CN102838104A - Carbon nanotube macro body with composite structure and preparation method thereof - Google Patents
Carbon nanotube macro body with composite structure and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 241
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 164
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 164
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000012010 growth Effects 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 89
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 84
- 239000000243 solution Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 62
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 229910052786 argon Inorganic materials 0.000 claims description 42
- 239000010453 quartz Substances 0.000 claims description 40
- 238000002347 injection Methods 0.000 claims description 37
- 239000007924 injection Substances 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 29
- 229940117389 dichlorobenzene Drugs 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 230000035484 reaction time Effects 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000003491 array Methods 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract 3
- 238000010952 in-situ formation Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 230000003321 amplification Effects 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
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- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002238 carbon nanotube film Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a carbon nanotube macro body with a continuous composite structure which is formed by in-situ assembly of spongy carbon nanotube and directional carbon nanotube, the carbon nanotube macro body is composed of carbon nanotube cavernosum and a carbon nanotube array, the composite structure is formed by the carbon nanotube cavernosum and the carbon nanotube array in in-situ mode, the carbon nanotube cavernosum is isotropic, and the carbon nanotube array is anisotropic. The composite structure comprises a multilayer series structure, a multiple parallel structure, a mutual cladding structure and combination of the multilayer series structure, the multiple parallel structure and the mutual cladding structure, wherein the multilayer series structure is formed by the carbon nanotube cavernosum and the carbon nanotube array, and the mutual cladding structure is positioned between the multilayer series structure and the multiple parallel structure. The in-situ formation refers to that the composite structure formed by the carbon nanotube cavernosum and the carbon nanotube array is formed directly during a growth process. The carbon nanotube macro body is convenient to directly apply and achieves mass preparation, a preparation method of the carbon nanotube macro body achieves rapid, efficient and large-scale preparation of the carbon nanotube macro body, and the carbon nanotube macro body can be used for vibration reduction of energy absorption, sound absorption of heat absorption, adsorption of toxic organic solution and the like.
Description
Technical field
The present invention relates to a kind of carbon nanomaterial, the synthetic and applied technical field of carbon nanomaterial particularly relates to a kind of carbon nano-tube macroscopic body with composite structure and preparation method thereof.
Background technology
Carbon nanotube is the tubular structure that is curled and formed by the graphite synusia; Its unique texture has determined it to have the performance of many excellences; Like low density, HS, high length-diameter ratio, adjustable electrology characteristic etc.; It reveals wide application prospect as structural reinforcement material and performance function bill of material, thereby enjoys academia and industrial community personage to pay close attention to.Carbon nanotube is self-assembled into the aggregate-carbon nano-tube macroscopic body with macro-size, has promoted the practical application of carbon nanotube to transform more.
Carbon nano-tube macroscopic body mainly contains unidimensional carbon nano-tube filament, rope; Carbon nano-tube film, the paper of two dimension; Structures such as three-dimensional carbon nano-array, spongy mass.The carbon nano-tube macroscopic body of different dimensions has shown advantage and application potential separately in different fields, especially the three dimensional carbon nanotubes macroscopic body receives much concern more.
Carbon nano pipe array in the three dimensional carbon nanotubes macroscopic body is anisotropy, and performances such as its mechanics, electricity, calorifics have good rigidity demonstrating greatest differences on the direction of growth with on the orthotropic direction macroscopic view on its vertical-growth direction.Open people (Rapid growth of well-aligned carbon nanotube arrays such as pioneer; Chemical Physics Letters; 2002; 362:285.) utilize chemical gas-phase method, directly synthesized overlength carbon nano pipe array fast, fields such as this array emission on the scene have application promise in clinical practice.In the three dimensional carbon nanotubes macroscopic body, except being anisotropic carbon nano pipe array, also have a kind of isotropic carbon nano-tube macroscopic body that is, such carbon nano-tube macroscopic body all directions on performance and structure keep homogeneity.People (Chinese invention patent, publication numbers: CN101607704A) utilize catalystic pyrolysis, directly synthesized and be isotropic three dimensional carbon nanotubes macroscopic body, and be referred to as the carbon nanotube spongy mass such as osmanthus Xu Chun.The carbon nanotube spongy mass has characteristics such as lightweight, porous, isotropy, high-flexibility, and it has good application prospects in fields such as adsorption filtrations.
