CN102838104B - 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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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 by the curling tubular structure forming of graphite synusia, its unique texture has determined that it has the performance of many excellences, as low density, high strength, 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 more promoted the practical application of carbon nanotube to transform.
Carbon nano-tube macroscopic body mainly contains carbon nano-tube filament, the rope of one dimension; Carbon nano-tube film, the paper of two dimension; The three-dimensional structure such as carbon nano-array, cavernous body.The carbon nano-tube macroscopic body of different dimensions has shown advantage and application potential separately in different fields, especially three dimensional carbon nanotubes macroscopic body receives much concern more.
Carbon nano pipe array in three dimensional carbon nanotubes macroscopic body, is anisotropy, and the performances such as its mechanics, electricity, calorifics present greatest differences in the direction of growth with in orthotropic direction macroscopic view, in its vertical-growth direction, have good rigidity.Open people (the Rapid growth of well-aligned carbon nanotube arrays such as pioneer, ChemicalPhysics Letters, 2002,362:285.) utilize chemical gas-phase method, directly synthesized fast overlength carbon nano pipe array, the fields such as this array transmitting on the scene have good application prospect.In three dimensional carbon nanotubes macroscopic body, except being anisotropic carbon nano pipe array, also have one to be isotropic carbon nano-tube macroscopic body, such carbon nano-tube macroscopic body all directions in performance and structure keep homogeneity.People's (Chinese invention patent, publication number: CN101607704A) such as osmanthus Xu Chun utilize catalystic pyrolysis, have directly synthesized and have been isotropic three dimensional carbon nanotubes macroscopic body, and be referred to as carbon nanotube cavernous body.Carbon nanotube cavernous body has the features such as lightweight, porous, isotropy, high-flexibility, and it has good application prospect in fields such as adsorption filtrations.
Can directly synthesize and there is the performance advantage separately of carbon nano pipe array and carbon nanotube cavernous body and the carbon nano-tube macroscopic body of feature, become one of difficult problem that field of carbon nanotubes need to capture.Therefore develop the carbon nano-tube macroscopic body with composite structure being formed by carbon nano pipe array and carbon nanotube cavernous body assemble in situ, and develop technique method simple, that can directly synthesize above-mentioned carbon nanometer macroscopic body and have great importance.
Summary of the invention
The object of the invention is to, a kind of three dimensional carbon nanotubes macroscopic body of the composite structure being 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 energy-obsorbing and damping field.
Another object of the present invention is to, provide one to utilize catalystic pyrolysis, low cost, high-level efficiency, controllably prepare continuously the method for the carbon nanotube of above-mentioned high quality isotropy and anisotropy composite structure, by regulating the processing parameters such as catalyst concn, carbon source rate of feed, the performance such as density, mechanical strength of regulation and control composite structure of carbon nano tube, to realize the controlledly synthesis of carbon nano-tube macroscopic body of this composite structure.
The object of the invention to solve the technical problems realizes by the following technical solutions.A kind of carbon nano-tube macroscopic body with composite structure proposing according to the present invention, is made up of carbon nanotube cavernous body and carbon nano pipe array, and between them, original position forms composite structure, and carbon nanotube cavernous body is isotropy, and carbon nano pipe array is anisotropy; This original position forms and refers to that the composite structure that carbon nanotube cavernous body and carbon nano pipe array form directly forms in process of growth; This composite structure comprises the multilayer cascaded structure that formed by carbon nanotube cavernous body and carbon nano pipe array, Multi-layer Parallel structure, mutual clad structure between them, and the combination of above structure.
