CN102431991A - Carbon nano-tube and nano-particle composite material - Google Patents
Carbon nano-tube and nano-particle composite material Download PDFInfo
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- CN102431991A CN102431991A CN2011102835416A CN201110283541A CN102431991A CN 102431991 A CN102431991 A CN 102431991A CN 2011102835416 A CN2011102835416 A CN 2011102835416A CN 201110283541 A CN201110283541 A CN 201110283541A CN 102431991 A CN102431991 A CN 102431991A
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Abstract
The invention relates to a carbon nano-tube and nano-particle composite material comprising a carbon nano-tube structure and a plurality of nano-particles. The carbon nano-tube structure comprises a plurality of carbon nano-tubes, wherein at least one carbon nano-tube is partially clad in each nano-particle.
Description
Technical field
The present invention relates to a kind of nano composite material and preparation method thereof, relate in particular to a kind of carbon nanotube particulate composite and preparation method thereof.
Background technology
(Carbon Nanotube CNT) is a kind of novel nano line structure to carbon nanotube.Carbon nanotube has great specific surface area, and good machinery and photoelectric properties are widely used in the preparation of matrix material.Nano particle itself has excellent specific properties such as great specific surface area and photochemical catalysis, but nano particle itself is reunited easily.So in carbon nano tube surface, preparation carbon nanotube particulate composite becomes the focus of research with nanoparticulate dispersed.
The notification number of announcing on March 14th, 2007 is that the Chinese patent of CN1304280C discloses a kind of carbon nanotube particulate composite and preparation method thereof.The cobaltosic oxide nano crystalline substance that this carbon nanotube particulate composite comprises a plurality of carbon nanotube dust and is coated on the carbon nanotube powders surface, and cobaltosic oxide nano is brilliant and carbon nanotube forms composite granule.The preparation method of this carbon nanotube particulate composite mainly may further comprise the steps: with carbon nanotube functionalization 6 ~ 8 hours in concentrated nitric acid, introduce hydroxyl, carboxyl isoreactivity functional group in carbon nano tube surface; With the carbon nanotube after the processing of deionized water cleaning function, and oven dry; Cobaltous nitrate hexahydrate is dissolved in the positive ethanol forms mixing solutions; Carbon nanotube was joined in this mixing solutions supersound process 15 ~ 60 minutes, and Cobaltous nitrate hexahydrate is adsorbed in carbon nano tube surface; With mixing solutions reflow treatment 5 ~ 10 hours in silicone oil bath, the Cobaltous nitrate hexahydrate that is adsorbed in carbon nano tube surface is decomposed into tricobalt tetroxide, thereby obtains the tricobalt tetroxide coated carbon nanotube; And the tricobalt tetroxide coated carbon nanotube cleaned respectively with ethane, ethanol, thereby obtain tricobalt tetroxide coated carbon nanotube powder.Yet this carbon nanotube particulate composite and preparation method thereof has following deficiency: preparing method's complex process of carbon nanotube particulate composite, cost is higher, and adopts pharmaceutical chemicals such as concentrated nitric acid, causes environmental pollution easily.
The one Chinese patent application that on September 3rd, 2008, disclosed publication number was CN101255591A discloses composite film material of a kind of carbon nanotube and nanometer nickel and preparation method thereof.The composite film material of this carbon nanotube and nanometer nickel comprises that one deck is deposited on the carbon nano-tube film on the tinsel and is deposited on the nano nickle granules on this carbon nano-tube film.The preparation method of the composite film material of this carbon nanotube and nanometer nickel mainly may further comprise the steps: a metal foil substrate is provided, and this metal foil substrate is carried out surface finish and oil removing skimming treatment; Carbon nanotube is mixed the back supersound process with methyl ethyl diketone, to form an electrophoresis suspensioning liquid; With the metal foil substrate is negative electrode, in above-mentioned electrophoresis suspensioning liquid, feeds direct current, carries out electrophoretic deposition, at metal foil substrate surface deposition one deck carbon nano-tube film; With the metal foil substrate that deposits carbon nano-tube film is that negative electrode is electroplated in a nickel plating solution, at carbon nano-tube film surface deposition nano nickle granules, thereby obtains the composite film material of a carbon nanotube and nanometer nickel.Yet composite film material of this carbon nanotube and nanometer nickel and preparation method thereof has following deficiency: the first, in the composite film material of this carbon nanotube and nanometer nickel; Owing to adopt electro-plating method to prepare the nickel particle; A plurality of nano nickle granules are formed at the carbon nano-tube film surface continuously, are easy to reunite, and make the specific surface area of whole composite film material reduce; So be affected, limited application.The second, the preparation method of the composite film material of this carbon nanotube and nanometer nickel needs electrophoretic deposition and plating, complex process, and cost is higher.