Can directly synthesize the performance advantage separately with carbon nano pipe array and carbon nanotube spongy mass and the carbon nano-tube macroscopic body of characteristics, become one of difficult problem that field of carbon nanotubes need capture.Therefore develop the carbon nano-tube macroscopic body that forms by carbon nano pipe array and carbon nanotube spongy mass assemble in situ with composite structure, and develop technology simply, the method that can directly synthesize above-mentioned carbon nanometer macroscopic body has great importance.
Summary of the invention
The objective of the invention is to, a kind of three dimensional carbon nanotubes macroscopic body of the composite structure that is formed by isotropic spongy carbon nanotube block and anisotropic carbon nano pipe array growth in situ is provided; This carbon nano-tube macroscopic body has important application in the energy-obsorbing and damping field.
Another object of the present invention is to; A kind of catalystic pyrolysis that utilizes is provided; Low-cost, high-level efficiency, the method for the carbon nanotube of continuous controllable ground above-mentioned high quality isotropy of preparation and anisotropy composite structure is through regulating processing parameters such as catalyst concn, carbon source rate of feed; The performances such as density, mechanical strength of regulation and control composite structure of carbon nano tube are with the controlledly synthesis of the carbon nano-tube macroscopic body of realizing this composite structure.
The object of the invention and solve its technical problem and adopt following technical scheme to realize.A kind of carbon nano-tube macroscopic body with composite structure according to the present invention proposes is made up of carbon nanotube spongy mass and carbon nano pipe array, and original position forms composite structure between them, and the carbon nanotube spongy mass is isotropy, and carbon nano pipe array is anisotropy; This original position forms and be meant that the composite structure that carbon nanotube spongy mass and carbon nano pipe array form directly forms in process of growth; This composite structure comprises multilayer cascaded structure, Multi-layer Parallel structure, the mutual clad structure between them that is formed by carbon nanotube spongy mass and carbon nano pipe array, and the combination of above structure.
In addition, the invention allows for a kind of above-mentioned preparation method with carbon nano-tube macroscopic body of composite structure, it may further comprise the steps:
(1) take by weighing the ferrocene powder and be dissolved in the YLENE, being mixed with concentration is ferrocene/YLENE carbon source solution (first solution) of 20-100mg/mL; Take by weighing the ferrocene powder and be dissolved in the dichlorobenzene, be mixed with concentration and be ferrocene/dichlorobenzene carbon source solution (second solution) of 20-100mg/mL, subsequent use;
(2) quartz substrate is put into the quartz reaction chamber of Reaktionsofen, enclosed reaction chamber, to reaction chamber feed flow be the argon gas of 500-1000mL/min to drain the air in the reaction chamber, heating reaction furnace simultaneously;
(3) when reaction chamber temperature reaches 820-940 ℃, regulate argon flow amount to 500-2000mL/min, feed the hydrogen that flow is 100-500mL/min simultaneously;
(4) then above-mentioned ferrocene/YLENE carbon source solution is injected the reaction chamber reaction, grow the carbon nanotube orthogonal array;
(5) above-mentioned ferrocene/YLENE carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution, injects the reaction chamber reaction, list at carbon nano-pipe array and directly grow the carbon nanotube spongy mass;
(6) tube furnace stops heating, closes hydrogen, regulates argon flow amount to 50-500mL/min, makes product cool to room temperature with the furnace, can collect the connect carbon nano-tube macroscopic body of composite structure of the bilayer that is block in a large number in quartz substrate and quartz reaction chamber interior walls.
Preparing method of the present invention, in the step (1), the mol ratio of said ferrocene powder and YLENE is 1:15-1:77; The mol ratio of said ferrocene powder and dichlorobenzene is 1:16-1:83.
