CN101868065B - Preparation method of plane heat source - Google Patents

Preparation method of plane heat source Download PDF

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Publication number
CN101868065B
CN101868065B CN200910106600.5A CN200910106600A CN101868065B CN 101868065 B CN101868065 B CN 101868065B CN 200910106600 A CN200910106600 A CN 200910106600A CN 101868065 B CN101868065 B CN 101868065B
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China
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carbon nano
tube
nano tube
tube structure
electrode
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CN101868065A (en
Inventor
冯辰
刘锴
王佳平
姜开利
刘长洪
范守善
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Priority to CN200910106600.5A priority Critical patent/CN101868065B/en
Priority to US12/655,507 priority patent/US20100122980A1/en
Priority to US12/658,198 priority patent/US20100147830A1/en
Priority to US12/658,184 priority patent/US20100147828A1/en
Priority to US12/658,193 priority patent/US20100147829A1/en
Priority to US12/658,182 priority patent/US20100147827A1/en
Priority to US12/658,237 priority patent/US20100154975A1/en
Priority to US12/660,356 priority patent/US20110024410A1/en
Priority to US12/660,820 priority patent/US20100163547A1/en
Priority to US12/661,115 priority patent/US20100200567A1/en
Priority to US12/661,110 priority patent/US20100218367A1/en
Priority to US12/661,133 priority patent/US20100200568A1/en
Priority to US12/661,165 priority patent/US20100170891A1/en
Priority to US12/661,150 priority patent/US20100170890A1/en
Priority to US12/661,926 priority patent/US20100187221A1/en
Priority to US12/750,186 priority patent/US20100180429A1/en
Priority to JP2010097284A priority patent/JP5457258B2/en
Publication of CN101868065A publication Critical patent/CN101868065A/en
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Abstract

The invention relates a preparation method of a plane heat source, comprising the following steps: providing a carbon nano-tube structure; alternately arranging a first electrode and a second electrode which are in electric connection with the carbon nano-tube structure; providing a matrix precursor; and finally compounding the matrix precursor with the carbon nano-tube structure to form a carbon nano-tube composite structure.

Description

The preparation method of plane heat source
Technical field
The present invention relates to a kind of preparation method of plane heat source, relate in particular to a kind of preparation method of the plane heat source based on carbon nano-tube.
Background technology
Thermal source plays an important role in people's production, life, scientific research.Plane heat source is the one of thermal source.Plane heat source is two-dimensional structure, and heat object the top that heated material is placed in to this two-dimensional structure, and therefore, plane heat source can heat each position of heated material simultaneously, heating surface is large, homogeneous heating and efficiency higher.Plane heat source is successfully for industrial circle, scientific research field or sphere of life etc., as electric heater, electric blanket, infrared therapeutic apparatus and electric heater etc.
Existing plane heat source generally comprises a heating element and at least two electrodes, and these at least two electrodes are arranged at the surface of this heating element, and is electrically connected with this heating element.In the time passing into voltage or electric current by electrode to heating element, because heating element has larger resistance, pass into the electric energy energy transform into heat energy of heating element, and discharge from heating element.Commercially available plane heat source adopts the heating wire that wire or carbon fiber are made to carry out electric heating conversion as heating element conventionally now.
But wire or carbon fiber all have the shortcoming that intensity is not high, electric conversion efficiency is lower and quality is larger.Wire is easy to fracture, and particularly repeatedly bending or in the time being converted into certain angle, easily produce tiredly, therefore application is restricted.In addition, the heat that heating wire was produced made from wire or carbon fiber is to extraradial with common wavelength, its electric conversion efficiency is not high is unfavorable for saving the energy, need add snearing to have the cotton thread of far ultrared paint to improve electric conversion efficiency, is unfavorable for energy-conserving and environment-protective.Carbon fiber and quality wiry are all larger, are unfavorable for making thermal source lightness.Meanwhile, carbon fiber size is not little, is unfavorable for being applied to miniature thermal source.
Since the early 1990s, (refer to Helical microtubules of graphitic carbon with carbon nano-tube, Nature, Sumio Iijima, vol 354, p56 (1991)) cause that with its unique structure and character people pay close attention to greatly for the nano material of representative.In recent years, along with deepening continuously of carbon nano-tube and nano materials research, its wide application prospect constantly displayed.The people such as Fan Shoushan disclose a kind of nanometer flexible electric heating material on December 19th, 2007 in No. CN101090586Ath, a disclosed Chinese patent application.This thermo electric material comprises a flexible substrate and is dispersed in the multiple carbon nano-tube in described flexible substrate.The plurality of carbon nano-tube exists with powdered form, and adhesion is very weak to each other, cannot form a self supporting structure with given shape.When the carbon nano-tube of this powdered form is mixed with polymer solution, the carbon nano-tube of this powdered form is very easily reunited, thereby it is inhomogeneous to cause carbon nano-tube to be disperseed in matrix.Agglomeration while dispersion in polymer solution for fear of carbon nano-tube, on the one hand, in the process of disperseing, need to process by supersonic oscillations the mixture of this carbon nano-tube and polymer solution, on the other hand, in this thermo electric material, the quality percentage composition of carbon nano-tube can not be too high, is only 0.1～4%.
And carbon nano-tube is through after above-mentioned dispersion treatment, even if carbon nano-tube can be in contact with one another to each other, its adhesion also a little less than, cannot form the carbon nano tube structure of a self-supporting.Because content of carbon nanotubes is few, the thermal response speed of thermoelectric material is fast not, and electric conversion efficiency is not high enough, therefore the heating temp of this thermo electric material is not high enough, has limited its range of application.In addition, for carbon nano-tube is disperseed in liquid phase, while preparing thermo electric material, its flexible substrate can only selective polymer material, polymeric material heat resisting temperature is lower, and the method for this kind of employing dispersing Nano carbon tubes formation thermo electric material in liquid phase has limited the selection of basis material.