Summary of the invention
In view of this, necessary a kind of carbon nanotube particulate composite with bigger specific surface area is provided.
A kind of carbon nanotube particulate composite, it comprises: a carbon nanotube structure and a plurality of nano particle, this carbon nanotube structure comprises a plurality of carbon nanotubes, wherein, each nano particle partly is coated at least one carbon nanotube wherein.
A kind of carbon nanotube particulate composite; It comprises: the surface that a self supporting structure that is formed by a plurality of carbon nanotubes and a plurality of nano particle are attached to these a plurality of carbon nanotubes; Said a plurality of nano particle is arranged along the length direction compartment of terrain of the carbon nanotube that it adhered to, and each nano particle partly is coated at least one carbon nanotube wherein.
A kind of carbon nanotube particulate composite; It comprises: the surface that a self supporting structure that is formed by a plurality of carbon nanotubes and a plurality of nano particle are attached to these a plurality of carbon nanotubes; Said a plurality of nano particle is arranged along the length direction compartment of terrain of the carbon nanotube that it adhered to, and at least one carbon nanotube runs through at least one nano particle.
Compared to prior art, because said each nano particle partly is coated at least one carbon nanotube wherein or at least one carbon nanotube runs through at least one nano particle, so the bonding force of this carbon nanotube and nano particle is more firm.
Description of drawings
Fig. 1 is the structural representation of carbon nanotube particulate composite provided by the invention.
Fig. 2 is the stereoscan photograph of the carbon nanotube membrane of the present invention's employing.
Fig. 3 is the structural representation of the carbon nanotube fragment in the carbon nanotube membrane among Fig. 2.
Fig. 4 and Fig. 5 are the stereoscan photograph of the carbon nanotube laminate of the present invention's employing.
Fig. 6 is the stereoscan photograph of the carbon nanotube waddingization film of the present invention's employing.
Fig. 7 is the stereoscan photograph of the non-carbon nano tube line that reverses of the present invention's employing.
Fig. 8 is the stereoscan photograph of the carbon nano tube line that reverses of the present invention's employing.
Fig. 9 is preparing method's schema of carbon nanotube particulate composite provided by the invention.
Figure 10 is preparation technology's schema of carbon nanotube particulate composite provided by the invention.
Figure 11 adopts the stereoscan photograph of the carbon nanotube particulate composite of sample 1 preparation for the embodiment of the invention.
Figure 12 adopts the stereoscan photograph of the carbon nanotube particulate composite of sample 2 preparations for the embodiment of the invention.
Figure 13 adopts the stereoscan photograph of the carbon nanotube particulate composite of sample 3 preparations for the embodiment of the invention.
Figure 14 is the transmission electron microscope photo of the carbon nanotube particulate composite among Figure 11.
Embodiment
Below will combine accompanying drawing that each embodiment of carbon nanotube particulate composite and preparation method thereof is done further detailed description.
See also Fig. 1, the embodiment of the invention provides a kind of carbon nanotube particulate composite 10, and it comprises a carbon nanotube structure 100 and a plurality of nano particle 104.Said carbon nanotube structure 100 can be to comprise that a plurality of carbon nanotubes closely are connected to form a self supporting structure through Van der Waals force.So-called self supporting structure is meant that this structure can need not a substrate and keep a specified shape, like wire or membranaceous.Said a plurality of nano particle 104 is uniformly distributed in this carbon nanotube structure 100.
Carbon nanotube in the said carbon nanotube structure 100 comprises one or more in SWCN, double-walled carbon nano-tube and the multi-walled carbon nano-tubes.The diameter of said SWCN is 0.5 nanometer ~ 10 nanometers, and the diameter of double-walled carbon nano-tube is 1.0 nanometers ~ 15 nanometers, and the diameter of multi-walled carbon nano-tubes is 1.5 nanometers ~ 50 nanometers.The length of said carbon nanotube is greater than 50 microns.Preferably, the length of this carbon nanotube is 200 ~ 900 microns.
