CN105819897B - The preparation method of carbon nanotubes coating ceramic - Google Patents
The preparation method of carbon nanotubes coating ceramic Download PDFInfo
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- CN105819897B CN105819897B CN201610146902.5A CN201610146902A CN105819897B CN 105819897 B CN105819897 B CN 105819897B CN 201610146902 A CN201610146902 A CN 201610146902A CN 105819897 B CN105819897 B CN 105819897B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5001—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with carbon or carbonisable materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
Abstract
The invention discloses a kind of carbon nanotubes coating ceramic and preparation method thereof, this method comprises the following steps：(1) ceramic source sprays into the reactor cavity full of reducing atmosphere from up to down with catalyst source from high―temperature nuclei furnace roof portion, 800~1500 DEG C of cavity temperature, and ceramic source is pyrolyzed with catalyst source, forms the equally distributed nano-ceramic particle of metallic catalyst；(2) while the above process carries out, carbon source material sprays into above-mentioned reactor cavity from up to down from high―temperature nuclei furnace roof portion, carbon source material high temperature pyrolysis under the catalytic action of metallic catalyst, generates the ceramic particle of carbon nanotubes cladding into high-activity carbon atom.Above-mentioned ceramic particle is compressing, and using inert gas as transmission medium, HIP sintering, that is, obtain carbon nanotubes coating ceramic product, its relative density is more than 99%, and hardness is higher than 20GPa, and fracture toughness is higher than 6.5MPam1/2。
Description
Technical field
The present invention relates to field of material technology, and in particular to a kind of original position (in-situ) synthesizing carbon nanotubes coating ceramic
The preparation method of powder.
Background technology
Carbon nanotubes is seamless, the hollow tube body that the graphene sheet layer formed by carbon atom is rolled into, it has high
Axial strength and very high elasticity modulus, draw ratio is big, high-temperature stable bigger than surface, anti-friction wear-resistant is good, thermal conductivity is good,
It can be used for manufacturing carbon nano-tube reinforced ceramic composite material.
In order in ceramic composite, give full play to the excellent properties of carbon nanotubes, it is necessary to have to carbon nanotubes
Effect is scattered, and improves the sympathy of carbon nanotubes and ceramic matrix material and combine power.
The content of the invention
The object of the present invention is to provide a kind of carbon nanotubes coating ceramic and preparation method thereof, in same reactor, leads to
Carbon is realized while crossing CVD method generation ceramics based metal catalysts, in ceramic surface formation carbon nanotubes, original position (in-situ)
Uniform cladding of the nanotube to ceramics.
To reach above-mentioned purpose, the first aspect of the present invention provides a kind of preparation method of carbon nanotubes coating ceramic, its
Include the following steps：
(1) ceramic source is sprayed into full of high-temperature reductibility atmosphere with catalyst source from high―temperature nuclei furnace roof portion, from up to down
In reactor cavity, reactor cavity temperature is 800~1500 DEG C, and ceramic source is pyrolyzed with catalyst source, and it is equal to form metallic catalyst
The nano-ceramic particle of even distribution；
(2) while the above process carries out, carbon source material from high―temperature nuclei furnace roof portion, spray into above-mentioned reaction from up to down
Device intracavitary, carbon source material high temperature pyrolysis is into high-activity carbon atom, under the catalytic action of metallic catalyst, in ceramic grain surface
In-situ growing carbon nano tube, up to the ceramic particle of carbon nanotubes cladding；
(3) ceramic particle that the carbon nanotubes obtained with (2) step coats is compressing, is situated between by pressure transmission of inert gas
Matter, HIP sintering, that is, obtain carbon nanotubes coating ceramic product.
Preferably, the carbon source material is selected from mixing more than one or both of methanol, ethanol, benzene or toluene.
Preferably, one or more of the reducing atmosphere in hydrogen, carbon monoxide or ammonia.
Preferably, the reducing atmosphere is the mixed gas of reducibility gas and inert gas.