In addition, the invention allows for a kind of preparation method of the above-mentioned carbon nano-tube macroscopic body with composite structure, it comprises the following steps:
(1) take ferrocene powder and be dissolved in dimethylbenzene, being mixed with concentration is ferrocene/dimethylbenzene carbon source solution (first solution) of 20-100mg/mL; Take ferrocene powder and be dissolved in dichlorobenzene, be mixed with concentration and be ferrocene/dichlorobenzene carbon source solution (second solution) of 20-100mg/mL, for subsequent use;
(2) quartz substrate is put into the quartz reaction chamber of Reaktionsofen, enclosed reaction chamber, to reaction chamber pass into flow be the argon gas of 500-1000mL/min to drain the air in reaction chamber, heating reaction furnace simultaneously;
(3) in the time that reaction chamber temperature reaches 820-940 DEG C, regulate argon flow amount to 500-2000mL/min, pass into the hydrogen that flow is 100-500mL/min simultaneously;
(4) then above-mentioned ferrocene/dimethylbenzene carbon source solution is injected to reaction chamber reaction, grow vertical carbon nanotube array;
(5) above-mentioned ferrocene/dimethylbenzene carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution, injects reaction chamber reaction, list and directly grow carbon nanotube cavernous body at carbon nano-pipe array;
(6) 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 the carbon nano-tube macroscopic body of the double-deck series composite structure that is in a large number block in quartz substrate and quartz reaction chamber interior walls.
Preparation method of the present invention, in step (1), the mol ratio of described ferrocene powder and dimethylbenzene is 1:15-1:77; The mol ratio of described ferrocene powder and dichlorobenzene is 1:16-1:83.
Preparation method of the present invention, in step (4), adopts precise injection pump that first solution is injected to reaction chamber with the rate of feed of 0.1-0.5mL/min, reacts 0.1-5h, can grow the vertical carbon nanotube array of thickness 0.05-5.0mm.
Preparation method of the present invention, in step (5), ferrocene/dimethylbenzene carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution, and inject reaction chamber with the rate of feed of 0.1-0.4mL/min, reaction 0.1-5h, lists and directly grows the carbon nanotube cavernous body that thickness is 0.1-10mm at carbon nano-pipe array.
Preparation method of the present invention, it also further comprises step (7), after the carbon nano-tube macroscopic body sample of above-mentioned double-deck series composite structure is taken out, with blade by sample from the quartz plate substrate shape that cuts into large slices, the carbon nanotube of bulk two-layer composite is inverted and is put on quartz plate, make carbon nano pipe array upward; Repeating step (2), (3), (5), (6), prepare the carbon nano-tube macroscopic body of the series composite structure of three layers, carbon nanotube sponge-carbon nano pipe array-carbon nanotube sponge.
Preparation method of the present invention, in step (6), described tube furnace keeps, after 850 DEG C of constant temperature, argon flow amount being increased to 2000mL/min, and passing into 300mL/min hydrogen, forms argon gas hydrogen mixed carrier gas; Using precise injection pump injection concentration is 20-100mg/mL ferrocene/dichlorobenzene carbon source solution, and the flow of injection is 0.1-0.4mL/min; After reaction times 0.1-5h, form the carbon nano-tube macroscopic body of three layers of cascaded structure of carbon nanotube cavernous body-carbon nano pipe array-carbon nanotube cavernous body.
Preparation method of the present invention, it also further comprises step (8), behind described 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 stacked in vertical-growth direction, centre separates by less array sheet, or the sheet-like array interval that is arranged in parallel is placed on quartz plate again, repeating step (2), (3), (5), (6), prepare the carbon nano-tube macroscopic body of the carbon nanotube sponge composite structure in parallel with carbon nano pipe array.
Preparation method of the present invention, the about 2mm of described directional carbon nanotube array thickness, array is along carbon nanotube differently-oriented directivity, is cut into several pieces very thin sheets with blade, and width is about 0.2-0.5mm; Described multi-disc sheet-like array is in the parallel placement of vertical carbon nanotube orientation 90 degree direction.
Preparation method of the present invention, in step (6), tube furnace keeps, after 850 DEG C of constant temperature, argon flow amount being increased to 2000mL/min, and passing into 300mL/min hydrogen, forms argon gas hydrogen mixed carrier gas; Using precise injection pump injection concentration is 20-100mg/mL ferrocene/dichlorobenzene carbon source solution, and the flow of injection is 0.1-0.4mL/min; After reaction times 0.1-5h, form the carbon nano-tube macroscopic body of carbon nanotube cavernous body-carbon nano pipe array-carbon nanotube cavernous body Multi-layer Parallel structure.