Summary of the invention
In view of this, necessaryly provide a kind of electric conversion efficiency higher, the preparation method of the plane heat source of heating temp wider range.
A kind of preparation method of plane heat source, it comprises: the membranaceous carbon nano tube structure that the one of multiple self-supportings is provided, make the setting of multiple membranaceous carbon nano tube structures space, wherein, each membranaceous carbon nano tube structure comprises multiple carbon nano-tube, the plurality of carbon nano-tube attracts each other by Van der Waals force, thereby forms a network configuration; Interval formation one first electrode and one second electrode are on described each carbon nano tube structure surface, and form and be electrically connected with this carbon nano tube structure, and provide a matrix precursor, by the membranaceous carbon nano tube structure direct combination of multiple self-supportings of the setting of matrix precursor and space, form a composite structure of carbon nano tube, each carbon nano tube structure described in this composite structure of carbon nano tube keeps not compound shape before.
A kind of preparation method of plane heat source, it comprises: the membranaceous carbon nano tube structure that the one of multiple self-supportings is provided, make the setting of multiple membranaceous carbon nano tube structures space, wherein, each membranaceous carbon nano tube structure comprises multiple carbon nano-tube, the plurality of carbon nano-tube attracts each other by Van der Waals force, thereby forms a network configuration; One matrix precursor is provided, by the carbon nano tube structure direct combination of multiple self-supportings of the setting of matrix precursor and space, forms a heating element, each carbon nano tube structure described in this heating element keeps not compound shape before; And interval forms one first electrode and one second electrode on described each carbon nano tube structure surface, and form and be electrically connected with heating element.
A preparation method for plane heat source, it comprises the following steps: the membranaceous carbon nano tube structure of the one of a self-supporting is provided, and it comprises multiple carbon nano-tube, and the plurality of carbon nano-tube attracts each other by Van der Waals force, thereby forms a network configuration; Interval forms one first electrode and one second electrode on described carbon nano tube structure surface, and forms and be electrically connected with this carbon nano tube structure; One matrix precursor is provided, by the membranaceous carbon nano tube structure direct combination of matrix precursor and self-supporting, forms a heating element, carbon nano tube structure described in this heating element keeps not compound shape before; One supporter and a reflector are provided, and reflector is formed at supporting body surface; And, described heating element is arranged to surface, reflector.
Compared with prior art, the carbon nano tube structure of this formation self-supporting, and by simple the method for this carbon nano tube structure and matrix direct combination formation heating element, and the content of carbon nano-tube in heating element can be controlled easily.After compound with matrix, this carbon nano tube structure still can keep original form, has the heating property suitable with pure nano-carbon tube structure.
Brief description of the drawings
Fig. 1 is the structural representation of the plane heat source of first embodiment of the invention.
Fig. 2 is the generalized section of Fig. 1 along II-II line.
Fig. 3 is the structural representation that the embodiment of the present invention comprises the plane heat source of multiple cross one another liner structure of carbon nano tube.
Fig. 4 is the structural representation that the embodiment of the present invention comprises the plane heat source of the liner structure of carbon nano tube of a bending coiling.
Fig. 5 is the structural representation of carbon nano-tube fragment in the carbon nano-tube membrane structure in embodiment of the present invention plane heat source.
Fig. 6 is the stereoscan photograph of the carbon nano-tube membrane structure in embodiment of the present invention plane heat source.
Fig. 7 is the stereoscan photograph of the carbon nano-tube waddingization membrane structure in embodiment of the present invention plane heat source.
Fig. 8 is the stereoscan photograph that in the carbon nano-tube laminate structure in embodiment of the present invention plane heat source, carbon nano-tube is arranged of preferred orient along different directions.
Fig. 9 is the stereoscan photograph that in the carbon nano-tube laminate structure in embodiment of the present invention plane heat source, carbon nano-tube is arranged of preferred orient in the same direction.
Figure 10 is the stereoscan photograph of the carbon nano tube line of the non-torsion in embodiment of the present invention plane heat source.
Figure 11 is the stereoscan photograph of the carbon nano tube line of the torsion in embodiment of the present invention plane heat source.
Figure 12 is the truncation surface stereoscan photograph of the heating element that is compounded to form of carbon nano-tube membrane in embodiment of the present invention plane heat source and epoxy resin.
Figure 13 is the structural representation that the embodiment of the present invention comprises the plane heat source of the carbon nano tube structure of multiple spaces.
Figure 14 uses heating element in Figure 12 temperature variation curve under different voltage.
Figure 15 is the structural representation of the plane heat source of second embodiment of the invention.
Figure 16 is the generalized section of Figure 15 along XVI-XVI line.
Figure 17 is the structural representation of the plane heat source of third embodiment of the invention.
Figure 18 is embodiment of the present invention plane heat source preparation method's flow chart.
Figure 19 is the photo of embodiment of the present invention plane heat source preparation method's carbon nanotube flocculent structure.
Embodiment
Describe plane heat source provided by the invention in detail below with reference to drawings and the specific embodiments.
Refer to Fig. 1 and Fig. 2, first embodiment of the invention provides a kind of plane heat source 10, and this plane heat source 10 is two-dimensional structure, and this plane heat source 10 is the structures of extending along two-dimensional directional.Even but it should be pointed out that to there is certain thickness two-dimensional structure, in macroscopic view, be still considered as or the approximate embodiment that is considered as two-dimentional structure, for example: tabular, the structure such as membranaceous, also should be considered as the scope of protection of the invention.