Said carbon nanotube structure 100 comprises at least one carbon nano-tube film, at least one liner structure of carbon nano tube or its combination.Said carbon nano-tube film comprises a plurality of equally distributed carbon nanotubes.Carbon nanotube ordered arrangement or lack of alignment in this carbon nano-tube film.When carbon nano-tube film comprised the carbon nanotube of lack of alignment, carbon nanotube twined each other or isotropy is arranged; When carbon nano-tube film comprised orderly carbon nanotubes arranged, carbon nanotube was arranged of preferred orient along a direction or a plurality of directions.Particularly, this carbon nano-tube film can comprise carbon nanotube waddingization film, carbon nanotube laminate or carbon nanotube membrane.This liner structure of carbon nano tube comprises at least one non-carbon nano tube line that reverses, at least one carbon nano tube line that reverses or its combination.When said liner structure of carbon nano tube comprises the many non-carbon nano tube lines that reverse or during the carbon nano tube line that reverses, this non-carbon nano tube line that reverses or the carbon nano tube line that reverses can be parallel to each other and be a pencil structure, or reverse each other and be the hank line structure.
See also Fig. 2 and Fig. 3, particularly, this carbon nanotube membrane comprise a plurality of continuously and the carbon nanotube fragment 143 that aligns.This a plurality of carbon nanotube fragment 143 joins end to end through Van der Waals force.Each carbon nanotube fragment 143 comprises a plurality of carbon nanotubes that are parallel to each other 145, and this a plurality of carbon nanotube that is parallel to each other 145 is combined closely through Van der Waals force.This carbon nanotube fragment 143 has width, thickness, homogeneity and shape arbitrarily.Carbon nanotube 145 in this carbon nanotube membrane is arranged of preferred orient along same direction.Be appreciated that in the carbon nanotube structure of forming by a plurality of carbon nanotube membranes 100 orientation of the carbon nanotube in adjacent two carbon nanotube membranes has an angle; And 0 °≤α≤90 °; Form a reticulated structure thereby carbon nanotube in the adjacent two layers carbon nanotube membrane is intersected each other, this reticulated structure comprises a plurality of micropores, these a plurality of micropores evenly and regular distribution in carbon nanotube structure; Wherein, this micro-pore diameter is 1 nanometer ~ 0.5 micron.The thickness of said carbon nanotube membrane is 0.01 ~ 100 micron.Said carbon nanotube membrane can directly obtain through pulling a carbon nano pipe array.Structure of said carbon nanotube membrane and preparation method thereof sees also people such as Fan Shoushan in application on February 9th, 2007; In disclosed CN101239712A number Chinese publication application " carbon nano-tube thin-film structure and preparation method thereof " in Augusts 13 in 2008; Applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be regarded as application technology of the present invention exposure.
Said carbon nanotube laminate comprises equally distributed carbon nanotube.See also Fig. 4, carbon nanotube is arranged of preferred orient along same direction.See also Fig. 5, carbon nanotube is arranged of preferred orient along different directions.Preferably, the carbon nanotube in the said carbon nanotube laminate is parallel to the surface of carbon nanotube laminate.Carbon nanotube in the said carbon nanotube laminate overlaps each other, and attracts each other through Van der Waals force, combines closely, and makes this carbon nanotube laminate have good flexible, can bending fold becomes random shape and does not break.And owing to attract each other through Van der Waals force between the carbon nanotube in the carbon nanotube laminate, combine closely, making the carbon nanotube laminate is the structure of a self-supporting, can need not substrate support.Said carbon nanotube laminate can obtain through rolling a carbon nano pipe array.Carbon nanotube in the said carbon nanotube laminate forms an angle with the surface of the substrate that forms carbon nano pipe array; Wherein, α is more than or equal to 0 degree and smaller or equal to 15 degree (0≤α≤15 °); This angle is with to be applied to the pressure that carbon nano-pipe array lists relevant, and pressure is big more, and this angle is more little.The length and the width of said carbon nanotube laminate are not limit.Said laminate comprises a plurality of microvoid structures, this microvoid structure evenly and regular distribution in the carbon nanotube laminate, wherein micro-pore diameter is 1 nanometer ~ 0.5 micron.Said carbon nanotube laminate and preparation method thereof sees also people such as Fan Shoushan in application on June 1st, 2007; In disclosed CN101314464A one Chinese patent application on December 3 " preparation method of carbon nano-tube film " in 2008; Applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be regarded as application technology of the present invention exposure.
Length, width and the thickness of said carbon nanotube waddingization film are not limit, and can select according to actual needs.The length of the carbon nanotube waddingization film that the embodiment of the invention provides is 1 ~ 10 centimetre, and width is 1 ~ 10 centimetre, and thickness is 1 micron ~ 2 millimeters.See also Fig. 6, said carbon nanotube waddingization film comprises the carbon nanotube of mutual winding, and the length of carbon nanotube is greater than 10 microns.Attract each other, twine through Van der Waals force between the said carbon nanotube, form network-like structure.Even carbon nanotube in the said carbon nanotube waddingization film distributes, and random arrangement makes this carbon nanotube waddingization film isotropy, and a large amount of micropore of formation between the carbon nanotube in the said carbon nanotube waddingization film, micropore size are 1 nanometer ~ 0.5 micron.Said carbon nanotube waddingization film and preparation method thereof sees also people such as Fan Shoushan in application on April 13rd, 2007; In disclosed CN101284662A one Chinese patent application on October 15 " preparation method of carbon nano-tube film " in 2008; Applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be regarded as application technology of the present invention exposure.
