CN100386258C - Aerogel carbon nanotube and its preparation method and application - Google Patents

Aerogel carbon nanotube and its preparation method and application Download PDF

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CN100386258C
CN100386258C CNB2006100893859A CN200610089385A CN100386258C CN 100386258 C CN100386258 C CN 100386258C CN B2006100893859 A CNB2006100893859 A CN B2006100893859A CN 200610089385 A CN200610089385 A CN 200610089385A CN 100386258 C CN100386258 C CN 100386258C
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carbon nanotube
aerogel
carbon nanometer
nanometer tube
tube bank
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CN1884058A (en
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魏飞
张强
周卫平
徐光辉
杨州
骞伟中
罗国华
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Tsinghua University
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Abstract

The present invention relates to an aerogel carbon nanometer tube, and also relates to a preparation method and an application of the aerogel carbon nanometer tube, which belongs to the technical field of nanometer material preparation. The aerogel carbon nanometer tube comprises a dispersed carbon nanometer tube or a carbon nanometer tube bundle, wherein the diameter of the carbon nanometer tube or the carbon nanometer tube bundle is from 1 nanometer to 100 microns, and the length-diameter ratio is from 10<1> to 10<6>. The bulk density of the aerogel carbon nanometer tube is from 0.1 to 100 g/L. The aerogel carbon nanometer tube is obtained through the following method which comprises the steps: the carbon nanometer tube bundle or a carbon nanometer array sample to be treated is crushed by outer force; then, the aerogel carbon nanometer tube is obtained through dispersion, deposition and grading collection in a gas phase. The aerogel carbon nanometer tube is shaped and processed as a heat conduction conductive material, or is compounded with an organic macromolecule, an inorganic material, a metal basal body and the like to form a transparent conductive membrane, a super conductive additive, a membrane material, a mechanical reinforcing and toughening composite material, a heat insulation composite material, a composite material for strengthening the heat conductivity of materials, a composite material for shielding electromagnetic radiation, etc.

Description

Aerogel carbon nanotube and its production and application
Technical field
The present invention relates to a kind of carbon nanotube and preparation method and application, relate in particular to a kind of aerogel carbon nanotube with and its production and application, belong to the novel nano-material preparing technical field.
Background technology
A kind of novel nano-material that carbon nanotube (Carbon Nanotubes is abbreviated as CNTs) is made up of carbon atom.Because its ideal one-dimentional structure has widely it and uses at aspects such as enhancing, heat conduction, conduction, electromagnetic shielding, Wave suction composite material, molecular device, support of the catalyst, nano electron devices.
People have obtained the carbon nanotube of multiple pattern at present.Use " the poly-group of nanometer bed catalystic pyrolysis " (number of patent application: 01118349.7; PCT/CN02/00044) can obtain large batch of carbon nanotube, use the method for swimming to obtain a certain amount of overlength carbon nano pipe array (patent publication No.: CN 1724343A).As the application of matrix material, often need to disperse carbon nanotube preferably can give play to the excellent properties of carbon nanotube.So for the practical application of carbon nanotube, carbon nanotube is a matter of utmost importance to obtain to disperse preferably.
At present, disperseing preferably, the carbon nanotube major part all is to carry out in liquid medium.(patent No.: ZL02117419.9) waiting generally all is to carry out in water for example " a kind of method of utilizing external force to crush, wash and purify slender carbon nanotube ".And the large-scale application of carbon nanotube is to be used for and the compound preparation matrix material of other matrix, and this just means all needs dispersed carbon nano tube is separated from liquid phase under many circumstances.If in gas phase, directly realize disperseing, avoided removing dissolving agent process, so the carbon nanotube of gas phase dispersion is a kind of material with important potential application.
Summary of the invention
The purpose of this invention is to provide a kind of scattered aerogel carbon nanotube and its production and application, can in gas phase, directly disperse in its preparation process, need not liquid phase dispersion medium, avoided the made of carbon nanotubes matrix material to use liquid phase to be dispersed in desolventizing step required in the recombination process.