This plane heat source 10 comprises a heating element 16, one first electrode 12 and one second electrode 14.This heating element 16 is electrically connected with the first electrode 12 and the second electrode 14, thereby for making described heating element 16 current flowing that switches on power.
Described heating element 16 comprises a composite structure of carbon nano tube, and this composite structure of carbon nano tube comprises that a matrix 162 and at least one carbon nano tube structure 164 and this matrix 162 are compound.Particularly, this carbon nano tube structure 164 comprises multiple holes, and the material of this matrix 162 infiltrates through in multiple holes of this carbon nano tube structure 164, thereby forms a composite structure of carbon nano tube.In the time that the volume of this matrix 162 is larger, this carbon nano tube structure 164 is arranged in matrix 162, and completely coated by this matrix 162.This heating element 16 is a layer structure, and particularly, this heating element 16 can be a planar structure or curved-surface structure.In the present embodiment, this matrix 162 is a tabular cuboid, and this carbon nano tube structure 164 is embedded in this matrix 162 completely.
This carbon nano tube structure 164 is a self supporting structure.So-called " self supporting structure " i.e. this carbon nano tube structure 164, without by a support body supports, also can keep self specific shape.The carbon nano tube structure 164 of this self supporting structure comprises multiple carbon nano-tube, the plurality of carbon nano-tube attracts each other by Van der Waals force, thereby form a network configuration, and make carbon nano tube structure 164 there is specific shape, to form the carbon nano tube structure of self-supporting of an one.In the present embodiment, this carbon nano tube structure 164 is the planar or one dimension linear structure of two dimension.Because this carbon nano tube structure 164 has self-supporting, in the time not supporting by supporting body surface, still can keep planar or linear structure.In this carbon nano tube structure 164, between carbon nano-tube, have a large amount of gaps, thereby make this carbon nano tube structure 164 have a large amount of holes, these matrix 162 materials infiltrate in this hole.
Described carbon nano tube structure 164 comprises equally distributed a large amount of carbon nano-tube, between carbon nano-tube, combines closely by Van der Waals force.Carbon nano-tube in this carbon nano tube structure 164 is unordered or ordered arrangement.The orientation of the unordered finger carbon nano-tube is here irregular, and the orientation of at least most carbon nano-tube of orderly finger here has certain rule.Particularly, in the time that carbon nano tube structure 164 comprises the carbon nano-tube of lack of alignment, carbon nano-tube can further be wound around mutually, carbon nano tube structure 164 isotropism that the carbon nano-tube of this lack of alignment forms; In the time that carbon nano tube structure 164 comprises the carbon nano-tube of ordered arrangement, carbon nano-tube is arranged of preferred orient along a direction or multiple directions.The thickness of this carbon nano tube structure 164 is preferably 0.5 nanometer～1 millimeter.Carbon nano-tube in this carbon nano tube structure 164 comprises one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes.The diameter of described Single Walled Carbon Nanotube is 0.5 nanometer～50 nanometer, and the diameter of described double-walled carbon nano-tube is 1.0 nanometer～50 nanometers, and the diameter of described multi-walled carbon nano-tubes is 1.5 nanometer～50 nanometers.Preferably, described carbon nano tube structure 164 comprises the carbon nano-tube of ordered arrangement, and carbon nano-tube is arranged of preferred orient along a fixed-direction.The thermal response speed that is appreciated that carbon nano tube structure 164 is relevant with its thickness.In situation of the same area city, the thickness of carbon nano tube structure 164 is larger, and thermal response speed is slower; Otherwise the thickness of carbon nano tube structure 164 is less, thermal response speed is faster.Because this carbon nano tube structure 164 is made up of pure nano-carbon tube, therefore the unit are thermal capacitance of this carbon nano tube structure 164 is less than 2 × 10 -4every square centimeter of Kelvin of joule, is preferably less than 1.7 × 10 -6every square centimeter of Kelvin of joule.This minimum unit are thermal capacitance makes this carbon nano tube structure 164 have thermal response speed faster.
Particularly, this carbon nano tube structure 164 comprises the composite construction of at least one carbon nano-tube film, at least one liner structure of carbon nano tube or described carbon nano-tube film and linear structure composition.Be appreciated that in the time that described carbon nano tube structure 164 comprises multiple carbon nano-tube film, the plurality of carbon nano-tube film can stacked setting or is arranged side by side.Refer to Fig. 3, in the time that described carbon nano tube structure 164 comprises multiple liner structure of carbon nano tube, the plurality of liner structure of carbon nano tube can be parallel to each other, side by side or the carbon nano tube structure 164 of one-tenth arranged in a crossed manner one two dimension or be mutually wound around or be woven into the carbon nano tube structure 164 of a two dimension.In addition, refer to Fig. 4, when this carbon nano tube structure 164 can bend the carbon nano tube structure 164 that be coiled into a two dimension by a liner structure of carbon nano tube.
This carbon nano-tube film comprises carbon nano-tube membrane, carbon nano-tube waddingization film or carbon nano-tube laminate.This liner structure of carbon nano tube can comprise at least one carbon nano tube line, multiple carbon nano tube line be arranged in parallel composition fascicular texture or multiple carbon nano tube line reverse composition twisted wire structure.