See also Fig. 7, this non-carbon nano tube line that reverses comprises this non-carbon nano tube line length direction carbon nanotubes arranged of reversing of a plurality of edges.Particularly, this non-carbon nano tube line that reverses comprises a plurality of carbon nanotube fragments, and these a plurality of carbon nanotube fragments join end to end through Van der Waals force, and each carbon nanotube fragment comprises a plurality of carbon nanotubes that are parallel to each other and combine closely through Van der Waals force.This carbon nanotube fragment has length, thickness, homogeneity and shape arbitrarily.This non-carbon nanotube line length of reversing is not limit, and diameter is 0.5 nanometer ~ 100 micron.The non-carbon nano tube line that reverses obtains for the carbon nanotube membrane is handled through organic solvent.Particularly; Organic solvent is soaked into the whole surface of said carbon nanotube membrane; Under the capillary effect that when volatile organic solvent volatilizees, produces; The a plurality of carbon nanotubes that are parallel to each other in the carbon nanotube membrane are combined closely through Van der Waals force, thereby make the carbon nanotube membrane be punctured into a non-carbon nano tube line that reverses.This organic solvent is a volatile organic solvent, like ethanol, methyl alcohol, acetone, ethylene dichloride or chloroform, adopts ethanol in the present embodiment.The non-carbon nano tube line that reverses through organic solvent is handled is compared with the carbon nano-tube film of handling without organic solvent, and specific surface area reduces, and viscosity reduces.
The said carbon nano tube line that reverses reverses acquisition for adopting a mechanical force with said carbon nanotube membrane two ends in opposite direction.See also Fig. 8, this carbon nano tube line that reverses comprises a plurality of around this carbon nano tube line axial screw carbon nanotubes arranged of reversing.Particularly, this carbon nano tube line that reverses comprises a plurality of carbon nanotube fragments, and these a plurality of carbon nanotube fragments join end to end through Van der Waals force, and each carbon nanotube fragment comprises a plurality of carbon nanotubes that are parallel to each other and combine closely through Van der Waals force.This carbon nanotube fragment has length, thickness, homogeneity and shape arbitrarily.The carbon nanotube line length that this reverses is not limit, and diameter is 0.5 nanometer ~ 100 micron.Further, can adopt a volatile organic solvent to handle this carbon nano tube line that reverses.Under the capillary effect that when volatile organic solvent volatilizees, produces, adjacent carbon nanotube is combined closely through Van der Waals force in the carbon nano tube line that reverses after the processing, and the specific surface area of the carbon nano tube line that reverses is reduced, and density and intensity increase.
Said liner structure of carbon nano tube and preparation method thereof sees also people such as Fan Shoushan in application on September 16th, 2002; CN100411979C number China's bulletin patent " a kind of carbon nanotube rope and method of manufacture thereof " in bulletin on August 20th, 2008; Applicant: Tsing-Hua University; Hongfujin Precise Industry (Shenzhen) Co., Ltd., and on December 16th, 2005 application, in disclosed CN1982209A number Chinese publication application " carbon nano-tube filament and preparation method thereof " on June 20 in 2007; Applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be regarded as application technology of the present invention exposure.
