derivatives thereof is 100 weight portions, and resin adds 10～30 weight portions.Used resin can be cyanamide resin (melamineresin), epoxy resin (epoxy resin), phenolic resins or graphitisable resin.Above-mentioned magnetic metal can be Sc, V, Cr, Fe, Co, Ni, Y, Zr, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ta, Os, Ir, Pt, Au, Th or U or its combination, and is wherein preferable with elements such as Co, Fe, Ni, La, Y or its combination again.The derivative of above-mentioned magnetic metal can be alloy, the oxide of this magnetic metal or the carbide of this magnetic metal of this magnetic metal and the formation of other element.
When the magnetic metal nano carbon microsphere was filled in preparation, to graphite cathode 10 and composite graphite anode 12, the electric energy that is provided need make was enough to produce arc discharge to form deposit on graphite cathode 10 between the two poles of the earth from power supply 2 supply electric energy.
According to technical scheme of the present invention, when carrying out the arc discharge reaction, utilize the pulse current (pulse current) of a CF to apply a voltage between negative electrode and the anode, be different from used direct current of known technology or alternating current.According to the present invention, the frequency range of pulse current is between 0.01--1000Hz.The controlled amount of electric current is built in the 50-800 ampere, and the voltage between the electrode is controlled at the scope of 10--30 volt approximately.
After carrying out arc discharge reaction according to above-mentioned condition, sedimental core can obtain the head product of black powder on negative carbon 10, comprising the primary product of filling the magnetic metal nano carbon microsphere more than about 90%--40%, and the metallic particles of the following hollow nano carbon microsphere of 10%--50%, CNT and a small amount of (below 10%) no carbon-coating coating.This head product can obtain highly purified filling magnetic metal nano carbon microsphere through after being further purified.Purifying procedure is scattered in head product in one solution at first being used in an interfacial agent; Then, with filling magnetic metal nano carbon microsphere and the CNT in tubing string chromatography or the filter membrane separation solution, and utilize magnetic attraction to isolate and fill the magnetic metal nano carbon microsphere, and utilize acidity or basic solvent to clean and remove kish particulate and interfacial agent, can obtain purity at last more than 80%, about 95% filling magnetic metal nano carbon microsphere.
Be applicable to that interfacial agent of the present invention can be cation interfacial active agent, as cetrimonium bromide (certyltrimethyl ammonium bromide), teepol, as lauryl sodium sulfate (sodium dodecyl sulfate), the both sexes interfacial agent, as alkyl betaine (alkylbetaine) or non-ionic interfacial agent, as lauryl alcohol (lauryl alcohol ether).Wherein be preferably cetrimonium bromide and lauryl sodium sulfate.The above-mentioned filter that is used for carrying out the tubing string chromatography can utilize the chromatography tubing string of (size exclusion) function that has size exclusion, and the front end of this chromatography tubing string preferably has the about 0.2 micron filter membranous layer in an aperture.In addition, also can use filter membrane to separate separately, and not use the tubing string chromatography.When using filter membrane to separate, filtrate heavily can be filtered for several times in the hope of obtaining preferable separating effect.
Compared with the prior art, the present invention is for obtaining (is principal product to fill the magnetic metal nano carbon microsphere) best approach of highly purified filling magnetic metal nano carbon microsphere at present.
Present embodiment utilization electric arc reaction chamber as shown in Figure 1 prepares fills the magnetic metal nano carbon microsphere, and wherein graphite rod is a negative electrode, and the composite stone inker is that (graphite rod and composite graphite diameter are 0.24 inch to anode.Negative electrode is shorter, the about 8--10 centimetre of length).The composite stone inker is with 100: 5 carbon dust of mol ratio and cobalt metal-powder, add the cyanamide resin that accounts for powder gross weight 20%, utilize hot press in 170 ℃ of following press formings after mixing, again this compound bar is heated to 700 ℃ under anaerobic, the complete graphitization of its resin is shaped.
In the electric arc reaction chamber, with 60-90cm
3The flow velocity of/min feeds argon gas, and the pressure of reative cell is controlled at 1.2 atmospheric pressure approximately.The cooling water of the periphery of electric arc reaction chamber for flowing.
