CN105819421A - Preparation method of ceramic coated carbon nanotube - Google Patents
Preparation method of ceramic coated carbon nanotube Download PDFInfo
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- CN105819421A CN105819421A CN201610146235.0A CN201610146235A CN105819421A CN 105819421 A CN105819421 A CN 105819421A CN 201610146235 A CN201610146235 A CN 201610146235A CN 105819421 A CN105819421 A CN 105819421A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention discloses an in-situ synthesized ceramic coated carbon nanotube and a preparation method thereof. The method comprises the following steps: (1) spraying a carbon source material and a catalyst source into a high temperature (800-1500 DEG C) reactor cavity full of reducing atmosphere from top to bottom from the top of a carbon nanotube synthesis furnace, wherein the carbon source material is thermally decomposed to form high activity carbon atoms, and in the presence of metal atoms (Ma), which are formed by thermally decomposing the catalyst source, the high activity carbon atoms are converted into carbon nanotubes; (2) at the same time, a ceramic source solution is spraying into the reactor cavity from bottom to top from the bottom part of the synthesis furnace, wherein the ceramic source forms ceramic particles, which deposit on the surface of carbon nanotubes to form ceramic coated carbon nanotubes. The provided preparation method has the advantages that the agglomeration of generated carbon nanotubes is avoided, at the same time, ceramic and carbon nanotubes are evenly dispersed in the nano level; moreover, the ceramic coated carbon nanotubes can be more easily dispersed, post treatment or processing is not needed, and the structure and characteristics of original carbon nanotubes can be maintained.
Description
Technical field
The present invention relates to field of material technology, be specifically related to the preparation method of a kind of (in-situ) in situ synthesis ceramic coatings CNT.
Background technology
CNT is seamless, the body of hollow that the graphene sheet layer formed by carbon atom is rolled into, it has high axial strength and the highest elastic modelling quantity, draw ratio is big, specific surface is big, high-temperature stable, anti-friction wear-resistant are good, heat conductivity is good, therefore can be used to be widely used in manufacturing high intensity, the nano novel composite of good stability.In order to give full play to CNT excellent properties in the composite, need CNT is effectively disperseed.
In recent years, it is concentrated mainly in post processing for improving the research of the dispersibility of CNT, by including the means such as ball milling mixing, surface chemical plating, alleviates the reunion degree of CNT self, and be uniformly dispersed in matrix material.And the potentiation that relatively uniform scattered CNT is in metallic matrix is clearly, the performance such as the tensile strength of material, yield strength, hardness, wearability is all obviously improved.But high speed ball milling easily damages carbon nano tube structure, low speed ball milling is opened CNT and is reunited inefficient, and Electroless Plating Procedure is complicated, coating inevitably contains other impurity (such as palladium etc.), and owing to processing cost is high, the reasons such as difficult quality control, above method all fails large-scale application in industrialized production.
Summary of the invention
The present invention is directed to the problems referred to above, it is provided that a kind of (in-situ) in situ synthesis ceramic coatings CNT and preparation method thereof.In CNT synthetic furnace, Nano Ceramic Particles uniform deposition is generated in carbon nano tube surface while synthesizing carbon nanotubes, form ceramic coatings CNT, in situ (in-situ) to realize CNT dispersed with the nanoscale of ceramic particle.
First aspect present invention provides a kind of (in-situ) in situ preparation method of synthesis ceramic coatings CNT, and it comprises the steps:
(1) carbon source material and catalyst source by CNT synthetic furnace top, from up to down spray into full reducing atmosphere high-temperature reactor intracavity 800～1500 DEG C, carbon source material is pyrolyzed into high-activity carbon atom, forms CNT under the catalysis of the metallic atom Ma of catalyst source pyrolysis formation；
(2) while above-mentioned course of reaction is carried out, by ceramics source solution bottom synthetic furnace, bottom-up spray in above-mentioned reactor cavity, ceramic source forms Nano Ceramic Particles and is deposited on the carbon nano tube surface of new life, and (in-situ) generates ceramic coatings CNT in situ.
Preferably, described carbon source material is hydrocarbon selected from methanol, ethanol, benzene or toluene etc. or one or more mixing in hydrocarbon oxygen compound.
Preferably, one or more during described reducing atmosphere comprises hydrogen, carbon monoxide or ammonia；Or the gaseous mixture of above-mentioned reducibility gas and noble gas, the one during wherein indifferent gas is argon or nitrogen or gaseous mixture.
Preferably, described catalyst source is selected from metal inorganic salt or metallo-organic compound.One or more the mixing in ferrous sulfate, nitric acid molybdenum or tungsten chloride of the described metal inorganic salt；One or more the mixing in cobalt oxalate, nickel acetylacetonate or ferrocene of the described metallo-organic compound.