Technical scheme of the present invention is as follows:
A kind of aerogel carbon nanotube is characterized in that: described aerogel carbon nanotube is made up of the tube bank of dispersed carbon nano tube or carbon nanotube, and the diameter that described carbon nanotube or carbon nanotube are restrained is between 1 nanometer to 100 micron, and length-to-diameter ratio is 10 1-10 6, this aerogel carbon nanotube bulk density is 0.1～100g/L.
The invention provides a kind of preparation method of described aerogel carbon nanotube, it is characterized in that this method comprises the steps:
1) utilize external force with the tube bank of pending carbon nanotube or carbon nano pipe array sample through the one or many fragmentation, forming bulk density is the poly-group of 0.1～100g/L carbon nanotube;
2) utilize air-flow in gas phase, to disperse sedimentation through the sample that step 1) is handled;
3) sediment of the feature that meets aerogel carbon nanotube is collected in classification, obtains described aerogel carbon nanotube.
In above-mentioned steps, described pending carbon nanotube tube bank or carbon nano pipe array sample are one or more in Single Walled Carbon Nanotube tube bank, multi-walled carbon nano-tubes tube bank, single-wall carbon nanotube array or the array of multi-walled carbon nanotubes.Described external force method adopts high velocity air shearing, mechanical high-speed shearing, sand milling or explosive method.
The present invention also provides a kind of application of described aerogel carbon nanotube, be described aerogel carbon nanotube by forming process as heat conduction, the material of conduction, or by with organic polymer, inorganic materials or metallic matrix are compound as the structural composite material that strengthens mechanical property, strengthen the functional materials of conductivity, increase the functional materials of electrode and electrical condenser specific surface area, the functional materials of electromagnetic radiation shielding, the matrix material of electrically conducting transparent performance, the functional materials of increased thermal conductivity energy, the application of heat-proof quality excellent function material and catalyst support material.
The present invention compared with prior art has the following advantages and useful effect: aerogel carbon nanotube provided by the present invention can directly disperse in gas phase, need not required dispersion medium such as liquid phase method; Can carry out once more stage treatment for the product after disperseing; Carbon nanotube not damaged for overlength; This processing method is simple to operate, and cost is low, is easy to engineering and amplifies.This aerogel carbon nanotube can form compound structure or functional materials with organic polymer, inorganic polymer, metal etc.Owing to there is not the participation of liquid phase, the matrix material that this method obtains can not comprise the dispersion agent of picture blend or other method introduction of carbon nanotube.This aerogel carbon nanotube can be by the material of forming process as heat conduction, conduction, or by strengthening the functional materials of the structural composite material of mechanical property, the functional materials that strengthens conductivity, the functional materials that increases electrode and electrical condenser specific surface area, electromagnetic radiation shielding, the matrix material of electrically conducting transparent performance, the functional materials of increased thermal conductivity energy, the application of heat-proof quality excellent function material and catalyst support material with the compound conduct of organic polymer, inorganic materials or metallic matrix.
Description of drawings
Fig. 1 is preparation technology's schema of aerogel carbon nanotube.
The preceding stereoscan photograph figure of carbon nano pipe array sample Mechanical Crushing that Fig. 2 a adopts for the present invention.
Fig. 2 b is that the present invention is to the carbon nanotube sample stereoscan photograph of the carbon nano pipe array shown in Fig. 2 a behind the mechanical high-speed shearing-crushing.
Fig. 2 c be with the sample after the fragmentation in gas phase, disperse, aerogel carbon nanotube stereoscan photograph behind the sedimentation 30s.
Fig. 2 d be with the sample after the fragmentation in gas phase, disperse, aerogel carbon nano scanning Electronic Speculum pipe photo behind the sedimentation 4min.
Fig. 3 be to carbon nano pipe array after air-flow is sheared, in gas phase, disperse, the aerogel carbon nanotube stereoscan photograph behind the sedimentation 1min.
Fig. 4 a restrains behind the mechanical high-speed shearing-crushing aerogel carbon nanotube stereoscan photograph in gas phase behind dispersion, the sedimentation 30s to carbon nanotube.
Fig. 4 b restrains behind the mechanical high-speed shearing-crushing aerogel carbon nanotube stereoscan photograph in gas phase behind dispersion, the sedimentation 3min to carbon nanotube.