Described carbon nano tube structure 164 can comprise at least one carbon nano-tube membrane, and this carbon nano-tube membrane is from carbon nano pipe array, directly to pull a kind of carbon nano-tube film with self-supporting obtaining.Each carbon nano-tube membrane comprises multiple preferred orientations in the same direction and is parallel to the carbon nano-tube of carbon nano-tube membrane surface alignment.Described carbon nano-tube joins end to end by Van der Waals force, to form the carbon nano-tube membrane of self-supporting of an one.Refer to Fig. 5 and Fig. 6, particularly, each carbon nano-tube membrane comprise multiple continuously and the carbon nano-tube fragment 143 aligning.The plurality of carbon nano-tube fragment 143 joins end to end by Van der Waals force.Each carbon nano-tube fragment 143 comprises multiple carbon nano-tube that are parallel to each other 145, and the plurality of carbon nano-tube being parallel to each other 145 is combined closely by Van der Waals force.This carbon nano-tube fragment 143 has width, thickness, uniformity and shape arbitrarily.The thickness of described carbon nano-tube membrane is 0.5 nanometer～100 micron, and width is relevant with the size of carbon nano pipe array that pulls this carbon nano-tube membrane, and length is not limit.When this carbon nano tube structure 164 is made up of carbon nano-tube membrane, and the Thickness Ratio of carbon nano tube structure 164 hour, for example, be less than 10 microns, and this carbon nano tube structure 164 has good transparency, its light transmittance can reach 90%, can be for the manufacture of a transparent thermal source.
In the time that described carbon nano tube structure 164 comprises the multilayer carbon nanotube membrane of stacked setting, between the carbon nano-tube being arranged of preferred orient in adjacent two layers carbon nano-tube membrane, form an intersecting angle α, α is more than or equal to 0 degree and is less than or equal to 90 degree (0 °≤α≤90 °).Between adjacent carbon nano-tube between described multiple carbon nano-tube membrane or among a carbon nano-tube membrane, have certain interval, thereby form multiple holes in carbon nano tube structure 164, the aperture size of hole is approximately less than 10 microns.Concrete structure of described carbon nano-tube membrane and preparation method thereof refers to the people such as Fan Shoushan on February 9th, 2007 application, in disclosed CN101239712A China's Mainland publication application (carbon nano-tube membrane structure and preparation method thereof Augusts 13 in 2008, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd.).For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
The carbon nano tube structure 164 of the embodiment of the present invention comprises multiple carbon nano-tube membranes along the stacked setting of equidirectional, thereby carbon nano-tube in carbon nano tube structure 164 is all arranged of preferred orient in the same direction.
Described carbon nano tube structure 164 can comprise at least one carbon nano-tube waddingization film, and this carbon nano-tube waddingization film comprises mutual winding and equally distributed carbon nano-tube.The length of carbon nano-tube is greater than 10 microns, is preferably 200～900 microns, thereby carbon nano-tube is intertwined mutually.Between described carbon nano-tube, attract each other, be wound around by Van der Waals force, form network-like structure, to form the carbon nano-tube waddingization film of self-supporting of an one.Described carbon nano-tube waddingization film isotropism.Carbon nano-tube in described carbon nano-tube waddingization film is for being uniformly distributed, and random arrangement, forms a large amount of pore structures, and hole aperture is approximately less than 10 microns.Length and the width of described carbon nano-tube waddingization film are not limit.Refer to Fig. 7, due in carbon nano-tube waddingization film, carbon nano-tube is wound around mutually, and therefore this carbon nano-tube waddingization film has good pliability, and is a self supporting structure, can become arbitrary shape and not break by bending fold.Area and the thickness of described carbon nano-tube waddingization film are not all limit, and thickness is 1 micron～1 millimeter, are preferably 100 microns.Concrete structure of described carbon nano-tube waddingization film and preparation method thereof refers to the people such as Fan Shoushan in No. 200710074027.5 China's Mainland patent application (preparation method of carbon nano-tube film of application on April 13rd, 2007, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd.).For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Described carbon nano tube structure 164 can comprise at least one carbon nano-tube laminate, and this carbon nano-tube laminate comprises equally distributed carbon nano-tube.Described carbon nano-tube is unordered, in the same direction or different directions be arranged of preferred orient.The mutual part of carbon nano-tube in described carbon nano-tube laminate is overlapping, and attracts each other by Van der Waals force, combines closely, and makes this carbon nano tube structure have good pliability, can become arbitrary shape and not break by bending fold.And owing to attracting each other by Van der Waals force between the carbon nano-tube in carbon nano-tube laminate, combine closely, making carbon nano-tube laminate is the structure of the self-supporting of an one.Described carbon nano-tube laminate can obtain by rolling a carbon nano pipe array.Carbon nano-tube in described carbon nano-tube laminate has angle 3 with the surperficial shape of the growth substrate that forms carbon nano pipe array, wherein, 3 are more than or equal to 0 degree and are less than or equal to 15 degree (0≤β≤15 °), this angle β is with to be applied to the pressure that carbon nano-pipe array lists relevant, pressure is larger, this angle is less, and preferably, the carbon nano-tube in this carbon nano-tube laminate is parallel to this growth substrate and arranges.This carbon nano-tube laminate is for obtaining by rolling a carbon nano pipe array, and according to the mode difference rolling, the carbon nano-tube in this carbon nano-tube laminate has different spread patterns.Refer to Fig. 8, in the time rolling along different directions, carbon nano-tube is arranged of preferred orient along different directions.Refer to Fig. 9, in the time rolling in the same direction, carbon nano-tube is arranged of preferred orient along a fixed-direction.In addition, in the time rolling direction for vertical this carbon nano pipe array surface, this carbon nano-tube can lack of alignment.In this carbon nano-tube laminate, the length of carbon nano-tube is greater than 50 microns.