Preparing method of the present invention in the step (4), adopts the precise injection pump that first solution is injected reaction chamber with the rate of feed of 0.1-0.5mL/min, reacts 0.1-5h, can grow the carbon nanotube orthogonal array of thickness 0.05-5.0mm.
Preparing method of the present invention; In the step (5); Ferrocene/YLENE carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution; And injecting reaction chamber with the rate of feed of 0.1-0.4mL/min, reaction 0.1-5h lists at carbon nano-pipe array and directly to grow the carbon nanotube spongy mass that thickness is 0.1-10mm.
Preparing method of the present invention; It also further comprises step (7); After the carbon nano-tube macroscopic body sample taking-up with above-mentioned double-deck series connection composite structure; With blade with sample from the quartz plate substrate shape that cuts into large slices, the carbon nanotube of bulk two-layer composite be inverted be put on the quartz plate, make carbon nano pipe array up; The carbon nano-tube macroscopic body of carbon nanotube sponge-carbon nano pipe array-trilaminar series connection composite structure of carbon nanotube sponge is prepared in repeating step (2), (3), (5), (6).
Preparing method of the present invention, in the step (6), said tube furnace increases to 2000mL/min with argon flow amount, and feeds 300mL/min hydrogen after keeping 850 ℃ of constant temperature, forms argon gas hydrogen mixed carrier gas; Use precise injection pump injection concentration to be 20-100mg/mL ferrocene/dichlorobenzene carbon source solution, the flow of injection is 0.1-0.4mL/min; Behind the reaction times 0.1-5h, form the carbon nano-tube macroscopic body of carbon nanotube spongy mass-carbon nano pipe array-three layers of cascaded structure of carbon nanotube spongy mass.
Preparing method of the present invention; It also further comprises step (8), and behind said step (1), (2), (3), (4), tube furnace stops heating; Close hydrogen; Regulate argon flow amount to 50-500mL/min, make product cool to room temperature with the furnace, can collect a large amount of directional carbon nanotube arrays at quartz substrate; Carbon nano pipe array is cut into strips (sheet); Parallel range upon range of in the vertical-growth direction; The centre separates with littler array sheet; Perhaps sheet-like array being arranged in parallel places on the quartz plate at interval again, repeating step (2), (3), (5), (6), the carbon nano-tube macroscopic body of the composite structure that preparation carbon nanotube sponge is parallelly connected with carbon nano pipe array.
Preparing method of the present invention, the about 2mm of said directional carbon nanotube array thickness, array are cut into several pieces very thin sheets along the carbon nanotube differently-oriented directivity with blade, and width is about 0.2-0.5mm; Said multi-disc sheet-like array is in the parallel placement of vertical carbon nanotube orientation 90 degree directions.
Preparing method of the present invention, in the step (6), tube furnace increases to 2000mL/min with argon flow amount, and feeds 300mL/min hydrogen after keeping 850 ℃ of constant temperature, forms argon gas hydrogen mixed carrier gas; Use precise injection pump injection concentration to be 20-100mg/mL ferrocene/dichlorobenzene carbon source solution, the flow of injection is 0.1-0.4mL/min; Behind the reaction times 0.1-5h, form the carbon nano-tube macroscopic body of carbon nanotube spongy mass-carbon nano pipe array-carbon nanotube spongy mass Multi-layer Parallel structure.
By technique scheme, advantage and beneficial effect that the present invention has are following:
(1) isotropy carbon nanotube and anisotropy carbon nanotube are in process of growth, and original position directly forms the carbon nanotube block with composite structure;
(2) isotropy carbon nanotube and anisotropy carbon nanotube can form multiple structures such as multilayer series connection, Multi-layer Parallel, a kind of coating another kind; Make the structure of carbon nano-tube macroscopic body become abundanter, its macroscopic body over-all properties is more outstanding;
(3) through changing processing parameters such as catalyst concn, carbon source rate of feed, can regulate and control the density of the carbon nano-tube macroscopic body of composite structure on a large scale, thereby reach performances such as its mechanics of regulation and control, electricity, calorifics;
(4) equipment is simple, controllable operating property is strong, is suitable for amplifying producing.