Fig. 5 be to carbon nano pipe array behind the mechanical high-speed shearing-crushing, in gas phase, disperse, the aerogel carbon nanotube stereoscan photograph behind the sedimentation 15min.
Fig. 6 utilizes aerogel carbon nanotube moulding in gas phase to obtain the stereoscan photograph of paper.
Fig. 7 is tiled in the nesa coating stereoscan photograph that forms on the transparent polymer film with aerogel carbon nanotube.
Embodiment
Further specify concrete enforcement of the present invention below in conjunction with drawings and Examples.The purpose that these embodiments are provided is to make the present invention can full disclosure, fully passes on thought of the present invention and implementation result to the those skilled in the art.Yet the present invention can implement by many different modes.
Embodiment 1
Present embodiment is investigated mechanical shearing to the effect of carbon nano pipe array gas phase dispersion and the actual effect of air-flow dispersing and settling acquisition aerogel carbon nanotube.The sample utilization of the using catalysis process that swims makes carbon nano pipe array, and wherein carbon nano pipe array length is 1.4mm, and the area of carbon nanotube is about tens square millimeters.Get this array 100mg and place in the high-speed shearing machine, regulating the mechanical shearing rotating speed is 10000 rev/mins, takes out behind the pulverizing 2min.In carbon nano pipe array, to direction, reactive force is very weak between the pipe that is arranged in parallel with respect to tubular axis, and when therefore mechanical shearing taking place, shearing force is easier to act on its carbon nanotube caliber direction, thereby has realized that carbon nano pipe array becomes thin tube bank.Because carbon nanotube and carbon nanotube tube bank itself have flexibility, guarantee its its easy fracture not in shear history like this, keep original length.Stereoscan photograph after the pulverizing is referring to Fig. 2 b.As can be seen, it is 1～25 μ m that the poly-group of the carbon nanotube of taking-up has become diameter, and length is the carbon nanotube tube bank of 100～1400 μ m, and bulk density is 2g/cm 3Can see that regular carbon nano pipe array broken up the aerogel carbon nanotube that has formed agglomerate.
Is in the silica tube of 75mm with above-mentioned aerogel carbon nanotube at a diameter, and feeding superficial gas velocity is the air of 0.2m/s, and this moment, the carbon nanotube volume further expanded suspended dispersed in gas phase.After waiting to stop bubbling air, the dispersive aerogel begins to fall.Collect the sediment that different time falls.The stereoscan photograph of the product behind the sedimentation 0.5min is referring to Fig. 2 c.Wherein the diameter of carbon nanotube tube bank is 1～25 μ m, and length is the carbon nanotube tube bank of 100～1400 μ m, has formed hundreds of microns the poly-group of aerogel carbon nanotube, and tap density is at 1.3g/L.
The stereoscan photograph of the product behind the sedimentation 4min is referring to Fig. 2 d.Wherein the diameter of carbon nanotube tube bank is 1～25 μ m, and length is the carbon nanotube tube bank of 100～1000 μ m, is the poly-group of the aerogel carbon nanotube that has formed monodispersed tube bank, and tap density is at 0.5g/L.
Embodiment 2 air-flows are sheared carbon nano pipe array
Present embodiment is investigated the effect of air-flow shearing to the carbon nano pipe array gas phase dispersion.The sample that uses is made by the catalysis process that swims, and mainly is the carbon nano pipe array that orientation is arranged, and wherein carbon nano pipe array length is 1.0mm, and the area of carbon nanotube is about tens square millimeters.Get this array 1.0g and place in the air-flow shears, regulating high speed shear flow line speed is 5m/s, takes out behind the broken shearing 2min.Stereoscan photograph after the pulverizing is referring to Fig. 3.As can be seen, the aerogel carbon nanotube diameter that obtains is at 15～30 μ m, and to several thousand microns, bulk density is at 4g/L at hundreds of for length.
Is in the silica tube of 75mm with above-mentioned aerogel carbon nanotube at a diameter, and feeding superficial gas velocity is the air of 0.2m/s, and this moment, the carbon nanotube volume further expanded suspended dispersed in gas phase.After waiting to stop bubbling air, the dispersive aerogel begins to fall.Collect the sediment that different time falls.Product behind the sedimentation 1min also is an aerogel carbon nanotube, and its tap density is at 1.4g/L.Aerogel carbon nanotube tap density behind the sedimentation 5min is at 0.2g/L.