Area and the thickness of this carbon nano-tube laminate are not limit, and can select according to actual needs.The area of this carbon nano-tube laminate and the size of carbon nano pipe array are basic identical.The height of this carbon nano-tube laminate thickness and carbon nano pipe array and the pressure rolling are relevant, can be 1 micron～1 millimeter.The height that is appreciated that carbon nano pipe array is larger and applied pressure is less, and the thickness of the carbon nano-tube laminate of preparation is larger; Otherwise the height of carbon nano pipe array is less and applied pressure is larger, the thickness of the carbon nano-tube laminate of preparation is less.Between adjacent carbon nano-tube among described carbon nano-tube laminate, have certain interval, thereby form multiple holes in carbon nano-tube laminate, the aperture of hole is approximately less than 10 microns.Concrete structure of described carbon nano-tube laminate and preparation method thereof refers to the people such as Fan Shoushan in No. 200710074699.6 China's Mainland patent application (preparation method of carbon nano-tube film of application on June 1st, 2007, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd.).For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Described carbon nano tube structure 164 can comprise at least one carbon nano tube line.This carbon nano tube line can be the carbon nano tube line of non-torsion or the carbon nano tube line of torsion.The carbon nano tube line of this non-torsion is for to obtain carbon nano-tube membrane by organic solvent processing.Refer to Figure 10, the carbon nano tube line of this non-torsion comprises multiple carbon nano-tube of arranging along carbon nano tube line length direction.Preferably, this carbon nano-tube joins end to end.Particularly, the carbon nano tube line of this non-torsion comprises multiple carbon nano-tube fragments, and the plurality of carbon nano-tube fragment joins end to end by Van der Waals force, and each carbon nano-tube fragment comprises multiple carbon nano-tube that are parallel to each other and combine closely by Van der Waals force.This carbon nano-tube fragment has length, thickness, uniformity and shape arbitrarily.The carbon nano-tube line length of this non-torsion is not limit, and diameter is 0.5 nanometer-100 micron.The concrete structure of described carbon nano tube line and preparation method refer to the people such as Fan Shoushan on September 16th, 2002 application, in No. CN100411979Cth, the Chinese patent of on August 20th, 2008 bulletin, and on December 16th, 2005 application, in No. CN1982209Ath, disclosed Chinese patent application on June 20th, 2007.For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
The carbon nano tube line of this torsion is for adopting a mechanical force that described carbon nano-tube membrane two ends are reversed to acquisition in opposite direction.Refer to Figure 11, the carbon nano tube line of this torsion comprises multiple carbon nano-tube of arranging around carbon nano tube line axial screw.Particularly, the carbon nano tube line of this torsion comprises multiple carbon nano-tube fragments, and the plurality of carbon nano-tube fragment joins end to end by Van der Waals force, and each carbon nano-tube fragment comprises multiple carbon nano-tube that are parallel to each other and combine closely by Van der Waals force.This carbon nano-tube fragment has length, thickness, uniformity and shape arbitrarily.The carbon nano-tube line length of this torsion is not limit, and diameter is 0.5 nanometer-100 micron.
Further, can adopt a volatile organic solvent to process the carbon nano tube line of this torsion.Under the capillary effect producing in the time that volatile organic solvent volatilizees, carbon nano-tube adjacent in the carbon nano tube line of torsion after treatment is combined closely by Van der Waals force, diameter and the specific area of the carbon nano tube line reversing are reduced, and density and intensity increase.
Because this carbon nano tube line obtains for adopting organic solvent or mechanical force to process above-mentioned carbon nano-tube membrane, this carbon nano-tube membrane is self supporting structure, therefore this carbon nano tube line is self supporting structure.This carbon nano tube line and carbon nano-tube membrane are similar, are joined end to end, to form the carbon nano tube line of self-supporting of an one by multiple carbon nano-tube by Van der Waals force.In addition, in this carbon nano tube line, between adjacent carbons nanotube, have gap, therefore this carbon nano tube line has a large amount of holes, the aperture of hole is approximately less than 10 microns.
The material of described matrix 162 can be chosen as macromolecular material or Inorganic Non-metallic Materials etc.This matrix 162 or the presoma that forms this matrix 162 are liquid state or gaseous state at a certain temperature, thereby the presoma of this matrix 162 or this matrix 162 can be penetrated in the gap or hole of this carbon nano tube structure 164 in the preparation process of the heating element 16 of plane heat source 10, and form the composite construction that a solid matrix 162 combines with carbon nano tube structure 164.The material of this matrix 162 should have certain heat resistance, makes it unlikelyly in the working temperature of this plane heat source 10 be subject to heat damage, distortion, fusing, gasification or decomposition.
Particularly, this macromolecular material can comprise one or more of thermoplastic polymer or thermosetting polymer, as one or more in cellulose, polyethylene terephthalate, acryl resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, phenolic resins, epoxy resin, silica gel and polyester etc.This Inorganic Non-metallic Materials can comprise one or more in glass, pottery and semi-conducting material.In the embodiment of the present invention, the material of this matrix 162 is epoxy resin.
Refer to Figure 12, owing to thering is gap between carbon nano-tube in this carbon nano tube structure 164, thereby in carbon nano tube structure 164, form multiple holes, and this matrix 162 or the presoma that forms this matrix 162 are liquid state or gaseous state at a certain temperature, thereby make this matrix 162 can infiltrate the hole inside of this carbon nano tube structure 164 with these carbon nano tube structure 164 compound tenses.Figure 12 stretches this heating element 16 to these heating element 16 fractures along the orientation that is parallel to carbon nano-tube in carbon nano-tube membrane, the truncation surface photo of this heating element 16 obtaining, can find, after compound with epoxy resin, this carbon nano tube structure 164 still can keep compound front form substantially, and carbon nano-tube is arranged of preferred orient substantially in the same direction in epoxy resin.