Said a plurality of nano particle 104 keeps at a certain distance away and is arranged in the carbon nanotube structure 100.Said nano particle 104 is attached on the carbon nano tube surface, and arranges along the carbon nanotube compartment of terrain that it adhered to.Preferably, the distance between the adjacent nano particle 104 can be more than or equal to the particle diameter of said nano particle 104.The particle diameter of said nano particle 104 can be more than or equal to 1 nanometer and smaller or equal to 500 nanometers.Preferably, the particle diameter of said nano particle 104 is more than or equal to 50 nanometers and smaller or equal to 200 nanometers.In the said carbon nanotube particulate composite 10, each nano particle 104 is coated on the part surface of at least one carbon nanotube, promptly all has at least one carbon nanotube partly to be coated on wherein in each nano particle 104.When being appreciated that size when carbon nanotube is less than nano particle 104 sizes, this nano particle 104 can be coated on the surface of whole carbon nanotube, and promptly whole carbon nanotube is coated in the nano particle 104.Said a plurality of carbon nanotube is formed carbon nano-tube bundle, and at least between the part nano particle 104 at a distance from being attached on the above-mentioned carbon nano-tube bundle, and arrange along this carbon nano-tube bundle length direction.When said a plurality of carbon nanotube twined each other, the part at least of the carbon nanotube of a plurality of mutual windings was coated in the nano particle 104.Carbon nanotube or carbon nano-tube bundle surface can be formed with the nano particle 104 that a plurality of intervals are provided with this carbon nanotube or carbon nano-tube bundle are partly coated.Because nano particle 104 is coated at least one carbon nano tube surface, combine closely through Van der Waals force or chemical bond between said nano particle 104 and the carbon nanotube, so nano particle 104 and firm the combining of carbon nanotube.Owing to have the gap between the carbon nanotube in the carbon nanotube structure, and a plurality of nano particle 104 is arranged at intervals in this carbon nanotube structure, so this carbon nanotube particulate composite 10 has bigger specific surface area.
Said nano particle 104 comprises one or more in metal nanoparticle, nonmetal nano particle, alloy nanoparticle, metal oxide nanoparticles and the polymer nano granules.Said metal oxide nanoparticles comprises one or more in titania nanoparticles, Zinc oxide nanoparticle, nickel oxide nano particle and the aluminum oxide nanoparticle.Present embodiment, said nano particle 104 is a titania nanoparticles.The shape of said nano particle 104 is not limit, and can be in spherical, ellipsoid shape etc. one or more.When said carbon nanotube structure 100 comprised a plurality of carbon nano tube line parallel or arranged in a crossed manner, said a plurality of nano particles 104 aligned along each carbon nano tube line.Adjacent two nano particles 104 are provided with at interval, and each nano particle 104 coats at least one carbon nanotube in the said carbon nano tube line.The size of said nano particle 104 is even, and promptly the grain size distribution range of nano particle 104 is less.In the present embodiment, the grain size of said nano particle 104 is more than or equal to 80 nanometers and smaller or equal to 120 nanometers.
Carbon nanotube particulate composite 10 provided by the present invention has the following advantages: first; Owing to have the gap between the carbon nanotube in the carbon nanotube structure; And a plurality of nano particles 104 are arranged at intervals in this carbon nanotube structure; So this carbon nanotube particulate composite 10 has bigger specific surface area, can be used as excellent catalystic material.The second, because the even carbon nanotube in the said carbon nanotube structure 100 distributes, and each nano particle 104 is coated at least one carbon nanotube part surface, reunites so nano particle 104 is difficult for forming.The 3rd, because said carbon nanotube structure 100 has the self-supporting characteristic, so this carbon nanotube particulate composite 10 is a self supporting structure.And the carbon nanotube in this carbon nanotube structure 100 has favorable conductive and thermal conductivity, and therefore, carbon nanotube structure 100 can play the function that supports and transmit.
See also Fig. 9 and Figure 10, the embodiment of the invention further provides the preparation method of above-mentioned carbon nanotube particulate composite 10, and it may further comprise the steps:
Step 1 provides a carbon nanotube structure 100.
Said carbon nanotube structure 100 comprises a plurality of carbon nanotubes, and a plurality of carbon nanotube is combined closely through Van der Waals force and formed a self supporting structure.Particularly, said carbon nanotube structure 100 comprises at least one carbon nano-tube film, at least one liner structure of carbon nano tube or its combination.Said carbon nano-tube film can comprise carbon nanotube waddingization film, carbon nanotube laminate or carbon nanotube membrane.Said carbon nanotube membrane, the carbon nanotube laminate, the preparation method of carbon nanotube waddingization film and liner structure of carbon nano tube sees also related patent U.S. Patent No. or patented claim.
Said carbon nanotube structure 100 can further be arranged on the supporter.This supporter can be substrate or framework.
In the present embodiment, two range upon range of being laid on of carbon nanotube membrane are obtained a carbon nanotube structure 100 on the metal ring, and the carbon nanotube orientation is identical in two carbon nanotube membranes.
The material of said reaction raw materials 102 is relevant with the material of the nano particle of required formation 104.Said reaction raw materials 102 can be solid-state, liquid state or gaseous state.The said method of in carbon nanotube structure 100, introducing at least two kinds of reaction raw materials 102 specifically comprises two kinds of situations.
First kind: at first, forming a layer thickness in these carbon nanotube structure 100 surfaces is the first reaction raw materials layer of 1 ~ 100 nanometer.