Embodiment 3
Present embodiment is investigated the effect of mechanical shearing to carbon nanotube tube bank gas phase dispersion.The sample that uses is made by the catalytic chemical gaseous phase deposition method, mainly is the carbon nanotube tube bank that orientation is arranged, and wherein carbon nano pipe array length is hundreds of microns.Carbon nanotube is restrained array 1000mg place in the high-speed shearing machine, regulating the mechanical shearing rotating speed is 10000 rev/mins, takes out behind the pulverizing 2min.Stereoscan photograph after the pulverizing is referring to Fig. 4 a.As can be seen, it is 50～250nm that the carbon nanotube of taking-up has become diameter, and length is that the carbon nanotube tube bank form of 10～100 μ m exists.Carbon nanotube forms the poly-group of micron level.This moment, bulk density was 42g/L.Can see that regular carbon nano pipe array broken up the aerogel carbon nanotube that forms agglomerate.
Is in the silica tube of 75mm with above-mentioned aerogel carbon nanotube at a diameter, and feeding superficial gas velocity is the air of 0.2m/s, and this moment, the carbon nanotube volume further expanded suspended dispersed in gas phase.After waiting to stop bubbling air, the dispersive aerogel begins to fall.Collect the sediment that different time falls.The stereoscan photograph of the product behind the sedimentation 3min is referring to Fig. 4 b.The carbon nanotube tube bank diameter that can wherein collect at this moment is littler, and carbon nanotube tube bank diameter is at 50～200nm, and length is 1～10 μ m, and bulk density is 2.2g/L.
Embodiment 4
Present embodiment investigation mechanical shearing and sedimentation are to the effect of carbon nanotube tube bank gas phase dispersion.The sample that uses is restrained as carbon nanotube.Carbon nanotube is restrained array 500mg place in the high-speed shearing machine, regulating the mechanical shearing rotating speed is 30000 rev/mins, takes out behind the pulverizing 20min.Carbon nanotube after the fragmentation being placed a diameter then is the silica tube of 75mm, and feeding superficial gas velocity is the air of 0.05m/s, and this moment, the carbon nanotube volume further expanded suspended dispersed in gas phase.After waiting to stop bubbling air, the dispersive aerogel begins to fall.Collect the sediment that different time falls.The stereoscan photograph of the product behind the sedimentation 15min is referring to Fig. 5.The carbon nanotube that collect this moment is 10～100nm, and length is the carbon nanotube pipe of 10～500 μ m, and bulk density is 0.1g/L.
Embodiment 5
Utilize air to be dispersion medium with obtaining aerogel carbon nanotube in the example 2, adopt the roller of high speed rotary, the aerogel carbon nanotube raw material is separated into carbon nanotube tube bank state, it is suspended in air, regulate vacuum tightness then the carbon nanotube tube bank is descended slowly and lightly to running copper mesh; Carbon nanotube tube bank is subjected to vacuum take-off effect under the copper mesh, and the interlaced uniform page of thickness that is overlapped into is in addition bonding, dry through Resins, epoxy again, batch etc., promptly obtains the paper of moulding.Become the micro image of paper referring to Fig. 6.This paper sheet thickness is 0.1mm, has very low resistivity, and its volume specific resistance can reach 10 -2Ω cm, thermal conductivity is at 1000W/mK, and breaking tenacity 20.2MPa, elongation at break are 9.4%, and Young's modulus is 436.3MPa.
Embodiment 6
Above-mentioned paper is fixed in the pumping and filtering device, makes 1% polyvinyl alcohol (PVA) solution suction filtration by aerogel carbon nanotube paper, PVA can be adsorbed onto carbon nano tube surface and formed the PVA-CNT matrix material this moment.With the further hot pressing of this matrix material, measuring its thickness is 0.1mm, has very low resistivity, its volume specific resistance can reach 1 Ω cm, thermal conductivity is at 300W/mK, and breaking tenacity 27.42MPa, elongation at break are 4.22%, Young's modulus is 1956.3MPa, is higher than the resistivity and the thermal conductivity of the equal thickness PVA film that adopts the same procedure preparation itself far away.So this matrix material can be used as the functional materials that is applied to mechanics enhanced structured material, the functional materials that strengthens conductivity, increased thermal conductivity energy.