By technique scheme, advantage and beneficial effect that the present invention has are as follows:
(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 the various structures such as multilayer series connection, Multi-layer Parallel, a kind of coated another kind; Make the structure of carbon nano-tube macroscopic body become abundanter, its macroscopic body over-all properties is more outstanding;
(3) by changing the 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 the performances such as its mechanics of regulation and control, electricity, calorifics;
(4) equipment is simple, controllable operating is strong, is suitable for amplifying producing.
The present invention has realized a kind of carbon nano-tube macroscopic body of novel texture, is convenient to directly apply and batch preparation, and the method for preparing fast, efficiently, on a large scale of this carbon nano-tube macroscopic body is provided; This carbon nano-tube macroscopic body can be applicable to the technical fields such as energy-obsorbing and damping, heat insulation and acoustic absorption, the poisonous organic solution of absorption.
Brief description of the drawings
Figure 1 shows that the apparatus structure schematic 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 composite structure; Fig. 2 b and 2c are respectively the stereoscan photograph of the different amplification of the carbon nanotube of double-deck series composite structure;
Fig. 3 is the photomacrograph of the carbon nanotube with composite structure of growing on quartz plate;
Fig. 4 a and 4b are respectively 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 cavernous body is swept according to electromicroscopic photograph.
Wherein: 1 is mass-flow gas meter, experiment shares two kinds of gases: argon gas (Ar) and hydrogen (H
2); 2 is silica tube; 3 is tubular react furnace; 4 is the quartz plate substrate for the product of growing; 5 is precise injection pump.
Embodiment
Refer to shown in Fig. 1, core of the present invention is the various composite structures that carbon nanotube cavernous body becomes with 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) take ferrocene ((C
5h
5)
2fe) powder is dissolved in dimethylbenzene (C
6h
4(CH
3)
2) in, being mixed with concentration is ferrocene/dimethylbenzene carbon source solution (first solution) of 20-100mg/mL; Take 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, for subsequent use;
(2) quartz substrate 4 is put into silica tube reaction chamber 2, enclosed reaction chamber, passes into silica tube reaction chamber 2 argon gas that flow is 500-1000mL/min by mass-flow gas meter 1, to drain the air in reaction chamber, and heated Tube Reaktionsofen 3 simultaneously;
(3) in the time that the temperature of tubular react furnace 3 reaches 820-940 DEG C, regulate argon flow amount to 2000mL/min, pass into the hydrogen that flow is 100-500mL/min simultaneously;
(4) then with precise injection pump 5, first solution is injected to reaction chamber with the rate of feed of 0.1-0.5mL/min, 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, close hydrogen, regulate argon flow amount to 50-500mL/min, make product cool to room temperature with the furnace, can collect the carbon nano-tube macroscopic body of the double-deck series composite structure that is in a large number block at the inwall of quartz substrate 4 and quartz reaction chamber 2.
(7) after the carbon nano-tube macroscopic body sample of above-mentioned double-deck series composite structure is taken out, with blade by sample from quartz plate substrate 4 shape that cuts into large slices, the carbon nanotube of bulk two-layer composite is inverted and is put on quartz plate, make carbon nano pipe array upward.The carbon nano-tube macroscopic body of the series composite structure of three layers, carbon nanotube sponge-carbon nano pipe array-carbon nanotube sponge can be prepared in repeating step (2), (3), (5), (6).
(8) behind above-mentioned steps (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), at vertical-growth direction parallel stacked (carbon nanotube is vertical with its former growth orientation), centre separates by less array sheet, or the sheet-like array interval that is arranged in parallel is being placed on quartz plate, repeating step (2), (3), (5), (6), can prepare the carbon nano-tube macroscopic body of the carbon nanotube sponge composite structure in parallel with carbon nano pipe array.
embodiment 1
prepare the carbon nano-tube macroscopic body of the double-deck series composite structure of high quality
Weigh ferrocene 2.0g, be dissolved in 100mL xylene solution, stir, form brown yellow solution, obtain ferrocene/xylene solution that concentration is 0.02g/mL, for subsequent use.Weigh ferrocene 6.0g, be dissolved in 100mL dichlorobenzene, stir, form the darker brown yellow solution of color, obtain ferrocene/dichlorobenzene solution that concentration is 0.06g/mL, for subsequent use.
