CN105819897A - Preparation method of carbon nanotube coated ceramic - Google Patents
Preparation method of carbon nanotube coated ceramic Download PDFInfo
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- CN105819897A CN105819897A CN201610146902.5A CN201610146902A CN105819897A CN 105819897 A CN105819897 A CN 105819897A CN 201610146902 A CN201610146902 A CN 201610146902A CN 105819897 A CN105819897 A CN 105819897A
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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 preparation method of carbon nanotube coated ceramic. The preparation method comprises the following steps: (1) spraying a ceramic source and a catalyst source from the top of top part of a high temperature synthesis furnace from top to bottom into a reactor cavity full of reducing atmosphere, wherein the temperature of the reactor cavity is 800 to 1500 DEG C, and the ceramic source and catalyst source are thermally decomposed in the reactor cavity to form nano ceramic particles with evenly distributed metal catalyst; (2) at the same time, spraying a carbon source material into the reactor cavity from the top part of the high temperature synthesis furnace from top to bottom, wherein the carbon source material is thermally decomposed at a high temperature to form high activity carbon atoms, and in the presence of metal catalyst, ceramic particles coated by carbon nanotubes are formed. The ceramic particles are pressed and moulded, inert gas is taken as the pressure transmission medium, and then a hot isostatic pressure sintering technology is adopted to prepare a carbon nanotube coated ceramic product, which has the following parameters: relative density>99%, hardness>20GPa, and fracture toughness>6.5 MPa.m<1/2>.
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) synthesizing carbon nanotubes coating ceramic powder in situ.
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, may be used for manufacturing carbon nano-tube reinforced ceramic composite.
In order to, in ceramic composite, give full play to the excellent properties of CNT, need CNT is effectively disperseed, and improve CNT and the sympathy of ceramic matrix material and adhesion.
Summary of the invention
It is an object of the invention to provide a kind of CNT coating ceramic and preparation method thereof, in same reactor, generate ceramic base metallic catalyst by CVD while, form CNT, in situ (in-situ) at ceramic surface and realize the CNT uniform cladding to pottery.
For reaching above-mentioned purpose, a first aspect of the present invention provides the preparation method of a kind of CNT coating ceramic, and it comprises the steps:
(1) ceramic source and catalyst source from high-temperature nuclei furnace roof portion, from up to down spray into full high-temperature reductibility atmosphere reactor cavity in, reactor cavity temperature is 800～1500 DEG C, ceramic source is pyrolyzed with catalyst source, forms the equally distributed nano-ceramic particle of metallic catalyst；
(2) while said process is carried out, carbon source material is from high-temperature nuclei furnace roof portion, from up to down spray in above-mentioned reactor cavity, carbon source material high temperature pyrolysis becomes high-activity carbon atom, under the catalytic action of metallic catalyst, at ceramic grain surface in-situ growing carbon nano tube, obtain the ceramic particle of CNT cladding；
(3) ceramic particle of the CNT cladding obtained by (2nd) step is compressing, with noble gas as transmission medium, and HIP sintering, i.e. obtain CNT coating ceramic goods.
Preferably, the described carbon source material one or more mixing in methanol, ethanol, benzene or toluene.
Preferably, one or more in hydrogen, carbon monoxide or ammonia of described reducing atmosphere.
Preferably, described reducing atmosphere is the mixed gas of reducibility gas and noble gas.
Preferably, the described catalyst source mixing of one or two or more kinds in ferrocene, ferrous sulfate, nitric acid molybdenum, tungsten chloride, cobalt oxalate, nickel acetylacetonate.
Preferably, the described ceramic source mixing of one or two or more kinds in aluminum nitrate, magnesium nitrate, zirconium nitrate.
Preferably, described metallic catalyst chosen from Fe, molybdenum, tungsten, cobalt, nickel.
Preferably, the HIP sintering temperature of described step (3) is 1000～2000 DEG C, pressure 50～200MPa.
Preferably, in step (1), ceramic source and catalyst source from up to down spray in reactor cavity from high-temperature nuclei furnace roof portion one pipeline；Carbon source material in step (2) another pipeline from high-temperature nuclei furnace roof portion from up to down sprays in reactor cavity.