This matrix 162 can only be filled in the hole of described carbon nano tube structure 164, also can further be coated as shown in Figure 2 whole carbon nano tube structure 164 completely.Refer to Figure 13, in the time that this heating element 16 comprises multiple carbon nano tube structure 164, what the plurality of carbon nano tube structure 164 can space (or being in contact with one another) is arranged in this matrix 162.In the time that this carbon nano tube structure 164 is two-dimensional structure, this two-dimensional structure can space or being arranged side by side or stacked being arranged in matrix 162 of being in contact with one another; In the time that this carbon nano tube structure 164 is linear structure, this linear structure can space or being arranged in matrix 162 of being in contact with one another.In the time that this carbon nano tube structure 164 is arranged at intervals in matrix 162, can save the consumption of the required carbon nano tube structure 164 of this heating element 16 of preparation.In addition, visual actual needs is arranged on carbon nano tube structure 164 ad-hoc location of matrix 162, thereby makes this heating element 16 have different heating-up temperatures at diverse location.
Be appreciated that, described matrix 162 permeates in the hole of carbon nano tube structure 164, can play the effect of fixing the carbon nano-tube in this carbon nano tube structure 164, make the not reason external force friction or scratch and come off of carbon nano-tube in carbon nano tube structure 164 in use.In the time of described matrix 162 coated whole carbon nano tube structure 164, this matrix 162 can further be protected this carbon nano tube structure 164.In the time of this matrix 162 high-molecular organic material that is insulating properties or Inorganic Non-metallic Materials, this matrix 162 ensures this heating element 16 and exterior insulation simultaneously.In addition, the object that this matrix 162 can further play heat conduction and make uniform heat distribution.Further, in the time of this carbon nano tube structure 164 steep temperature rise, this matrix 162 can play the effect of buffering heat, makes the variations in temperature of this heating element 16 comparatively soft.The material of this matrix 162 can adopt flexible high molecular material, thereby can strengthen flexibility and the toughness of whole plane heat source 10.
Be appreciated that, because this carbon nano-tube is uniformly distributed in carbon nano tube structure 164, by matrix 162 and carbon nano tube structure 164 direct combinations of self-supporting are formed to heating element 16, can make carbon nano-tube be uniformly distributed in heating element 16, and the content of carbon nano-tube reaches 99%, improve the heating temp of thermal source 10.Because this carbon nano tube structure 164 is a self supporting structure, and carbon nano-tube is uniformly distributed in carbon nano tube structure 164, by the carbon nano tube structure of this self-supporting 164 and matrix 162 direct combinations, can make in the heating element 16 of compound rear formation carbon nano-tube still mutually combine and keep the form of a carbon nano tube structure 164, thereby make carbon nano-tube in heating element 16 can be uniformly distributed formation conductive network, be not subject to again carbon nano-tube in solution, to disperse the restriction of concentration, make the quality percentage composition of carbon nano-tube in heating element 16 can reach 99%.
Described the first electrode 12 and the second electrode 14 are made up of electric conducting material, and the shape of this first electrode 12 and the second electrode 14 is not limit, and can be conducting film, sheet metal or metal lead wire.Preferably, the first electrode 12 and the second electrode 14 are one deck conducting film.When for micro face thermal source 10, the thickness of this conducting film is 0.5 nanometer～100 micron.The material of this conducting film can be metal, alloy, indium tin oxide (ITO), antimony tin oxide (ATO), conductive silver glue, conducting polymer or conductive carbon nanotube etc.This metal or alloy material can be the alloy of aluminium, copper, tungsten, molybdenum, gold, titanium, neodymium, palladium, caesium or its combination in any.In the present embodiment, the material of described the first electrode 12 and the second electrode 14 is Metal Palladium film, and thickness is 5 nanometers.Described Metal Palladium and carbon nano-tube have good wetting effect, are conducive to form good electrically contacting between described the first electrode 12 and the second electrode 14 and described heating element 16, reduce ohmic contact resistance.
The first described electrode 12 and the second electrode 14 are directly electrically connected with the carbon nano tube structure 164 in heating element 16.Wherein, the first electrode 12 and the second electrode 14 intervals arrange, and avoid short circuit phenomenon to produce so that heating element 16 accesses certain resistance while being applied to plane heat source 10.
Particularly, in the time that 162 of the matrixes of this heating element 16 are filled in the hole of this carbon nano tube structure 164, because part carbon nano-tube part in this carbon nano tube structure 164 is exposed to heating element 16 surfaces, this first electrode 12 and the second electrode 14 can be arranged on the surface of heating element 16, thereby this first electrode 12 and the second electrode 14 are electrically connected with carbon nano tube structure 164.The same surface that this first electrode 12 and the second electrode 14 can be arranged on heating element 16 also can be arranged on the different surfaces of heating element 16.In addition, in the time that the matrix 162 of this heating element 16 is coated whole carbon nano tube structure 164, for this first electrode 12 and the second electrode 14 are electrically connected with this carbon nano tube structure 164, this first electrode 12 and the second electrode 14 can be arranged in the matrix 162 of heating element 16, and directly contact with carbon nano tube structure 164.Now, for making this first electrode 12 and the second electrode 14 and external power source conducting, this first electrode 12 and the second electrode 14 can partly be exposed to outside heating element 16; Or this thermal source 10 can further comprise two lead-in wires, be electrically connected with this first electrode 12 and the second electrode 14 respectively, and draw from these matrix 162 inside.