Preferably, the catalyst source is selected from ferrocene, ferrous sulfate, nitric acid molybdenum, tungsten chloride, cobalt oxalate, acetylacetone,2,4-pentanedione
One or two or more kinds of mixing in nickel.
Preferably, one or two or more kinds of mixing of the ceramic source in aluminum nitrate, magnesium nitrate, zirconium nitrate.
Preferably, the metallic catalyst is selected from iron, molybdenum, tungsten, cobalt, nickel.
Preferably, the HIP sintering temperature of the step (3) is 1000~2000 DEG C, 50~200MPa of pressure.
Preferably, ceramic source sprays into instead from up to down with catalyst source from one pipeline of high―temperature nuclei furnace roof portion in step (1)
Answer device intracavitary；Another pipeline in carbon source material from high―temperature nuclei furnace roof portion in step (2) is sprayed into reactor cavity from up to down.
The second aspect of the present invention provides a kind of carbon nanotubes coating ceramic, it is prepared by the following method：
(1) ceramic source is sprayed into full of high-temperature reductibility atmosphere with catalyst source from high―temperature nuclei furnace roof portion, from up to down
In reactor cavity, reactor cavity temperature is 800~1500 DEG C, and ceramic source is pyrolyzed with catalyst source, and it is equal to form metallic catalyst
The nano-ceramic particle of even distribution；
(2) while the above process carries out, carbon source material from high―temperature nuclei furnace roof portion, spray into above-mentioned reaction from up to down
Device intracavitary, carbon source material high temperature pyrolysis is into high-activity carbon atom, under the catalytic action of metallic catalyst, in ceramic grain surface
In-situ growing carbon nano tube, up to the ceramic particle of carbon nanotubes cladding；
(3) ceramic particle that the carbon nanotubes obtained with (2) step coats is compressing, is situated between by pressure transmission of inert gas
Matter, HIP sintering, that is, obtain carbon nanotubes coating ceramic product.
Preferably, grain size is that the metal of 5~10nm is dispersed in the ceramic matrix of 10~100nm of particle diameter, is made pottery
Porcelain surface is uniformly distributed the carbon nanotubes of a diameter of 5~20nm.
Preferably, in ceramic matrix metal catalyst content 0.05~0.5wt.%, content of carbon nanotubes 1.0~
5.0wt.%.
Preferably, the metallic catalyst is selected from iron, molybdenum, tungsten, cobalt, nickel.
The preparation method of carbon nanotubes coating ceramic powder provided by the invention, had both avoided the group of nano-ceramic powder itself
It is poly-, the reunion of carbon nano tube itself is it also avoid, also achieves ceramics with carbon nanotubes in the dispersed of nanoscale.
Original position (in-situ) synthetic method production efficiency higher that the present invention uses, newborn Nano Ceramic Particles and newborn carbon nanometer
Pipe combination is more firm, and building-up process does not introduce other impurity, and the more readily dispersible use of ceramic powder of carbon nanotubes cladding.Profit
The ceramic component of the carbon nanotubes coating ceramic powder sintering generated with the present invention, its hardness are higher than 20GPa, and fracture toughness is higher than
6.5MPa·m1/2, far above the ceramic member fired after carbon nanotubes is mixed with ceramic powder.
Brief description of the drawings
Fig. 1 is the synthetic method schematic diagram for the ceramic powder that the present invention prepares carbon nanotubes cladding,
Fig. 2 coats zirconium oxide (content of carbon nanotubes 1.5%) XRD curves for carbon nanotubes shown in the embodiment of the present invention 1,
Fig. 3 is the microscopic appearance that carbon nanotubes shown in the embodiment of the present invention 1 coats zirconium oxide,
Fig. 4 is the hardness and fracture toughness that carbon nanotubes shown in the embodiment of the present invention 1 coats zirconia ceramics.
Wherein, 1 is synthetic furnace, and 2 be rewinding mouth.