The material of the said first reaction raw materials layer with the material of the nano particle 104 that will prepare relevant, can be in metal, the nonmetal and semi-conductor one or more.For example, when the material of nano particle 104 is a metallic compound, like MOX or metal silicide, the first reaction raw materials layer is a metal level, like titanium layer, aluminium lamination or nickel dam etc.; When the material of nano particle 104 is a nonmetallic compound, like silicon nitride or silit, the first reaction raw materials layer is a silicon layer.
The carbon nanotube structure that the is set forth in 100 surface methods that form one first reaction raw materials layers do not limit, can comprise in physical vaporous deposition, chemical Vapor deposition process, pickling process, spraying method and the silk screen print method etc. one or more.Be appreciated that material difference, can select the carbon nano tube surface of diverse ways in carbon nanotube structure 100 to form the material of the first reaction raw materials layer according to the first reaction raw materials layer.For example, can be through physical vaporous deposition with metal sputtering to carbon nano tube surface; Can form nonmetal in carbon nano tube surface through chemical Vapor deposition process; Can the organic ink that contain metal be formed at the surface of carbon nanotube through spraying method or silk screen print method.
Secondly, introduce gaseous state or liquid second reaction raw materials to this carbon nanotube structure 100.
Said gaseous state second reaction raw materials can be in oxygen, nitrogen, silicon source gas and the carbon-source gas one or more.Said method from gaseous state second reaction raw materials to carbon nanotube structure 100 that introduce can comprise directly gaseous state second reaction raw materials being passed into the reaction chamber (figure does not show) that is provided with carbon nanotube structure 100 or carbon nanotube structure 100 being arranged at one and contain in the atmosphere of gaseous state second reaction raw materials, thereby gaseous state second reaction raw materials is distributed in around the carbon nanotube structure 100 and the first reaction raw materials layer.
Said liquid second reaction raw materials can be in methyl alcohol, ethanol, acetone and the liquid resin etc. one or more.Said method from liquid second reaction raw materials to carbon nanotube structure 100 that introduce can comprise and directly liquid second reaction raw materials dripped to carbon nanotube structure 100 surfaces or carbon nanotube structure 100 is infiltrated in liquid second reaction raw materials, thereby liquid second reaction raw materials is distributed in around the carbon nanotube structure 100 and the first reaction raw materials layer.
Second kind: at first, form one first reaction raw materials layer in these carbon nanotube structure 100 surfaces; Secondly, on this first reaction raw materials layer, form one second reaction raw materials layer.The total thickness of the said first reaction raw materials layer and the second reaction raw materials layer is 1 ~ 100 nanometer.As, the first reaction raw materials layer is a metal level, the second reaction raw materials layer is a silicon layer; The first reaction raw materials layer and the second reaction raw materials layer are metal level, as: the first reaction raw materials layer and the second reaction raw materials layer are aluminium lamination and titanium layer, aluminium lamination and nickel dam etc. respectively.
Be appreciated that when the thickness of the reaction raw materials layer that be deposited on said carbon nanotube structure 100 surfaces hour, be 1 ~ 100 nanometer like thickness, can form the nano particle 104 at a plurality of intervals after the reaction raw materials reaction.When the thickness of the reaction raw materials layer on said carbon nanotube structure 100 surfaces was big, as greater than 100 nanometers, reaction raw materials reaction back formed the successive nano wire easily.
The requirement that is appreciated that 102 pairs of thickness of different reaction raw materials is different.In the present embodiment, deposit a titanium layer respectively on carbon nanotube structure 100 relative two sides through magnetron sputtering method.Present embodiment has prepared 3 samples, and wherein, the thickness of titanium layer is respectively 10 nanometers, 20 nanometers, 50 nanometers in the sample 1 to 3.Then, this carbon nanotube structure 100 that deposits titanium layer is placed atmospheric environment, make the titanium particle on carbon nanotube structure 100 surface contact with oxygen in the atmosphere.When the thickness of titanium layer is 10 ~ 50 nanometers, can form the titania nanoparticles at a plurality of intervals behind titanium layer and the oxygen reaction.When the thickness of titanium layer during, form the successive titanium dioxide nano thread behind titanium layer and the oxygen reaction easily greater than 50 nanometers.
Step 3, initiation reaction raw material 102 reacts, and generates nano particle 104, thereby obtains a carbon nanotube particulate composite 10.
The method that said initiation reaction raw material 102 reacts comprises heating, uses electrical spark, and with in the laser scanning one or more.Be appreciated that difference, can select diverse ways to come initiation reaction raw material 102 to react according to reaction conditions.As making silicon and carbon source solid/liquid/gas reactions prepare the nanometer silicon carbide particle through heating; Can make metal and oxygen reaction prepare metal oxide nanoparticles through laser scanning.