When in this carbon nano tube structure 164 when carbon nano-tube ordered arrangement, preferably, the orientation of this carbon nano-tube is extended along the first electrode 12 to second electrodes 14.Particularly, in the time that this carbon nano tube structure 164 comprises at least one carbon nano-tube membrane, described the first electrode 12 and the second electrode 14 are arranged at the two ends of this carbon nano-tube membrane, make in carbon nano-tube membrane carbon nano-tube join end to end and extend to the second electrode 14 from the first electrode 12.In the time that this carbon nano tube structure 164 comprises multiple liner structure of carbon nano tube being arranged in parallel, similar to resistance wire, these liner structure of carbon nano tube two ends are electrically connected with the second electrode 14 with this first electrode 12 respectively.
The first described electrode 12 and the second electrode 14 can be arranged at this heating element 16 or carbon nano tube structure 164 surfaces by a conductive adhesive (not shown), conductive adhesive, in realizing the first electrode 12 and the second electrode 14 and electrically contacting with carbon nano tube structure 164, can also be fixed on described the first electrode 12 and the second electrode 14 on the surface of carbon nano tube structure 164 better.Particularly, this conductive adhesive can be elargol.
The structure and material that is appreciated that the first electrode 12 and the second electrode 14 is not all limit, and it arranges object is in order to make carbon nano tube structure 164 current flowings in described heating element 16.Therefore, 14 needs of described the first electrode 12 and the second electrode conduction, and and the carbon nano tube structure 164 of described heating element 16 between form and electrically contact all in protection scope of the present invention.
The plane heat source 10 of the embodiment of the present invention in use, accesses power supply after can first the first electrode 12 of plane heat source 10 being connected to wire with the second electrode 14.Carbon nano tube structure 164 after access power supply in thermal source 10 can give off the electromagnetic wave of certain wave-length coverage.Described plane heat source 10 can directly contact with the surface of heated material.Or described plane heat source 10 can at intervals arrange with heated material.
Plane heat source 10 in the embodiment of the present invention, in size one timing of carbon nano tube structure 164, by the thickness of regulating power source voltage size and carbon nano tube structure 164, can give off the electromagnetic wave of different wavelength range.Particularly, this carbon nano tube structure 164 can produce an infrared heat radiation.Size one timing of supply voltage, the variation tendency that the thickness of carbon nano tube structure 164 and plane heat source 10 give off electromagnetic wavelength is contrary.When one timing of supply voltage size, the thickness of carbon nano tube structure 164 is thicker, and it is shorter that plane heat source 10 gives off electromagnetic wavelength; The thickness of carbon nano tube structure 164 is thinner, and it is longer that plane heat source 10 gives off electromagnetic wavelength.Thickness one timing of carbon nano tube structure 164, the size of supply voltage and plane heat source 10 give off electromagnetic wavelength and are inversely proportional to.When thickness one timing of carbon nano tube structure 164, supply voltage is larger, and it is shorter that plane heat source 10 spokes go out electromagnetic wavelength; Supply voltage is less, and it is longer that plane heat source 10 gives off electromagnetic wavelength.Be appreciated that, this plane heat source 10 should be applied to according to the material of matrix 162 voltage swing at the first electrode 12 and the second electrode 14 two ends in the time of application by a circuit limitations, the heating temp of carbon nano tube structure 164 is controlled in the tolerant temperature range of this matrix 162.For example, in the time that the material of this matrix 162 is organic high molecular polymer, this voltage range is 0～10 volt, and the heating temp of this plane heat source 10 is below 120 DEG C, and lower than the fusing point of this high molecular polymer.In the time that the material of this matrix 162 is pottery, this voltage range is 10 volts～30 volts, and the heating temp of this plane heat source 10 is 120 DEG C～500 DEG C.Refer to Figure 14, the embodiment of the present invention is by measuring the carbon nano tube structure 164 of the mutual stacked formation of 100 layers of carbon nano-tube membrane and the plane heat source 10 of the heating element 16 that epoxy resin-base 162 is compounded to form, can find that this plane heat source 10 is applied to voltage higher, this plane heat source 10 heats up faster, and heating temp is higher.
Carbon nano-tube has good electric conductivity and thermal stability, and as a desirable black matrix structure, has higher radiation efficiency.In another embodiment, when matrix 162 adopts heat proof material, this plane heat source 10 is exposed in the environment of oxidizing gas or atmosphere, wherein the thickness of carbon nano tube structure 164 is 5 millimeters, by at 10 volts～30 volts regulating power source voltages, this plane heat source 10 can give off the electromagnetic wave that wavelength is grown.Find that by temperature measuring set the temperature of this plane heat source 10 is 50 DEG C～500 DEG C.For the object with black matrix structure, when being 200 DEG C～450 DEG C, its corresponding temperature just can send thermal radiation invisible to the human eye (infrared ray), and thermal radiation is now the most stable, most effective.Apply the plane heat source 10 that this carbon nano tube structure 164 is made, can be applicable to the fields such as electric heater, infrared therapeutic apparatus, electric blanket, electric heater.
In addition, when the thickness of carbon nano tube structure 164 in the heating element 16 of this plane heat source 10 is less, be a transparent carbon nano tube structure 164, and the material of this matrix 162 is while being transparent organic or inorganic material, this plane heat source 10 is a transparent area thermal source 10.In addition, in the time that the matrix 162 in the heating element 16 of this plane heat source 10 is made up of flexible polymeric material, this plane heat source 10 is a flexible face thermal source 10.Further, because the matrix 162 of this polymeric material can form various shapes by die pressing, and this carbon nano tube line can be woven into difformity, and this flexible plane heat source 10 can be for the manufacture of the garment with heating element of spontaneous heating, Warming gloves or heating shoes etc.