Embodiment
The specific embodiment of the invention is described below in conjunction with attached drawing.
Embodiment 1
Under hydrogen, nitrogen mixture protection, stove is warming up to 800~1500 DEG C, by the ethanol solution of aluminum nitrate+nickel nitrate
(1mol/L aluminium, 0.003mol/L nickel), by high―temperature nuclei furnace roof portion, sprays into the reaction full of high-temperature reductibility atmosphere from up to down
Device intracavitary, aluminum nitrate are uniformly distributed nano alumina particles therein with nickel nitrate pyrolysis, formation nickel；Carried out in the above process
Meanwhile ethanol high temperature pyrolysis be split into high-activity carbon atom, under the catalytic action of nickel, in Membranes On Alumina Particles Surface, original position (in-
Situ carbon nanotubes coated aluminum oxide ceramic particle) is generated.
Fig. 1 is the XRD spectrum of the said goods.As a result carbon nanotubes about 1.5% in product is proved, the particle of aluminium oxide is big
Small 50~200nm.
Fig. 2 is product electron scanning micrograph.Photo shows aluminium oxide ceramics powder surface homoepitaxial a diameter of 5
The carbon nanotubes of~20nm.
The ceramic component of the carbon nanotubes coating ceramic powder sintering generated using the present invention, its hardness are higher than 20GPa, are broken
Toughness is higher than 6.5MPam1/2, far above the ceramic member fired after carbon nanotubes is mixed with ceramic powder, as shown in Figure 4.
Embodiment 2
Under hydrogen, nitrogen mixture protection, stove is warming up to 800~1500 DEG C, by the benzole soln of zirconium nitrate+cobalt oxalate
(1mol/L zirconiums, 0.003mol/L cobalts), by high―temperature nuclei furnace roof portion, sprays into the reaction full of high-temperature reductibility atmosphere from up to down
Device intracavitary, zirconium nitrate and cobalt oxalate pyrolysis, formation cobalt are uniformly distributed nano zircite particle therein；Carried out in the above process
Meanwhile benzene high temperature pyrolysis be split into high-activity carbon atom, under the catalytic action of cobalt, in zirconia particles surface, original position (in-
Situ carbon nanotubes cladding zirconia ceramics particle) is generated.
Embodiment 3
Under hydrogen, nitrogen mixture protection, stove is warming up to 800~1500 DEG C, by the methanol solution of magnesium nitrate+ferrocene
(1mol/L magnesium, 0.003mol/L iron), by high―temperature nuclei furnace roof portion, sprays into the reaction full of high-temperature reductibility atmosphere from up to down
Device intracavitary, magnesium nitrate and ferrocene pyrolysis, formation nickel are uniformly distributed nano oxidized magnesium granules therein；Carried out in the above process
Meanwhile methanol high temperature pyrolysis be split into high-activity carbon atom, under the catalytic action of nickel, in magnesium oxide particle surface, original position (in-
Situ carbon nanotubes coated magnesium oxide ceramic particle) is generated.
Basic principle, main feature and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention simply illustrates the present invention described in examples detailed above and specification from the limitation of examples detailed above
Principle, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these change and
Improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its is equal
Thing defines.
Claims (10)
1. a kind of preparation method of carbon nanotubes coating ceramic, it is characterised in that it includes the following steps：
（1）Ceramic source and catalyst source from high―temperature nuclei furnace roof portion, spray into the reaction full of high-temperature reductibility atmosphere from up to down
Device intracavitary, reactor cavity temperature are 800 ~ 1500 DEG C, and ceramic source is pyrolyzed with catalyst source, form metallic catalyst and are uniformly distributed
Nano-ceramic particle；
（2）While the above process carries out, carbon source material from high―temperature nuclei furnace roof portion, spray into above-mentioned reactor cavity from up to down
Interior, carbon source material high temperature pyrolysis is into high-activity carbon atom, under the catalytic action of metallic catalyst, on nano-ceramic particle surface
In-situ growing carbon nano tube, up to the ceramic particle of carbon nanotubes cladding；
（3）With（2）It is compressing to walk the ceramic particle of obtained carbon nanotubes cladding, using inert gas as transmission medium, heat
Isostatic sintering, that is, obtain carbon nanotubes coating ceramic product.