Preferably, described ceramic source is selected from metal inorganic salt or organic compound；One or more the mixing in aluminum nitrate, magnesium nitrate or zirconium nitrate of the described metal inorganic salt；One or more the mixing in methyl-silicone oil, ethyl silicon oil or phenyl silicone oil of the described organic compound.
Preferably, the temperature in described reactor cavity is 1000～1200 DEG C.Preferably, by the high-temperature reactor intracavity from up to down spraying into full reducing atmosphere in an input pipe at CNT synthetic furnace top after carbon source material mixes with catalyst source.
A second aspect of the present invention provides a kind of (in-situ) in situ synthesis ceramic coatings CNT, and it is prepared by the following step:
(1) carbon source material and catalyst source by CNT synthetic furnace top, from up to down spray into full reducing atmosphere high-temperature reactor intracavity 800～1500 DEG C, carbon source material is pyrolyzed into high-activity carbon atom, forms CNT under the catalysis of the metallic atom Ma of catalyst source pyrolysis formation；
(2) while above-mentioned course of reaction is carried out, by ceramics source solution bottom synthetic furnace, bottom-up spray in above-mentioned reactor cavity, ceramic source forms Nano Ceramic Particles, is deposited on the carbon nano tube surface of new life, in-situ preparation ceramic coatings CNT.
Preferably, the carbon pipe a diameter of 5～100nm of described ceramic coatings CNT, the ceramic thickness in carbon nano tube surface cladding is 1～100nm, and carbon/pottery weight ratio is 0.1～1.0.
Preferably, the mixture of the one or both during described pottery is silicon dioxide, zirconium oxide.
A kind of (in-situ) in situ synthesis ceramic coatings CNT of the present invention and preparation method thereof, in same reactor, while CVD synthesizing carbon nanotubes, ceramic particle is deposited on carbon nano tube surface and forms equally distributed ceramic coating.
The preparation method of ceramic coatings CNT that the present invention provides, had both avoided self reuniting after CNT generates, and achieved again dispersed at nanoscale of pottery and CNT.Original position (in-situ) the synthetic method production efficiency that the present invention uses is higher, newborn Nano Ceramic Particles is combined more firm with newborn CNT, building-up process does not introduce other impurity, and the more readily dispersible use of the CNT of ceramic coatings, process without postorder and processing, be conducive to keeping structure and the feature of primary CNT.
Accompanying drawing explanation
Fig. 1 is the synthetic method schematic diagram that the present invention prepares ceramic coatings CNT,
Fig. 2 is zirconia ceramics enveloped carbon nanometer tube shown in the embodiment of the present invention 1 (zirconia content 68%) XRD curve,
Fig. 3 is the microscopic appearance of zirconia ceramics enveloped carbon nanometer tube shown in the embodiment of the present invention 1.
Wherein, 1 is synthetic furnace, and 2 is rewinding mouth.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the invention is described.
Embodiment 1
Under hydrogen, nitrogen mixed gas protection; stove is warming up to 800～1500 DEG C; the methanol solution (0.10mol/L ferrum) of ferrocene is sprayed into synthetic furnace from synthetic furnace top; by the ethanol solution (1.0mol/L zirconium) of zirconium nitrate, bottom synthetic furnace, spout sprays into synthetic furnace simultaneously; the charging rate of the ethanol solution of the charging rate/zirconium nitrate of the methanol solution of ferrocene is 1/7, i.e. can get the ceramic coatings CNT that zirconium oxide/carbon weight ratio is 2.
Fig. 2 is the XRD testing result of the said goods, it was demonstrated that containing zirconium oxide about 68% in product, carbon nanotubes about 32%, zirconic particle size 20～50nm.
Fig. 3 is product scanning electron microscope testing result, the CNT that zirconium oxide is uniformly coated with, and forms the ceramic coatings CNT of diameter 50～150nm, without substantially reuniting between CNT.
Embodiment 2
Under hydrogen, nitrogen mixed gas protection; stove is warming up to 800～1500 DEG C; the methanol solution (0.10mol/L ferrum) of ferrous sulfate is sprayed into synthetic furnace from synthetic furnace top; methyl-silicone oil spout bottom synthetic furnace is sprayed into synthetic furnace simultaneously; the charging rate of the charging rate/methyl-silicone oil of the methanol solution of ferrous sulfate is 1/14, i.e. can get the ceramic coatings CNT that zirconium oxide/carbon weight ratio is 2.
Embodiment 3
Under hydrogen, nitrogen mixed gas protection; stove is warming up to 800～1500 DEG C; the methanol solution (0.10mol/L tungsten) of tungsten chloride is sprayed into synthetic furnace from synthetic furnace top; by the aqueous solution (1.0mol/L aluminum) of aluminum nitrate, bottom synthetic furnace, spout sprays into synthetic furnace simultaneously; the charging rate of the aqueous solution of the charging rate/aluminum nitrate of the methanol solution of tungsten chloride is 2/17, i.e. can get the ceramic coatings CNT that zirconium oxide/carbon weight ratio is 2.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.Skilled person will appreciate that of the industry; the present invention is not limited by examples detailed above; the principle that the present invention is simply described described in examples detailed above and description; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements both fall within scope of the claimed invention.Claimed scope is defined by appending claims and equivalent thereof.