The quartz plate cleaning up is placed in to the reaction chamber in the middle of tube furnace flat-temperature zone in silica tube, enclosed reaction chamber.Pass into 500mL/min argon gas to discharge the air in reaction chamber, heated Tube stove to 850 DEG C to reaction chamber.After 850 DEG C of tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and pass into 400mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Using precise injection pump injection concentration is 0.02g/mL ferrocene/dimethylbenzene carbon source solution, and the flow of injection is 0.4mL/min; Reaction times 1.5h, can grow the vertical carbon nanotube array of thickness 2.7-3.0mm.Reaching after the default reaction times, will put H
2flow is made as 300mL/min, and Ar flow is still 2000mL/min; Ferrocene/dichlorobenzene carbon source the solution that carbon source solution is changed to 0.06g/mL, injection rate is 0.3mL/min; Reaction times 1h, can list and directly grow carbon nanotube cavernous body at carbon nano-pipe array.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 carbon nano-tube macroscopic body of the double-deck series composite structure that is in a large number block in quartz substrate and quartz reaction chamber interior walls.
Fig. 2 a is the photomacrograph of the carbon nanotube of double-deck series composite structure, the about 4.8mm of total thickness, and the wherein about 2.2mm of carbon nano pipe array thickness, the about 2.6mm of carbon nanotube cavernous body thickness, mean density is 0.116g/cm
3.Fig. 2 b and 2c are respectively the stereoscan photograph of the different amplification of the carbon nanotube of double-deck series composite structure, can find out that carbon nano pipe array is certain directivity, carbon nanotube cavernous body is wound around isotropic microtexture, between them by anisotropy to isotropic transitional region in conjunction with fine, interpenetrate.
embodiment 2
prepare the carbon nano-tube macroscopic body of the double-deck series composite structure of high quality
Weigh ferrocene 2.0g, be dissolved in 100mL xylene solution, stir, form brown yellow solution, obtain ferrocene/xylene solution that concentration is 0.02g/mL, for subsequent use.Weigh ferrocene 6.0g, be dissolved in 100mL dichlorobenzene, stir, form the darker brown yellow solution of color, obtain ferrocene/dichlorobenzene solution that concentration is 0.06g/mL, for subsequent use.
Reaction chamber by the quartz plate cleaning up as for centre, tube furnace flat-temperature zone in silica tube, enclosed reaction chamber.Pass into 500mL/min argon gas to discharge the air in reaction chamber, heated Tube stove to 850 DEG C to reaction chamber.After 850 DEG C of tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and pass into 400mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Using precise injection pump injection concentration is 0.02g/mL ferrocene/dimethylbenzene carbon source solution, and the flow of injection is 0.4mL/min; Reaction times 2.5h, can grow the vertical carbon nanotube array of thickness 2.7-3.0mm.Reaching after the default reaction times, will put H
2flow is made as 300mL/min, and Ar flow is still 2000mL/min; Ferrocene/dichlorobenzene carbon source the solution that carbon source solution is changed to 0.06g/mL, injection rate is 0.2mL/min; Reaction times 2h, can list and directly grow carbon nanotube cavernous body at carbon nano-pipe array.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 carbon nano-tube macroscopic body of the double-deck series composite structure that is in a large number block in quartz substrate and quartz reaction chamber interior walls.
Fig. 3 a is the photomacrograph of the carbon nanotube with composite structure of length on quartz plate, total thickness position 5.9mm, and the wherein about 2.6mm of carbon nano pipe array thickness, the about 3.3mm of carbon nanotube cavernous body thickness, mean density is 0.102g/cm
3.
embodiment 3
prepare the carbon nano-tube macroscopic body of three layers of series composite structure of high quality
Weigh ferrocene 2.0g, be dissolved in 100mL xylene solution, stir, form brown yellow solution, obtain ferrocene/xylene solution that concentration is 0.02g/mL, for subsequent use.Weigh ferrocene 6.0g, be dissolved in 100mL dichlorobenzene, stir, form the darker brown yellow solution of color, obtain ferrocene/dichlorobenzene solution that concentration is 0.06g/mL, for subsequent use.