With the pulse current of about 60Hz frequency, about 20 volts with about 100 amperes condition under carry out arc discharge (carbon arc) reaction.React after about 30 minutes and stop exoelectrical reaction, on negative carbon, can get deposit (the about 3--4 centimetre of deposit length; Diameter is approximately identical with graphite rod), cut deposit, can obtain the head product of black powder in its core, wherein contain the nano carbon microsphere of the 70% filling cobalt of having an appointment and about 30% hollow nano carbon microsphere, short CNT, and do not have the cobalt metal particle that carbon-coating coats on a small quantity.Please refer to Fig. 2, be depicted as electron microscope (TEM) photo that nano carbon microsphere is bored in filling behind the purifying.
Head product utilizes an interfacial agent to be scattered in the solution, and the filter method with the tubing string chromatography separates the filling magnetic Nano carbon ball in the solution with short CNT again.At last, utilize magnetic attraction to isolate and fill the magnetic metal nano carbon microsphere, and utilize acidity or basic solvent and alcohols to clean and remove kish particulate and interfacial agent.The result can be purified to 80～99.9%, and the high-purity that is preferably more than 95% is filled the magnetic metal nano carbon microsphere.Please refer to Fig. 3, be depicted as electron microscope (TEM) photo of the filling magnetic Nano carbon ball of amplification.
Though the present invention with preferred embodiment openly as above, so it is not to be used to limit the present invention.Any those of ordinary skill in the art without departing from the spirit and scope of the present invention, can do some equivalences and change and change, so protection scope of the present invention is as the criterion with claim.
Claims (27)
1, a kind of manufacture method of filling the magnetic metal nano carbon microsphere is characterized in that, comprises the following steps:
(a) provide an electric arc reaction chamber, contain graphite cathode and composite graphite anode, this composite graphite anode contains at least a magnetic metal or derivatives thereof, and feeds an inert gas in this electric arc reaction chamber;
(b) apply a voltage between above-mentioned negative electrode and the anode with a pulse current, thereby produce the arc discharge reaction, wherein the frequency of this pulse current is 0.01～1000Hz; And
(c) be collected in the deposit of graphite cathode,
Wherein, this magnetic metal is selected from the group that Sc, V, Cr, Fe, Co, Ni, Y, Zr, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ta, Os, Ir, Pt, Au, Th and U element formed,
The derivative of this magnetic metal is selected in the group that the carbide of the oxide of the alloy of this magnetic metal and the formation of other element and this magnetic metal and this magnetic metal is formed.
2, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 1 is characterized in that, this graphite cathode is constituted by graphite rod.
3, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 1 is characterized in that, this composite graphite anode is for being mixed the composite stone inker that compacting forms with the powder of at least a magnetic metal or derivatives thereof by carbon dust.
4, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 3 is characterized in that, but the composite stone inker of this composite graphite anode for comprising that further the compacting of graphitization mixed with resin forms.
5, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 3 is characterized in that, the mole mixture ratio example of the powder of this carbon dust and magnetic metal or derivatives thereof is between 100: 1 to 100: 20.
6, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 4 is characterized in that, but should the graphitization resin system select in the group that cyanamide resin and epoxy resin and phenolic resins are formed.
As the manufacture method of claim 4 or 6 described filling magnetic metal nano carbon microspheres, it is characterized in that 7, the ratio that this resin adds is when the summation of the powder of this carbon dust and magnetic metal or derivatives thereof is 100 weight portions, resin adds 10～30 weight portions.
8, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 1 is characterized in that, the flow velocity of this inert gas is controlled at 10～200mm
3/ min.
9, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 1 is characterized in that, the pressure of this electric arc reaction chamber is controlled at 0.1～5 atmospheric pressure.
10, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 1 is characterized in that, this arc discharge be reflected at 10～30 volts with 50～800 amperes condition under carry out.
11, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 1 is characterized in that, step (c) is collected the sedimental core of graphite cathode.
12, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 11 is characterized in that, comprises principal product, hollow nano carbon microsphere and the CNT of filling magnetic metal nano carbon microsphere in the deposit of graphite cathode.
13, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 1 is characterized in that, this graphite cathode is constituted by graphite rod; But this composite graphite anode is for suppressing the composite stone inker that forms by the powder of carbon dust and at least a magnetic metal or derivatives thereof with the graphitization mixed with resin; Deposit on this graphite cathode comprises principal product, hollow nano carbon microsphere and the CNT of filling the magnetic metal nano carbon microsphere; And this method also further comprises step (d): go out to fill the magnetic metal nano carbon microsphere from above-mentioned deposit separation and purification.
14, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 13 is characterized in that, the mole mixture ratio example of the powder of this carbon dust and magnetic metal or derivatives thereof is between 100: 1 to 100: 20.
15, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 13 is characterized in that, but should select in the group that cyanamide resin and epoxy resin and phenolic resins are formed by the graphitization resin.
16, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 13 is characterized in that, the ratio that this resin adds is when the summation of the powder of this carbon dust and magnetic metal or derivatives thereof is 100 weight portions, and resin adds 10～30 weight portions.
17, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 13 is characterized in that, the flow velocity system of this inert gas is controlled at 10～200mm
3/ min.
18, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 13 is characterized in that, the pressure system of this electric arc reaction chamber is controlled at 0.1～5 atmospheric pressure.
19, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 13 is characterized in that, the reaction of this arc discharge tie up to 10～30 volts with 50～800 amperes condition under carry out.
20, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 13 is characterized in that, step (c) is to collect the sedimental core of negative electrode graphite rod.
21, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 13 is characterized in that, step (d) comprising:
(d1) with an interfacial agent above-mentioned product is scattered in the solution;
(d2) separate the principal product of the filling magnetic metal nano carbon microsphere in the above-mentioned solution and lack CNT with the tubing string chromatography; And
(d3) utilize magnetic attraction to isolate and fill the magnetic metal nano carbon microsphere, and utilize acidity or basic solvent and alcohols to clean and remove kish particulate and interfacial agent.
22, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 21 is characterized in that, this interfacial agent is cation interfacial active agent, teepol, both sexes interfacial agent or non-ionic interfacial agent.
23, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 21 is characterized in that, this interfacial agent is cetrimonium bromide or lauryl sodium sulfate.
24, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 21 is characterized in that, step (d2) is to use a front end to have the chromatography tubing string of filter membrane.
25, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 24 is characterized in that, it is 0.2 micron hole that this filter membranous layer has size.
26, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 21 is characterized in that, the filling magnetic metal nano carbon microsphere purity of step (d3) gained is 80～99.9%.
27, the manufacture method of filling magnetic metal nano carbon microsphere as claimed in claim 21 is characterized in that, the filling magnetic metal nano carbon microsphere purity of step (d3) gained is greater than 95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02141949.3A CN1254306C (en) | 2002-08-28 | 2002-08-28 | Manufacturing method of packed magnetic metal nanometer carbon ball |
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|---|---|---|---|
| CN02141949.3A CN1254306C (en) | 2002-08-28 | 2002-08-28 | Manufacturing method of packed magnetic metal nanometer carbon ball |
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| CN1478593A CN1478593A (en) | 2004-03-03 |
| CN1254306C true CN1254306C (en) | 2006-05-03 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100537411C (en) * | 2004-08-20 | 2009-09-09 | 财团法人工业技术研究院 | Nanometer carbon ball with heteroatom and its preparation method |
| CN100453955C (en) * | 2005-01-07 | 2009-01-21 | 鸿富锦精密工业（深圳）有限公司 | Heat pipe and manufacturing method thereof |
| CN100537082C (en) * | 2005-10-26 | 2009-09-09 | 财团法人工业技术研究院 | Manufacturing device and method of nano metal ball and nano metal powder |
| TW201725385A (en) * | 2016-01-05 | 2017-07-16 | 財團法人工業技術研究院 | Raman detecting chip for thin layer chromatography and method for separating and detecting an analyte |
| CN107127334B (en) * | 2017-05-09 | 2018-12-28 | 东北大学 | A kind of nano particle and preparation method thereof of carbide-metal nucleocapsid structure |
| CN108298520B (en) * | 2018-04-08 | 2021-02-02 | 苏州大学张家港工业技术研究院 | Water-soluble embedded thorium fullerene and preparation method and application thereof |
| JP7127452B2 (en) * | 2018-09-20 | 2022-08-30 | トヨタ自動車株式会社 | Active materials and fluoride ion batteries |
| CN110976896A (en) * | 2019-12-16 | 2020-04-10 | 河南英能新材料科技有限公司 | Preparation method of carbon nanohorn metal composite material |
| CN111872407B (en) * | 2020-07-27 | 2022-12-27 | 北华大学 | Preparation method of carbon-coated noble metal ultrafine nanoparticles and product thereof |
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Granted publication date: 20060503 |