The present invention has realized a kind of carbon nano-tube macroscopic body of novel texture, be convenient to directly use and batch preparations, and provide this carbon nano-tube macroscopic body fast, the method for efficient, mass preparation; This carbon nano-tube macroscopic body can be applicable to technical fields such as energy-obsorbing and damping, heat insulation and acoustic absorption, the poisonous organic solution of absorption.
Description of drawings
Shown in Figure 1 is the apparatus structure synoptic diagram of the carbon nano-tube macroscopic body growth of composite structure of the present invention;
Fig. 2 a is the photomacrograph of the carbon nanotube of double-deck series connection composite structure; Fig. 2 b and 2c are respectively the stereoscan photograph of different amplification of the carbon nanotube of double-deck series connection composite structure;
Fig. 3 is the photomacrograph of the carbon nanotube with composite structure of on quartz plate, growing;
Fig. 4 a and 4b are respectively the picture in kind and the stereoscan photograph of the carbon nano-tube macroscopic body of three-layer composite structure;
Fig. 5 a is the stereoscan photograph of the carbon nano-tube macroscopic body of Multi-layer Parallel composite structure; The high power of Fig. 5 b demonstration carbon nano pipe array and carbon nanotube spongy mass is swept according to electromicroscopic photograph.
Wherein: 1 is mass-flow gas meter, tests shared to two kinds of gases: argon gas (Ar) and hydrogen (H
2); 2 is silica tube; 3 is tubular react furnace; 4 quartz plate substrates for the product that is used to grow; 5 is the precise injection pump.
Embodiment
See also shown in Figure 1ly, core of the present invention is the various composite structures that the carbon nanotube spongy mass becomes with the carbon nano pipe array assemble in situ.The preparation method of the carbon nano-tube macroscopic body of this composite structure comprises the steps:
(1) takes by weighing ferrocene ((C
5H
5)
2Fe) powder is dissolved in YLENE (C
6H
4(CH
3)
2) in, being mixed with concentration is ferrocene/YLENE carbon source solution (first solution) of 20-100mg/mL; Take by weighing the ferrocene powder and be dissolved in dichlorobenzene (C
6H
4Cl
2) in, be mixed with concentration and be ferrocene/dichlorobenzene carbon source solution (second solution) of 20-100mg/mL, subsequent use;
(2) quartz substrate 4 is put into silica tube reaction chamber 2, enclosed reaction chamber, feeding flow through mass-flow gas meter 1 to silica tube reaction chamber 2 is the argon gas of 500-1000mL/min, to drain the air in the reaction chamber, heats tubular react furnace 3 simultaneously;
(3) when the temperature of tubular react furnace 3 reaches 820-940 ℃, regulate argon flow amount to 2000mL/min, feed the hydrogen that flow is 100-500mL/min simultaneously;
(4) with precise injection pump 5 first solution is injected reaction chamber with the rate of feed of 0.1-0.5mL/min then, reaction 0.1-5h;
(5) first solution is changed to second solution, second solution injects reaction chamber with the rate of feed of 0.1-0.4mL/min, reaction 0.1-5h;
(6) tube furnace stops heating, closes hydrogen, regulates argon flow amount to 50-500mL/min, makes product cool to room temperature with the furnace, can collect the carbon nano-tube macroscopic body of the bilayer series connection composite structure that is block in a large number at the inwall of quartz substrate 4 and quartz reaction chamber 2.
(7) the carbon nano-tube macroscopic body sample of above-mentioned double-deck series connection composite structure is taken out after, with blade with sample from quartz plate substrate 4 shape that cuts into large slices, the carbon nanotube of bulk two-layer composite be inverted be put on the quartz plate, make carbon nano pipe array up.Repeating step (2), (3), (5), (6) can prepare the carbon nano-tube macroscopic body of carbon nanotube sponge-carbon nano pipe array-trilaminar series connection composite structure of carbon nanotube sponge.