A second aspect of the present invention provides a kind of CNT coating ceramic, and it prepares by the following method:
(1) ceramic source and catalyst source from high-temperature nuclei furnace roof portion, from up to down spray into full high-temperature reductibility atmosphere reactor cavity in, reactor cavity temperature is 800～1500 DEG C, ceramic source is pyrolyzed with catalyst source, forms the equally distributed nano-ceramic particle of metallic catalyst；
(2) while said process is carried out, carbon source material is from high-temperature nuclei furnace roof portion, from up to down spray in above-mentioned reactor cavity, carbon source material high temperature pyrolysis becomes high-activity carbon atom, under the catalytic action of metallic catalyst, at ceramic grain surface in-situ growing carbon nano tube, obtain the ceramic particle of CNT cladding；
(3) ceramic particle of the CNT cladding obtained by (2nd) step is compressing, with noble gas as transmission medium, and HIP sintering, i.e. obtain CNT coating ceramic goods.
Preferably, grain size be 5～10nm metal be dispersed in the ceramic matrix of particle diameter 10～100nm, ceramic surface is uniformly distributed the CNT of a diameter of 5～20nm.
Preferably, in ceramic matrix metal catalyst content 0.05～0.5wt.%, content of carbon nanotubes is 1.0～5.0wt.%.
Preferably, described metallic catalyst chosen from Fe, molybdenum, tungsten, cobalt, nickel.
The preparation method of CNT coating ceramic powder that the present invention provides, had both avoided the reunion of nano-ceramic powder self, it also avoid the reunion of carbon nano tube self, also achieved dispersed at nanoscale of pottery and CNT.Original position (in-situ) the synthetic method production efficiency that the present invention uses is higher, and newborn Nano Ceramic Particles is combined more firmly with newborn CNT, and building-up process does not introduce other impurity, and the more readily dispersible use of ceramics that CNT is coated with.Utilizing the ceramic component of the CNT coating ceramic powder sintering that the present invention generates, its hardness is higher than 20GPa, and fracture toughness is higher than 6.5MPa m1/2, far above the ceramic member fired after CNT is mixed with ceramics.
Accompanying drawing explanation
Fig. 1 is the synthetic method schematic diagram that the present invention prepares the ceramics of CNT cladding,
Fig. 2 is that CNT shown in the embodiment of the present invention 1 is coated with zirconium oxide (content of carbon nanotubes 1.5%) XRD curve,
Fig. 3 is that CNT shown in the embodiment of the present invention 1 is coated with zirconic microscopic appearance,
Fig. 4 is hardness and the fracture toughness of the cladding zirconia ceramics of CNT 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 mixture protection; stove is warming up to 800～1500 DEG C; by ethanol solution (the 1mol/L aluminum of aluminum nitrate+nickel nitrate; 0.003mol/L nickel); by high-temperature nuclei furnace roof portion, from up to down spray into full high-temperature reductibility atmosphere reactor cavity in, the pyrolysis of aluminum nitrate and nickel nitrate, form nickel and be uniformly distributed nano alumina particles therein；While said process is carried out, ethanol high temperature pyrolysis is split into high-activity carbon atom, under the catalytic action of nickel, at Membranes On Alumina Particles Surface, in situ (in-situ) generation CNT coated aluminum oxide ceramic particle.
Fig. 1 is the XRD figure spectrum of the said goods.Result proves carbon nanotubes about 1.5% in product, the granular size 50～200nm of aluminium oxide.
Fig. 2 is product electron scanning micrograph.Photo shows aluminium oxide ceramics powder surface homoepitaxial a diameter of 5～the CNT of 20nm.
Utilizing the ceramic component of the CNT coating ceramic powder sintering that the present invention generates, its hardness is higher than 20GPa, and fracture toughness is higher than 6.5MPa m1/2, far above the ceramic member fired after CNT is mixed with ceramics, as shown in Figure 4.
Embodiment 2
Under hydrogen, nitrogen mixture protection; stove is warming up to 800～1500 DEG C; by benzole soln (the 1mol/L zirconium of zirconium nitrate+cobalt oxalate; 0.003mol/L cobalt); by high-temperature nuclei furnace roof portion, from up to down spray into full high-temperature reductibility atmosphere reactor cavity in, zirconium nitrate and cobalt oxalate pyrolysis, formed cobalt be uniformly distributed nano zircite granule therein；While said process is carried out, benzene high temperature pyrolysis be split into high-activity carbon atom, under the catalytic action of cobalt, on zirconia particles surface, in situ (in-situ) generate CNT cladding zirconia ceramics granule.