Embodiment 7
Be dissolved in the deionized water obtaining aerogel carbon nanotube in the example 2, form the carbon nano-tube solution that concentration is about 10ppm.Under 3000 rev/mins rotating speed this solution is coated onto above the transparent substrate, forms the nesa coating of transmittance to 80%, its stereoscan photograph is referring to Fig. 7.Can measure its surface resistivity by four point probe resistance instrument and can reach 1000 Ω/mouths, form the nesa coating of transmittance height, good conductivity.
Embodiment 8
Disperse back and Resins, epoxy to carry out blend the aerogel carbon nanotube that obtains in the example 2, even back to be mixed adds solidifying agent and has formed carbon nanotube-epoxy resin composition.Form the conductive network of knowing clearly when content of carbon nanotubes surpasses 0.003wt%, its specific conductivity has reached 10 -3S/m as long as add a spot of aerogel carbon nanotube in macromolecule matrix, can realize that promptly this matrix material is as electro-conductive material like this.
Embodiment 9
Disperse back and aluminium sesquioxide to carry out ball milling 12hr the aerogel carbon nanotube that obtains in the example 2 and realize its uniform mixing.In baking oven, dry the composite powder that 24hr obtains aerogel carbon nanotube and aluminium sesquioxide then under 110 ℃.Be 1500 ℃ of following hot pressing 60min under the 20MPa with this composite powder at pressing pressure then, prepare aerogel carbon nanotube-aluminium sesquioxide sample.The density of alumina carrier is 3.80g/cm 3, breaking tenacity is 362MPa, fracture toughness property is at 2.81MPa m 0.5After the aerogel carbon nanotube of adding 1%, the density of alumina carrier is 3.76g/cm 3, breaking tenacity is 420MPa, fracture toughness property is at 5.10MPa m 0.5As can be seen, add aerogel carbon nanotube, improved stupalith toughness, also improved the bending strength of material simultaneously.This mainly is because dispersed carbon nano tube can be pinned on the ceramic crystalline grain crystal boundary, can make the ceramic toughening reinforced composite.

Claims (5)

1. aerogel carbon nanotube is characterized in that: described aerogel carbon nanotube is made up of dispersed carbon nano tube or carbon nanotube tube bank, and the diameter that described carbon nanotube or carbon nanotube are restrained is between 1 nanometer to 100 micron, and length-to-diameter ratio is 10 1-10 6Between, this aerogel carbon nanotube bulk density is 0.1～100g/L.
2. the preparation method of aerogel carbon nanotube according to claim 1 is characterized in that this method comprises the steps:
1) utilize external force with the tube bank of pending carbon nanotube or carbon nano pipe array sample through the one or many fragmentation, forming bulk density is the poly-group of 0.1～100g/L carbon nanotube;
2) utilize air-flow in gas phase, to disperse sedimentation through the sample that step 1) is handled;
3) sediment of the feature that meets aerogel carbon nanotube is collected in classification, obtains described aerogel carbon nanotube.
3. according to the preparation method of the described aerogel carbon nanotube of claim 2, it is characterized in that: described pending carbon nanotube tube bank or carbon nano pipe array sample are one or more in Single Walled Carbon Nanotube tube bank, multi-walled carbon nano-tubes tube bank, single-wall carbon nanotube array or the array of multi-walled carbon nanotubes.
4. according to the preparation method of the described aerogel carbon nanotube of claim 2, it is characterized in that: the external force method described in the step (1) adopts high velocity air shearing, mechanical high-speed shearing, sand milling or explosive method.
5. want as described in 1 aerogel carbon nanotube by the material of forming process as right as heat conduction, conduction, or by with organic polymer, inorganic materials or metallic matrix compound as the structural composite material that strengthens mechanical property, strengthen conductivity functional materials, increase electrode and the functional materials of electrical condenser specific surface area, the functional materials of electromagnetic radiation shielding, matrix material, increased thermal conductivity with electrically conducting transparent performance can functional materials, the application of heat-proof quality excellent function material and catalyst support material.
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