(8) behind above-mentioned steps (1), (2), (3), (4), tube furnace stops heating, closes hydrogen, regulates argon flow amount to 50-500mL/min, makes product cool to room temperature with the furnace, can collect a large amount of directional carbon nanotube arrays at quartz substrate.Carbon nano pipe array is cut into strips (sheet); At vertical-growth direction parallel range upon range of (carbon nanotube is vertical with its former growth orientation); The centre separates with littler array sheet; Perhaps sheet-like array being arranged in parallel is placing on the quartz plate at interval, and repeating step (2), (3), (5), (6) can prepare the carbon nano-tube macroscopic body of the carbon nanotube sponge composite structure parallelly connected with carbon nano pipe array.
The carbon nano-tube macroscopic body of the double-deck series connection of preparation high quality composite structure
Weighing ferrocene 2.0g is dissolved in the 100mL xylene solution, stirs, and forms brown yellow solution, obtains ferrocene/xylene solution that concentration is 0.02g/mL, and is subsequent use.Weighing ferrocene 6.0g is dissolved in the 100mL dichlorobenzene, stirs, and forms the darker brown yellow solution of color, obtains ferrocene/dichlorobenzene solution that concentration is 0.06g/mL, and is subsequent use.
The quartz plate that cleans up is placed tube furnace flat-temperature zone intermediary reaction chamber in the silica tube, enclosed reaction chamber.Feed the 500mL/min argon gas discharging the air in the reaction chamber to reaction chamber, heating tubular type stove to 850 ℃.Behind 850 ℃ of the tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and feed 400mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Use precise injection pump injection concentration to be 0.02g/mL ferrocene/YLENE carbon source solution, the flow of injection is 0.4mL/min; Reaction times 1.5h can grow the carbon nanotube orthogonal array of thickness 2.7-3.0mm.After reaching the preset reaction times, will put H
2Flow is made as 300mL/min, and the Ar flow still is 2000mL/min; Carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution of 0.06g/mL, and injection rate is 0.3mL/min; Reaction times 1h can list at carbon nano-pipe array and directly grow the carbon nanotube spongy mass.Tube furnace stops heating, closes hydrogen, regulates argon flow amount to 50mL/min, makes product cool to room temperature with the furnace, can collect the connect carbon nano-tube macroscopic body of composite structure of the bilayer that is block in a large number in quartz substrate and quartz reaction chamber interior walls.
Fig. 2 a is the photomacrograph of the carbon nanotube of double-deck series connection composite structure, the about 4.8mm of total thickness, and the about 2.2mm of carbon nano pipe array thickness wherein, the about 2.6mm of carbon nanotube spongy mass thickness, mean density is 0.116g/cm
3Fig. 2 b and 2c are respectively the stereoscan photograph of different amplification of the carbon nanotube of double-deck series connection composite structure; Can find out that carbon nano pipe array is certain directivity; The carbon nanotube spongy mass twines isotropic microtexture; Fine to isotropic transitional region combination between them by anisotropy, interpenetrate.
Embodiment 2
The carbon nano-tube macroscopic body of the double-deck series connection of preparation high quality composite structure
Weighing ferrocene 2.0g is dissolved in the 100mL xylene solution, stirs, and forms brown yellow solution, obtains ferrocene/xylene solution that concentration is 0.02g/mL, and is subsequent use.Weighing ferrocene 6.0g is dissolved in the 100mL dichlorobenzene, stirs, and forms the darker brown yellow solution of color, obtains ferrocene/dichlorobenzene solution that concentration is 0.06g/mL, and is subsequent use.
With the quartz plate that cleans up as for tube furnace flat-temperature zone intermediary reaction chamber in the silica tube, enclosed reaction chamber.Feed the 500mL/min argon gas discharging the air in the reaction chamber to reaction chamber, heating tubular type stove to 850 ℃.Behind 850 ℃ of the tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and feed 400mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Use precise injection pump injection concentration to be 0.02g/mL ferrocene/YLENE carbon source solution, the flow of injection is 0.4mL/min; Reaction times 2.5h can grow the carbon nanotube orthogonal array of thickness 2.7-3.0mm.After reaching the preset reaction times, will put H
2Flow is made as 300mL/min, and the Ar flow still is 2000mL/min; Carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution of 0.06g/mL, and injection rate is 0.2mL/min; Reaction times 2h can list at carbon nano-pipe array and directly grow the carbon nanotube spongy mass.Tube furnace stops heating, closes hydrogen, regulates argon flow amount to 50mL/min, makes product cool to room temperature with the furnace, can collect the connect carbon nano-tube macroscopic body of composite structure of the bilayer that is block in a large number in quartz substrate and quartz reaction chamber interior walls.