In the present embodiment, adopt laser scanning initiation reaction raw material 102 to react.Adopt laser scanning initiation reaction raw material 102 to react and comprise two kinds of situations: first kind of surface for the whole carbon nanotube structure 100 of employing laser scanning reacted the reaction raw materials 102 on carbon nanotube structure 100 surfaces; Second kind for adopting the part surface of laser scanning carbon nanotube structure 100, and the reaction raw materials 102 that makes carbon nanotube structure 100 surfaces is begun to carry out the self-diffusion reaction along the carbon nanotube orientation by the position of laser scanning.When adopting second method, can carbon nanotube structure 100 be arranged on the substrate (figure does not show), the substrate through selecting different thermal conductivitys is with the speed of control growing nano particle 104.The thermal conductivity of said substrate is big more, and heat is just fast more to the substrate conduction, and just slow more along the conduction of carbon nanotube direction, the speed of growth of nano particle 104 is slow more.Otherwise then the speed of growth is fast more.Because the thermal conductivity of air is very little, so when carbon nanotube structure 100 unsettled settings, nano particle 104 has optimum growth speed.In addition, the part surface that can also realize carbon nanotube structure 100 through the position of selecting laser scanning is growing nano particle 104 selectively.
Be appreciated that because the thickness of said reaction raw materials layer is 1 ~ 100 nanometer, can't form successive nanometer film or nano wire after reaction raw materials 102 reactions, and growth obtain a plurality of nano particles 104.These nano particle 104 homodisperse, and be coated on carbon nano tube surface and carbon nanotube is combined closely.Since the carbon nanotube in the carbon nanotube structure 100 that is adopted among the present invention through Van der Waals force combine closely form one have the self-supporting characteristic carbon nanotube structure 100, also have self supporting structure so this reaction obtains carbon nanotube particulate composite 10.
In the present embodiment, adopt laser scanning carbon nanotube structure frontside edge, cause the self-diffusion reaction, obtain carbon nanotube titania nanoparticles matrix material.Wherein, the speed of laser scanning is 10 ~ 200 cels, and the power of laser scanning is more than or equal to 0.5 watt.The speed of this self-diffusion reaction is greater than 10 cels.
See also Figure 11 to 13, it is respectively the carbon nanotube titania nanoparticles matrix material that present embodiment adopts sample 1 to 3 preparation.Said carbon nanotube titania nanoparticles matrix material comprises carbon nanotube structure and a plurality of equally distributed titania nanoparticles.When the titanium layer thickness of carbon nanotube structure 100 surface depositions hour, the size of the titania nanoparticles of formation evenly, promptly the grain size distribution range of titania nanoparticles is less.And along with the titanium layer thickness increase of carbon nanotube structure 100 surface depositions, it is big that the grain size distribution range of the titania nanoparticles of formation becomes.See also Figure 14, be the transmission electron microscope photo of the carbon nanotube particulate composite among Figure 11.Each titania nanoparticles is coated on a plurality of carbon nano tube surface, and the carbon nano-tube bundle that is promptly formed by a plurality of carbon nanotubes partly is coated in the titania nanoparticles.
The present invention is formed on the surface of carbon nanotube structure 100 through initiation reaction raw materials 102 reaction growing nano particles 104 prepare carbon nanotube particulate composite 10, and technology is simple, and is with low cost.
In addition, those skilled in the art also can do other variations in spirit of the present invention, and certainly, these all should be included within the present invention's scope required for protection according to the variation that the present invention's spirit is done.
Claims (10)
1. carbon nanotube particulate composite, it comprises: a carbon nanotube structure and a plurality of nano particle, this carbon nanotube structure comprises a plurality of carbon nanotubes, it is characterized in that, each nano particle coats the part surface of at least one carbon nanotube.
2. carbon nanotube particulate composite as claimed in claim 1 is characterized in that, said at least one carbon nanotube runs through at least one nano particle.
3. carbon nanotube particulate composite as claimed in claim 1; It is characterized in that; Said carbon nanotube structure comprises at least one carbon nano-tube bundle; This carbon nano-tube bundle is laterally arranged by a plurality of carbon nanotubes and forms, and the part surface of at least two carbon nanotubes that this carbon nanotube is intrafascicular is coated by a nano particle.
4. carbon nanotube particulate composite as claimed in claim 1 is characterized in that, said carbon nanotube structure comprises a plurality of carbon nanotubes that join end to end and be arranged of preferred orient along same direction.