2. preparation method according to claim 1, it is characterised in that the carbon source material is selected from methanol, ethanol, benzene or first
Mixing more than one or both of benzene；The one kind or several of the reducing atmosphere in hydrogen, carbon monoxide or ammonia
Kind.
3. preparation method according to claim 1, it is characterised in that the reducing atmosphere is reducibility gas and inertia
The mixed gas of gas.
4. preparation method according to claim 1, it is characterised in that the catalyst source be selected from ferrocene, ferrous sulfate,
One or two or more kinds of mixing in nitric acid molybdenum, tungsten chloride, cobalt oxalate, nickel acetylacetonate.
5. preparation method according to claim 1, it is characterised in that the ceramic source is selected from aluminum nitrate, magnesium nitrate, nitric acid
One or two or more kinds of mixing in zirconium.
6. preparation method according to claim 1, it is characterised in that the metallic catalyst be selected from iron, molybdenum, tungsten, cobalt,
Nickel.
7. preparation method according to claim 1, it is characterised in that the step（3）HIP sintering temperature for 1000 ~
2000 DEG C, 50 ~ 200MPa of pressure.
8. a kind of carbon nanotubes coating ceramic, it is prepared by claim 1-7 any one of them methods.
9. carbon nanotubes coating ceramic according to claim 8, it is characterised in that grain size is that the metal of 5 ~ 10nm is equal
Even to be dispersed in the ceramic matrix of 10 ~ 100nm of particle diameter, ceramic matrix surface is uniformly distributed the carbon nanotubes of a diameter of 5 ~ 20nm.
10. carbon nanotubes coating ceramic according to claim 8, it is characterised in that metal catalyst content for 0.05 ~
0.5 wt.%, content of carbon nanotubes are 1.0 ~ 5.0 wt.%.
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| CN110292927A (en) * | 2019-04-30 | 2019-10-01 | 北京氦舶科技有限责任公司 | Monoatomic metal catalyst and its preparation and the application in degradation air pollutants |
| CN113929493A (en) * | 2021-11-02 | 2022-01-14 | 湖南湘瓷科艺有限公司 | Ceramic surface toughening process based on carbon nano powder heat sink procedure |
| CN116462185A (en) * | 2023-04-27 | 2023-07-21 | 深圳材启新材料有限公司 | Preparation method of carbon nano tube |
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|---|---|---|---|---|
| CN101054297A (en) * | 2007-04-11 | 2007-10-17 | 宁波工程学院 | Method for preparing nano polyphase ceramic powder |
| CN101215431A (en) * | 2008-01-18 | 2008-07-09 | 天津大学 | Silicon oxide coating nano carbon composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ES2427715B1 (en) * | 2012-03-30 | 2014-05-09 | Asociación De Investigación De La Industria Del Juguete, Conexas Y Afines | Procedure for the manufacture of monolithic systems of a ceramic or carbonaceous nature |
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Patent Citations (4)
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|---|---|---|---|---|
| CN101054297A (en) * | 2007-04-11 | 2007-10-17 | 宁波工程学院 | Method for preparing nano polyphase ceramic powder |
| CN101215431A (en) * | 2008-01-18 | 2008-07-09 | 天津大学 | Silicon oxide coating nano carbon composite material and preparation method thereof |
| CN103022434A (en) * | 2012-11-23 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Precursor ceramic-carbon nano tube composite material and preparation method thereof |
| CN104725031A (en) * | 2015-03-16 | 2015-06-24 | 上海交通大学 | Method for growing carbon nano fibers on ceramic hollow microsphere surface in situ |
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