Fig. 3 a is the photomacrograph of the carbon nanotube with composite structure long on quartz plate, total thickness position 5.9mm, and the about 2.6mm of carbon nano pipe array thickness wherein, the about 3.3mm of carbon nanotube spongy mass thickness, mean density is 0.102g/cm
3
The carbon nano-tube macroscopic body of three layers of series connection of preparation high quality composite structure
Weighing ferrocene 2.0g is dissolved in the 100mL xylene solution, stirs, and forms brown yellow solution, obtains ferrocene/xylene solution that concentration is 0.02g/mL, and is subsequent use.Weighing ferrocene 6.0g is dissolved in the 100mL dichlorobenzene, stirs, and forms the darker brown yellow solution of color, obtains ferrocene/dichlorobenzene solution that concentration is 0.06g/mL, and is subsequent use.
With the quartz plate that cleans up as for tube furnace flat-temperature zone intermediary reaction chamber in the silica tube, enclosed reaction chamber.Feed the 500mL/min argon gas discharging the air in the reaction chamber to reaction chamber, heating tubular type stove to 850 ℃.Behind 850 ℃ of the tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and feed 400mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Use precise injection pump injection concentration to be 0.02g/mL ferrocene/YLENE carbon source solution, the flow of injection is 0.4mL/min; Reaction times 1.5h, direct growth goes out carbon nano pipe array on quartz substrate.After reaching the preset reaction times, will put H
2Flow is made as 300mL/min, and the Ar flow still is 2000mL/min; Carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution of 0.06g/mL, and injection rate is 0.3mL/min; Reaction times 1h can list at carbon nano-pipe array and directly grow the carbon nanotube spongy mass.
Stop heating; Tube furnace is to reduce to room temperature among the 100mL/min naturally at argon flow amount, behind the taking-up sample, with blade sample is cut out big bulk from the quartz plate substrate; The carbon nanotube inversion of bulk two layer composite structure is put on the quartz plate, makes carbon nano pipe array up.Again with quartz plate as in the tube furnace flat-temperature zone in the silica tube, enclosed reaction chamber.Feed the 500mL/min argon gas discharging the air in the reaction chamber to reaction chamber, heating tubular type stove to 850 ℃.
Behind 850 ℃ of the tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and feed 300mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Use precise injection pump injection concentration to be 0.06g/mL ferrocene/dichlorobenzene carbon source solution, the flow of injection is 0.3mL/min; Behind the reaction times 1h, can form the carbon nanotube of carbon nanotube spongy mass-carbon nano pipe array-three layers of cascaded structure of carbon nanotube spongy mass.
Fig. 4 a is the picture in kind of the carbon nano-tube macroscopic body of three-layer composite structure, and total thickness is 5mm, the about 2mm of intermediate arrays thickness, and both sides spongy mass thickness is respectively 1.5mm.Fig. 4 b is the stereoscan photograph of three-layer composite structure.
Embodiment 4
The carbon nano-tube macroscopic body of three layers of parallelly connected composite structure of preparation high quality
Weighing ferrocene 2.0g is dissolved in the 100mL xylene solution, stirs, and forms brown yellow solution, and obtaining concentration is that 0.02g/mL is ferrocene/xylene solution, subsequent use.Weighing ferrocene 6.0g is dissolved in the 100mL dichlorobenzene, stirs, and forms the darker brown yellow solution of color, and obtaining concentration is that 0.06g/mL is ferrocene/dichlorobenzene solution, subsequent use.