Reaction chamber by the quartz plate cleaning up as for centre, tube furnace flat-temperature zone in silica tube, enclosed reaction chamber.Pass into 500mL/min argon gas to discharge the air in reaction chamber, heated Tube stove to 850 DEG C to reaction chamber.After 850 DEG C of tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and pass into 400mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Using precise injection pump injection concentration is 0.02g/mL ferrocene/dimethylbenzene carbon source solution, and the flow of injection is 0.4mL/min; Reaction times 1.5h, on quartz substrate, direct growth goes out carbon nano pipe array.Reaching after the default reaction times, will put H
2flow is made as 300mL/min, and Ar flow is still 2000mL/min; Ferrocene/dichlorobenzene carbon source the solution that carbon source solution is changed to 0.06g/mL, injection rate is 0.3mL/min; Reaction times 1h, can list and directly grow carbon nanotube cavernous body at carbon nano-pipe array.
Stop heating, tube furnace is in 100mL/min, to be naturally down to room temperature at argon flow amount, takes out after sample, sample is cut out to large bulk from quartz plate substrate with blade, the carbon nanotube of bulk two layer composite structure is inverted and is put on quartz plate, make carbon nano pipe array upward.Again by quartz plate as in tube furnace flat-temperature zone in silica tube, enclosed reaction chamber.Pass into 500mL/min argon gas to discharge the air in reaction chamber, heated Tube stove to 850 DEG C to reaction chamber.
After 850 DEG C of tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and pass into 300mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Using precise injection pump injection concentration is 0.06g/mL ferrocene/dichlorobenzene carbon source solution, and the flow of injection is 0.3mL/min; After reaction times 1h, can form the carbon nanotube of three layers of cascaded structure of carbon nanotube cavernous body-carbon nano pipe array-carbon nanotube cavernous body.
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 cavernous body thickness is respectively 1.5mm.Fig. 4 b is the stereoscan photograph of three-layer composite structure.
embodiment 4
prepare the carbon nano-tube macroscopic body of three layers of composite structure in parallel of high quality
Weigh ferrocene 2.0g, be dissolved in 100mL xylene solution, stir, form brown yellow solution, obtaining concentration is that 0.02g/mL is ferrocene/xylene solution, for subsequent use.Weigh ferrocene 6.0g, be dissolved in 100mL dichlorobenzene, stir, form the darker brown yellow solution of color, obtaining concentration is that 0.06g/mL is ferrocene/dichlorobenzene solution, for subsequent use.
Reaction chamber by the quartz plate cleaning up as for centre, tube furnace flat-temperature zone in silica tube, enclosed reaction chamber.Pass into 500mL/min argon gas to discharge the air in reaction chamber, heated Tube stove to 850 DEG C to reaction chamber.After 850 DEG C of tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and pass into 400mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Using precise injection pump injection concentration is 0.02g/mL ferrocene/dimethylbenzene carbon source solution, and the flow of injection is 0.4mL/min; Reaction times 1.5h, on quartz substrate, direct growth goes out carbon nano pipe array.Stopped reaction, is down to room temperature naturally by stove.Take out the array of thickness about 2mm, array, along carbon nanotube differently-oriented directivity, is cut into several pieces very thin sheets with blade, width is about 0.2-0.5mm; Multi-disc sheet-like array, in the parallel placement of vertical carbon nanotube orientation 90 degree direction, is separated with being cut into more scutellate array between strip array, build up several pieces parallel carbon nano pipe arrays; This parallel array is moved on quartz plate, and send tube furnace flat-temperature zone, enclosed reaction chamber to.Pass into 500mL/min argon gas to discharge the air in reaction chamber, heated Tube stove to 850 DEG C to reaction chamber.