Embodiment 3
Under hydrogen, nitrogen mixture protection; stove is warming up to 800～1500 DEG C; by methanol solution (the 1mol/L magnesium of magnesium nitrate+ferrocene; 0.003mol/L ferrum); by high-temperature nuclei furnace roof portion, from up to down spray into full high-temperature reductibility atmosphere reactor cavity in, magnesium nitrate and ferrocene pyrolysis, formed nickel be uniformly distributed nano oxidized magnesium granules therein；While said process is carried out, methanol high temperature pyrolysis be split into high-activity carbon atom, under the catalytic action of nickel, on magnesium oxide particle surface, in situ (in-situ) generate CNT coated magnesium oxide ceramic particle.
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 (10)
1. the preparation method of a CNT coating ceramic, it is characterised in that it comprises the steps:
(1) ceramic source and catalyst source from high-temperature nuclei furnace roof portion, from up to down spray into full high-temperature reductibility atmosphere reactor cavity in, reactor cavity temperature is 800～1500 DEG C, ceramic source is pyrolyzed with catalyst source, forms the equally distributed nano-ceramic particle of metallic catalyst；
(2) while said process is carried out, carbon source material is from high-temperature nuclei furnace roof portion, from up to down spray in above-mentioned reactor cavity, carbon source material high temperature pyrolysis becomes high-activity carbon atom, under the catalytic action of metallic catalyst, at ceramic grain surface in-situ growing carbon nano tube, obtain the ceramic particle of CNT cladding；
(3) ceramic particle of the CNT cladding obtained by (2nd) step is compressing, with noble gas as transmission medium, and HIP sintering, i.e. obtain CNT coating ceramic goods.
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.
Preparation method the most according to claim 1 and 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 the described catalyst source mixing of one or two or more kinds in ferrocene, ferrous sulfate, nitric acid molybdenum, tungsten chloride, cobalt oxalate, nickel acetylacetonate.
Preparation method the most according to claim 1, it is characterised in that the described ceramic source mixing of one or two or more kinds in aluminum nitrate, magnesium nitrate, zirconium nitrate.
Preparation method the most according to claim 1, it is characterised in that described metallic catalyst chosen from Fe, molybdenum, tungsten, cobalt, nickel.
Preparation method the most according to claim 1, it is characterised in that the HIP sintering temperature of described step (3) is 1000～2000 DEG C, pressure 50～200MPa.
8. a CNT coating ceramic, it is prepared by the method described in any one of claim 1-7.
CNT coating ceramic the most according to claim 8, it is characterised in that grain size be 5～10nm metal be dispersed in the ceramic matrix of particle diameter 10～100nm, ceramic surface is uniformly distributed the CNT of a diameter of 5～20nm.
CNT coating ceramic the most according to claim 8, it is characterised in that in ceramic matrix metal catalyst content 0.05～0.5wt.%, content of carbon nanotubes is 1.0～5.0wt.%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| WO2013144399A1 (en) * | 2012-03-30 | 2013-10-03 | Asociación De Investigación De La Industria Del Juguete, Conexas Y Afines | Method for the production of monolithic carbonaceous or ceramic systems |
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- 2016-03-15 CN CN201610146902.5A patent/CN105819897B/en active Active
Patent Citations (5)
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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 |
| WO2013144399A1 (en) * | 2012-03-30 | 2013-10-03 | Asociación De Investigación De La Industria Del Juguete, Conexas Y Afines | Method for the production of monolithic carbonaceous or ceramic systems |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| CN105819897B (en) | 2018-04-24 |
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Effective date of registration: 20190327 Address after: 221000 South Side of No.4 Road, Yangtun Town Industrial Park, Peixian County, Xuzhou City, Jiangsu Province Patentee after: Sayfo (Xuzhou) Co., nano science and technology Address before: 215123 Room 207, Building 99 Jinjihu Avenue, Suzhou Industrial Park, Jiangsu Province Patentee before: SUZHOU SAIFU DEBEI TRADE CO., LTD. |
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