With the quartz plate that cleans up as for tube furnace flat-temperature zone intermediary reaction chamber in the silica tube, enclosed reaction chamber.Feed the 500mL/min argon gas discharging the air in the reaction chamber to reaction chamber, heating tubular type stove to 850 ℃.Behind 850 ℃ of the tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and feed 400mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Use precise injection pump injection concentration to be 0.02g/mL ferrocene/YLENE carbon source solution, the flow of injection is 0.4mL/min; Reaction times 1.5h, direct growth goes out carbon nano pipe array on quartz substrate.Stopped reaction is reduced to room temperature naturally with stove.Take out the array of the about 2mm of thickness, array along the carbon nanotube differently-oriented directivity, is cut into several pieces very thin sheets with blade, width is about 0.2-0.5mm; The multi-disc sheet-like array in the parallel placement of vertical carbon nanotube orientation 90 degree directions, is separated with being cut into more scutellate array between the strip array, build up several pieces parallel carbon nano pipe arrays; This parallel array is moved on the quartz plate, and send tube furnace flat-temperature zone, enclosed reaction chamber to.Feed the 500mL/min argon gas discharging the air in the reaction chamber to reaction chamber, heating tubular type stove to 850 ℃.
Behind 850 ℃ of the tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and feed 300mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Use precise injection pump injection concentration to be 0.06g/mL ferrocene/dichlorobenzene carbon source solution, the flow of injection is 0.3mL/min; Behind the reaction times 1h, can form the carbon nano-tube macroscopic body of carbon nanotube spongy mass-carbon nano pipe array-carbon nanotube spongy mass Multi-layer Parallel structure.
Fig. 5 a is the stereoscan photograph of the carbon nano-tube macroscopic body of Multi-layer Parallel composite structure, can see that carbon nano pipe array combines with the carbon nanotube sponge is parallelly connected.High power is swept according to electromicroscopic photograph (Fig. 5 b) and is shown that carbon nano pipe array combines finely with the bonding interface of carbon nanotube spongy mass, intert mutually and permeate, and purity is very high.
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any pro forma restriction; Former every technical scheme content of the present invention that do not break away from, all still belongs in the scope of technical scheme of the present invention any simple modification, equivalent variations and modification that above embodiment did according to technical spirit of the present invention.
Claims (10)
1. carbon nano-tube macroscopic body with composite structure, it is characterized in that: the carbon nano-tube macroscopic body of this composite structure is to be made up of carbon nanotube spongy mass and carbon nano pipe array, original position forms composite structure between them; Said carbon nanotube spongy mass is isotropy, and said carbon nano pipe array is anisotropy; Said original position forms and be meant that the composite structure that carbon nanotube spongy mass and carbon nano pipe array form directly forms in process of growth; Said composite structure comprises multilayer cascaded structure, Multi-layer Parallel structure, the mutual clad structure between them that is formed by carbon nanotube spongy mass and carbon nano pipe array, and the combination of above structure.
2. preparation method with carbon nano-tube macroscopic body of composite structure is characterized in that it may further comprise the steps:
(1) take by weighing the ferrocene powder and be dissolved in the YLENE, being mixed with concentration is ferrocene/YLENE carbon source solution of 20-100mg/mL; Take by weighing the ferrocene powder and be dissolved in the dichlorobenzene, be mixed with concentration and be ferrocene/dichlorobenzene carbon source solution of 20-100mg/mL, subsequent use;
(2) quartz substrate is put into the quartz reaction chamber of Reaktionsofen, enclosed reaction chamber, to reaction chamber feed flow be the argon gas of 500-1000mL/min to drain the air in the reaction chamber, heating reaction furnace simultaneously;
(3) when reaction chamber temperature reaches 820-940 ℃, regulate argon flow amount to 500-2000mL/min, feed the hydrogen that flow is 100-500mL/min simultaneously;
(4) then above-mentioned ferrocene/YLENE carbon source solution is injected the reaction chamber reaction, grow the carbon nanotube orthogonal array;
(5) above-mentioned ferrocene/YLENE carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution, injects the reaction chamber reaction, list at carbon nano-pipe array and directly grow the carbon nanotube spongy mass;
(6) tube furnace stops heating, closes hydrogen, regulates argon flow amount to 50-500mL/min, makes product cool to room temperature with the furnace, can collect the connect carbon nano-tube macroscopic body of composite structure of the bilayer that is block in a large number in quartz substrate and quartz reaction chamber interior walls.