Claims (9)
1. the preparation method of a ceramic coatings CNT, it is characterised in that it comprises the steps:
(1) carbon source material and catalyst source by CNT synthetic furnace top, from up to down spray into full reducing atmosphere high-temperature reactor intracavity 800～1500 DEG C, carbon source material is pyrolyzed into high-activity carbon atom, forms CNT under the catalysis of the metallic atom Ma of catalyst source pyrolysis formation；
(2) while above-mentioned course of reaction is carried out, by ceramics source solution bottom synthetic furnace, bottom-up spray in above-mentioned reactor cavity, ceramic source forms Nano Ceramic Particles, is deposited on the carbon nano tube surface of new life, in-situ preparation ceramic coatings CNT.
Preparation method the most according to claim 1, it is characterised in that the described carbon source material one or more mixing in methanol, ethanol, benzene or toluene；One or more in hydrogen, carbon monoxide or ammonia of described reducing atmosphere.
3. according to the preparation method of claim 1 or 2, it is characterised in that described reducing atmosphere is the mixed gas of reducibility gas and noble gas.
Preparation method the most according to claim 1, it is characterised in that described catalyst source is selected from metal inorganic salt or metallo-organic compound.
Preparation method the most according to claim 4, it is characterised in that the described metal inorganic salt one or more mixing in ferrous sulfate, nitric acid molybdenum or tungsten chloride；One or more the mixing in cobalt oxalate, nickel acetylacetonate or ferrocene of the described metallo-organic compound.
Preparation method the most according to claim 1, it is characterised in that described ceramic source is selected from metal inorganic salt or organic compound.
Preparation method the most according to claim 6, it is characterised in that the described metal inorganic salt one or more mixing in aluminum nitrate, magnesium nitrate or zirconium nitrate；One or more the mixing in methyl-silicone oil, ethyl silicon oil or phenyl silicone oil of the described organic compound.
8. a ceramic coatings CNT, it is prepared by method described in any one of claim 1-7.
Ceramic coatings CNT the most according to claim 8, it is characterised in that the carbon pipe a diameter of 5～100nm of ceramic coatings CNT, the ceramic thickness in carbon nano tube surface cladding is 1～100nm, and carbon/pottery weight ratio is 0.1～1.0.
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| CN201610146235.0A CN105819421A (en) | 2016-03-15 | 2016-03-15 | Preparation method of ceramic coated carbon nanotube |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106145089A (en) * | 2016-08-31 | 2016-11-23 | 无锡东恒新能源科技有限公司 | The synthesizer of batch production CNT |
| CN112846212A (en) * | 2021-01-04 | 2021-05-28 | 宇辰新能源材料科技无锡有限公司 | High-thermal-conductivity cobalt powder and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215431A (en) * | 2008-01-18 | 2008-07-09 | 天津大学 | Silicon oxide coating nano carbon composite material and preparation method thereof |
| CN104941645A (en) * | 2015-06-27 | 2015-09-30 | 江苏兰谷环保科技股份有限公司 | Preparation method of high-performance composite photocatalyst dispersed solution |
| CN105198447A (en) * | 2015-10-23 | 2015-12-30 | 河海大学 | Preparation method of aluminum oxide-carbon nano tube composite powder material |
-
2016
- 2016-03-15 CN CN201610146235.0A patent/CN105819421A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215431A (en) * | 2008-01-18 | 2008-07-09 | 天津大学 | Silicon oxide coating nano carbon composite material and preparation method thereof |
| CN104941645A (en) * | 2015-06-27 | 2015-09-30 | 江苏兰谷环保科技股份有限公司 | Preparation method of high-performance composite photocatalyst dispersed solution |
| CN105198447A (en) * | 2015-10-23 | 2015-12-30 | 河海大学 | Preparation method of aluminum oxide-carbon nano tube composite powder material |
Non-Patent Citations (1)
| Title |
|---|
| SANGRAM MAZUMDER ET AL.;: "Carbon nanotubes - porous ceramic composite by in situ CCVD growth of CNTs", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106145089A (en) * | 2016-08-31 | 2016-11-23 | 无锡东恒新能源科技有限公司 | The synthesizer of batch production CNT |
| CN112846212A (en) * | 2021-01-04 | 2021-05-28 | 宇辰新能源材料科技无锡有限公司 | High-thermal-conductivity cobalt powder and preparation method thereof |
| CN112846212B (en) * | 2021-01-04 | 2023-02-21 | 宇辰新能源材料科技无锡有限公司 | High-thermal-conductivity cobalt powder and preparation method thereof |
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Application publication date: 20160803 |