After 850 DEG C of tube furnace maintenance constant temperature, argon flow amount is increased to 2000mL/min, and pass into 300mL/min hydrogen, form argon gas hydrogen mixed carrier gas.Using precise injection pump injection concentration is 0.06g/mL ferrocene/dichlorobenzene carbon source solution, and the flow of injection is 0.3mL/min; After reaction times 1h, can form the carbon nano-tube macroscopic body of carbon nanotube cavernous body-carbon nano pipe array-carbon nanotube cavernous body 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 is in parallel with carbon nanotube sponge to combine.High power sweeps that (Fig. 5 b) shows that carbon nano pipe array be combined finely with the bonding interface of carbon nanotube cavernous body, mutual interspersed infiltration, and purity is very high according to electromicroscopic photograph.
The above, it is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, do not depart from technical solution of the present invention content therefore every, any simple modification, equivalent variations and the modification above embodiment done according to technical spirit of the present invention, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. a carbon nano-tube macroscopic body with composite structure, is characterized in that: the carbon nano-tube macroscopic body of this composite structure is to be made up of carbon nanotube cavernous body and carbon nano pipe array, and between them, original position forms composite structure; Described carbon nanotube cavernous body is isotropy, and described carbon nano pipe array is anisotropy; Described original position forms the composite structure directly formation in process of growth that refers to that carbon nanotube cavernous body and carbon nano pipe array form, and interpenetrates and combine closely, and forms seamless one-piece construction; Described composite structure comprises the multilayer cascaded structure that formed by carbon nanotube cavernous body and carbon nano pipe array, Multi-layer Parallel structure, mutual clad structure between them, and the combination of above structure.
2. there is a preparation method for the carbon nano-tube macroscopic body of composite structure, it is characterized in that it comprises the following steps:
(1) take ferrocene powder and be dissolved in dimethylbenzene, being mixed with concentration is ferrocene/dimethylbenzene carbon source solution of 20-100mg/mL; Take ferrocene powder and be dissolved in dichlorobenzene, be mixed with concentration and be ferrocene/dichlorobenzene carbon source solution of 20-100mg/mL, for subsequent use;
(2) quartz substrate is put into the quartz reaction chamber of Reaktionsofen, enclosed reaction chamber, to reaction chamber pass into flow be the argon gas of 500-1000mL/min to drain the air in reaction chamber, heating reaction furnace simultaneously;
(3) in the time that reaction chamber temperature reaches 820-940 DEG C, regulate argon flow amount to 500-2000mL/min, pass into the hydrogen that flow is 100-500mL/min simultaneously;
(4) then above-mentioned ferrocene/dimethylbenzene carbon source solution is injected to reaction chamber reaction, grow vertical carbon nanotube array;
(5) above-mentioned ferrocene/dimethylbenzene carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution, injects reaction chamber reaction, list and directly grow carbon nanotube cavernous body at carbon nano-pipe array;
(6) 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 the carbon nano-tube macroscopic body of the double-deck series composite structure that is in a large number block in quartz substrate and quartz reaction chamber interior walls.
3. preparation method according to claim 2, is characterized in that: in step (1), the mol ratio of described ferrocene powder and dimethylbenzene is 1:15-1:77; The mol ratio of described ferrocene powder and dichlorobenzene is 1:16-1:83.
4. preparation method according to claim 2, it is characterized in that: in step (4), adopt precise injection pump that ferrocene/dimethylbenzene carbon source solution is injected to reaction chamber with the rate of feed of 0.1-0.5mL/min, react 0.1-5h, can grow the vertical carbon nanotube array of thickness 0.05-5.0mm.
5. preparation method according to claim 4, it is characterized in that: in step (5), described ferrocene/dimethylbenzene carbon source solution is changed to ferrocene/dichlorobenzene carbon source solution, and inject reaction chamber with the rate of feed of 0.1-0.4mL/min, reaction 0.1-5h, lists and directly grows the carbon nanotube cavernous body that thickness is 0.1-10mm at carbon nano-pipe array.
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 of above-mentioned double-deck series composite structure is taken out, with blade by sample from the quartz plate substrate shape that cuts into large slices, the carbon nanotube of bulk two-layer composite is inverted and is put on quartz plate, make carbon nano pipe array upward; Repeating step (2), (3), (5), (6), prepare the carbon nano-tube macroscopic body of the series composite structure of three layers, carbon nanotube sponge-carbon nano pipe array-carbon nanotube sponge.