3. preparation method according to claim 2 is characterized in that: in the step (1), the mol ratio of said ferrocene powder and YLENE is 1:15-1:77; The mol ratio of said ferrocene powder and dichlorobenzene is 1:16-1:83.
4. preparation method according to claim 2; It is characterized in that: in the step (4); Adopt the precise injection pump that ferrocene/YLENE carbon source solution is injected reaction chamber with the rate of feed of 0.1-0.5mL/min, react 0.1-5h, can grow the carbon nanotube orthogonal array of thickness 0.05-5.0mm.
5. preparation method according to claim 4; It is characterized in that: in the step (5); Said ferrocene/YLENE carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution; And injecting reaction chamber with the rate of feed of 0.1-0.4mL/min, reaction 0.1-5h lists at carbon nano-pipe array and directly to grow the carbon nanotube spongy mass that thickness is 0.1-10mm.
6. preparation method according to claim 2; It is characterized in that: it also further comprises step (7); After the carbon nano-tube macroscopic body sample taking-up with above-mentioned double-deck series connection composite structure; With blade with sample from the quartz plate substrate shape that cuts into large slices, the carbon nanotube of bulk two-layer composite be inverted be put on the quartz plate, make carbon nano pipe array up; The carbon nano-tube macroscopic body of carbon nanotube sponge-carbon nano pipe array-trilaminar series connection composite structure of carbon nanotube sponge is prepared in repeating step (2), (3), (5), (6).
7. preparation method according to claim 2 is characterized in that: in the step (6), said tube furnace increases to 2000mL/min with argon flow amount, and feeds 300mL/min hydrogen after keeping 850 ℃ of constant temperature, forms argon gas hydrogen mixed carrier gas; Use precise injection pump injection concentration to be 20-100mg/mL ferrocene/dichlorobenzene carbon source solution, the flow of injection is 0.1-0.4mL/min; Behind the reaction times 0.1-5h, form the carbon nano-tube macroscopic body of carbon nanotube spongy mass-carbon nano pipe array-three layers of cascaded structure of carbon nanotube spongy mass.
8. preparation method according to claim 2; It is characterized in that: it also further comprises step (8), and behind said step (1), (2), (3), (4), tube furnace stops heating; Close hydrogen; Regulate argon flow amount to 50-500mL/min, make product cool to room temperature with the furnace, can collect a large amount of directional carbon nanotube arrays at quartz substrate; Carbon nano pipe array is cut into strips (sheet); Parallel range upon range of in the vertical-growth direction; The centre separates with littler array sheet; Perhaps sheet-like array being arranged in parallel places on the quartz plate at interval again, and the carbon nano-tube macroscopic body of the carbon nanotube sponge composite structure parallelly connected with carbon nano pipe array is prepared in repeating step (2), (3), (5), (6).
9. preparation method according to claim 8 is characterized in that: the about 2mm of said directional carbon nanotube array thickness, array are cut into several pieces very thin sheets along the carbon nanotube differently-oriented directivity with blade, and width is about 0.2-0.5mm; Said multi-disc sheet-like array is in the parallel placement of vertical carbon nanotube orientation 90 degree directions.
10. preparation method according to claim 8 is characterized in that: in the step (6), tube furnace increases to 2000mL/min with argon flow amount, and feeds 300mL/min hydrogen after keeping 850 ℃ of constant temperature, forms argon gas hydrogen mixed carrier gas; Use precise injection pump injection concentration to be 20-100mg/mL ferrocene/dichlorobenzene carbon source solution, the flow of injection is 0.1-0.4mL/min; Behind the reaction times 0.1-5h, form the carbon nano-tube macroscopic body of carbon nanotube spongy mass-carbon nano pipe array-carbon nanotube spongy mass Multi-layer Parallel structure.
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