5. carbon nanotube particulate composite as claimed in claim 1 is characterized in that said carbon nanotube structure comprises the carbon nanotube of a plurality of windings.
6. carbon nanotube particulate composite as claimed in claim 1 is characterized in that, said carbon nanotube structure comprise a plurality of parallel, intersect or liner structure of carbon nano tube that braiding is provided with.
7. carbon nanotube particulate composite as claimed in claim 1 is characterized in that, said nano particle comprises one or more in titania nanoparticles, Zinc oxide nanoparticle, nickel oxide nano particle and the aluminum oxide nanoparticle.
8. carbon nanotube particulate composite, it is characterized in that it comprises: a carbon nanotube structure, this carbon nanotube structure comprise that a plurality of carbon nanotubes interconnect through Van der Waals force; And a plurality of nano particles are attached to the surface of a plurality of carbon nanotubes in this carbon nanotube structure, and each nano particle coats the part surface of at least two carbon nanotubes simultaneously.
9. carbon nanotube particulate composite as claimed in claim 8 is characterized in that each nano particle is coated on two parallel carbon nanotubes wherein at least.
10. carbon nanotube particulate composite; It is characterized in that; It comprises: the surface that a self supporting structure that is formed by a plurality of carbon nanotubes and a plurality of nano particle are attached to these a plurality of carbon nanotubes, at least one carbon nanotube runs through at least one nano particle.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190948A (en) * | 2014-08-25 | 2014-12-10 | 西安近代化学研究所 | Method for preparing carbon nanotube - aluminium powder composite material |
| CN104882346A (en) * | 2015-04-02 | 2015-09-02 | 天津师范大学 | Method for preparing field emission cathode of carbon nanotube array coated with carbon nanoparticles |
| CN105097428A (en) * | 2014-04-24 | 2015-11-25 | 清华大学 | Carbon nanotube composite membrane |
| CN106058273A (en) * | 2016-05-26 | 2016-10-26 | 昆明理工大学 | Method for modifying and treating carbon nanotube by nickel oxide to prepare supported palladium nano-catalyst |
| CN116374999A (en) * | 2023-03-21 | 2023-07-04 | 华中科技大学 | Thermal interface material interconnected through secondary carbon nano tubes and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982209A (en) * | 2005-12-16 | 2007-06-20 | 清华大学 | Carbon nano-tube filament and its production |
| CN101239712A (en) * | 2007-02-09 | 2008-08-13 | 清华大学 | Carbon nano-tube thin film structure and preparation method thereof |
| CN101372330A (en) * | 2008-10-08 | 2009-02-25 | 长沙理工大学 | Method for coating carbon nano-tube with metal doped zinc oxide nano-particle |
-
2009
- 2009-03-21 CN CN2011102835416A patent/CN102431991A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982209A (en) * | 2005-12-16 | 2007-06-20 | 清华大学 | Carbon nano-tube filament and its production |
| CN101239712A (en) * | 2007-02-09 | 2008-08-13 | 清华大学 | Carbon nano-tube thin film structure and preparation method thereof |
| CN101372330A (en) * | 2008-10-08 | 2009-02-25 | 长沙理工大学 | Method for coating carbon nano-tube with metal doped zinc oxide nano-particle |
Non-Patent Citations (1)
| Title |
|---|
| JOSHUA M. GREEN ET AL.: "ZnO-nanoparticle-coated carbon nanotubes demonstrating enhanced electron field-emission properties", 《JOURNAL OF APPLIED PHYSICS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105097428A (en) * | 2014-04-24 | 2015-11-25 | 清华大学 | Carbon nanotube composite membrane |
| CN105097428B (en) * | 2014-04-24 | 2017-12-01 | 清华大学 | Carbon nano-tube compound film |
| CN104190948A (en) * | 2014-08-25 | 2014-12-10 | 西安近代化学研究所 | Method for preparing carbon nanotube - aluminium powder composite material |
| CN104882346A (en) * | 2015-04-02 | 2015-09-02 | 天津师范大学 | Method for preparing field emission cathode of carbon nanotube array coated with carbon nanoparticles |
| CN106058273A (en) * | 2016-05-26 | 2016-10-26 | 昆明理工大学 | Method for modifying and treating carbon nanotube by nickel oxide to prepare supported palladium nano-catalyst |
| CN106058273B (en) * | 2016-05-26 | 2018-08-31 | 昆明理工大学 | The method for preparing load type palladium nanocatalyst using nickel oxide moditied processing carbon nanotube |
| CN116374999A (en) * | 2023-03-21 | 2023-07-04 | 华中科技大学 | Thermal interface material interconnected through secondary carbon nano tubes and preparation method thereof |
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