7. preparation method according to claim 6, is characterized in that: in step (7), tube furnace keeps, after 850 DEG C of constant temperature, argon flow amount being increased to 2000mL/min, and passing into 300mL/min hydrogen, forms argon gas hydrogen mixed carrier gas; Using precise injection pump injection concentration is 20-100mg/mL ferrocene/dichlorobenzene carbon source solution, and the flow of injection is 0.1-0.4mL/min; After reaction times 0.1-5h, form the carbon nano-tube macroscopic body of three layers of cascaded structure of carbon nanotube cavernous body-carbon nano pipe array-carbon nanotube cavernous body.
8. preparation method according to claim 2, it is characterized in that: it also further comprises step (8), behind described 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; By carbon nano pipe array cut into inch strips band shape or sheet, parallel stacked in vertical-growth direction, centre separates by less array sheet, or the sheet-like array interval that is arranged in parallel is placed on quartz plate again, repeating step (2), (3), (5), (6), prepare the carbon nano-tube macroscopic body of the carbon nanotube sponge composite structure in parallel with carbon nano pipe array.
9. preparation method according to claim 8, is characterized in that: described directional carbon nanotube array thickness is 2mm, and array is along carbon nanotube differently-oriented directivity, is cut into several pieces very thin sheets with blade, and width is 0.2-0.5mm; Described multi-disc sheet-like array is in the parallel placement of vertical carbon nanotube orientation 90 degree direction.
10. preparation method according to claim 8, is characterized in that: in step (8), tube furnace keeps, after 850 DEG C of constant temperature, argon flow amount being increased to 2000mL/min, and passing into 300mL/min hydrogen, forms argon gas hydrogen mixed carrier gas; Using precise injection pump injection concentration is 20-100mg/mL ferrocene/dichlorobenzene carbon source solution, and the flow of injection is 0.1-0.4mL/min; After reaction times 0.1-5h, form the carbon nano-tube macroscopic body of carbon nanotube cavernous body-carbon nano pipe array-carbon nanotube cavernous body Multi-layer Parallel structure.
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| CN103241722B (en) * | 2013-05-16 | 2014-10-22 | 中山大学 | Carbon nano-tube macroscopic body with gradient structure and preparation method thereof |
| CN104418316B (en) * | 2013-08-27 | 2017-01-25 | 清华大学 | Carbon nanotube sponge body and preparation method thereof |
| CN103979522B (en) * | 2014-04-19 | 2015-12-30 | 东风商用车有限公司 | Multiple film layer is divided into the macroscopic body in multiple regularly arranged duct and preparation method thereof mutually |
| CN106315550B (en) * | 2016-08-08 | 2018-11-09 | 南京航空航天大学 | A kind of preparation method of carbon nanotube cavernous body |
| CN107758647A (en) * | 2017-11-22 | 2018-03-06 | 哈尔滨工业大学 | A kind of preparation method of low defect graphene ribbon sponge composite |
| CN107804838A (en) * | 2017-11-22 | 2018-03-16 | 哈尔滨工业大学 | A kind of preparation method of low defect graphene ribbon sponge ultracapacitor |
| CN107814379A (en) * | 2017-11-22 | 2018-03-20 | 哈尔滨工业大学 | A kind of method that low defect graphene ribbon sponge is prepared using CNT sponge |
| CN107986261B (en) * | 2018-01-09 | 2021-01-05 | 郑州大学 | Device and method for preparing oversized carbon nanotube three-dimensional porous block |
| CN110357073B (en) * | 2019-08-23 | 2022-03-15 | 哈尔滨工业大学 | Preparation method of gradient rigidity carbon nanotube sponge |
| CN110540189A (en) * | 2019-09-17 | 2019-12-06 | 哈尔滨工业大学 | Preparation method of self-adaptive variable-stiffness damper based on sponge structure |
| CN114852997A (en) * | 2022-05-26 | 2022-08-05 | 陕西科技大学 | Three-dimensional carbon nanotube-mesoporous carbon composite sponge, and preparation method and application thereof |
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