Refer to Figure 15 and Figure 16, second embodiment of the invention provides a kind of plane heat source 20, and this plane heat source 20 comprises a heating element 26, one first electrode 22 and one second electrode 24.This heating element 26 comprises that a matrix 262 and at least one carbon nano tube structure 264 are arranged in matrix 262.This heating element 26 is a class two-dimensional structure, is one and has certain thickness two-dimensional structure.Particularly, this heating element 26 can be a planar structure or curved-surface structure.The carbon nano tube structure 264 of this heating element 26 is electrically connected with the first electrode 22 and the second electrode 24, thereby for making described heating element 26 current flowing that switches on power.
The plane heat source 10 of the structure of this plane heat source 20 and the first embodiment is basic identical, and its difference is, this plane heat source 20 further comprises a supporter 28, a heat-reflecting layer 27 and a protective layer 25.Described heat-reflecting layer 27 is arranged at the surface of supporter 28.Described heating element 26 is arranged at the surface of described heat-reflecting layer 27.Described the first electrode 22 and the second electrode 24 are arranged at intervals at the surface of described heating element 26, and electrically contact with this heating element 26, for making described heating element 26 current flowings.Described protective layer 25 is arranged at the surface of described heating element 26, for avoiding described heating element 26 to adsorb introduced contaminants.Described supporter 28, heat-reflecting layer 27 and protective layer 25 are optional structure.Further, this plane heat source 20 comprises two electrical leads 29, is connected respectively with described the first electrode 22 with the second electrode 24, leads to outside matrix 262 from the first electrode 22 and the second electrode 24 that are embedded in matrix 262.
Described supporter 28 shapes are not limit, and it has a surface for supporting heating element 16 or heat-reflecting layer 27.This surface can be plane or curved surface.Preferably, described supporter 28 is a platy structure, and its material can be hard material, as: pottery, glass, resin, quartz etc., can also select flexible material, as: plastics or resin etc.Wherein, the size of supporter 28 is not limit, and can change according to actual needs.The preferred supporter 28 of the present embodiment is a ceramic substrate.
The setting of described heat-reflecting layer 27 is used for reflecting the heat that heating element 26 is sent out, thereby controls the direction of heating, for single-side heating, and further improves the efficiency of heating.The material of described heat-reflecting layer 27 is a white insulating material, as: metal oxide, slaine or pottery etc.In the present embodiment, heat-reflecting layer 27 is alundum (Al2O3) layer, and its thickness is 100 microns～0.5 millimeter.This heat-reflecting layer 27 can be formed at this supporter 28 surfaces by sputter or additive method.Be appreciated that described heat-reflecting layer 27 also can be arranged on the surface of supporter 28 away from heating element 26, described supporter 28 is arranged between described heating element 26 and described heat-reflecting layer 27.Described heat-reflecting layer 27 is a selectable structure.Described heating element 26 can be set directly at the surface of supporter 28, and now the heating direction of plane heat source 10 is not limit, and can be used for Double-side Heating.
Described protective layer 25 is an optional structure, and its material is an insulating material, as: plastics, rubber or resin etc.Described protective layer 25 thickness are not limit, and can select according to actual conditions.Described protective layer 25 is covered on described the first electrode 22, the second electrode 24 and heating element 26, and in the present embodiment, the material of this insulating protective layer 25 is heat resistant rubber, and its thickness is 0.5～2 millimeter.Described protective layer 25 can be protected heating element 26; especially in the time that matrix 262 in this heating element 26 is only filled in the hole of carbon nano tube structure 264; this protective layer 25 can prevent that the carbon nano-tube that is exposed to heating element 26 surfaces is subject to external force friction and damages; in addition, can ensure this heating element 26 except described the first electrode 22 and the second electrode 24 and exterior insulation.
Refer to Figure 17, third embodiment of the invention provides a kind of plane heat source 30, and this plane heat source 30 comprises a heating element 36, one first electrode 32 and one second electrode 34.This heating element 36 is a two-dimensional structure, has certain thickness two-dimensional structure.Particularly, this heating element 36 can be a planar structure or curved-surface structure.This heating element 36 is electrically connected with the first electrode 32 and the second electrode 34, thereby for making the carbon nano-tube of described heating element 36 current flowing that switches on power.
The plane heat source 10 of the structure of this plane heat source 30 and the first embodiment is basic identical, and its difference is, this heating element 36 comprises multiple carbon nano-tube wire composite constructions 366.The plurality of carbon nano-tube wire composite construction 366 mutually braiding forms two-dimentional heating element 36.This carbon nano-tube wire composite construction 366 is by a liner structure of carbon nano tube and a basis material is compound obtains.This basis material is filled in the hole of this liner structure of carbon nano tube.This carbon nano tube compound linear structure 366 can directly be woven into the heating element 36 of various shapes easily.This basis material is preferably flexible polymer.
Refer to Figure 18, the embodiment of the present invention provides a kind of preparation method of plane heat source 10, and it comprises the following steps:
Step 1, provides a carbon nano tube structure 164, and this carbon nano tube structure 164 comprises multiple holes.
According to the difference of carbon nano tube structure 164, the preparation method of described carbon nano tube structure 164 comprises: directly membrane method, rolled-on method, wadding method etc.In the present embodiment, this carbon nano tube structure 164 can be that one-dimentional structure can be also two-dimensional structure.To the preparation method of above-mentioned several carbon nano tube structures 164 be narrated respectively below.
(1) when this carbon nano tube structure 164 comprises at least one carbon nano-tube membrane, the preparation method of this carbon nano tube structure 164 specifically comprises the following steps:
First, provide a carbon nano pipe array to be formed at a growth substrate, the carbon nano pipe array that this array is super in-line arrangement.
The preparation method of this carbon nano pipe array adopts chemical vapour deposition technique, its concrete steps comprise: a smooth growth substrate (a) is provided, this growth substrate can be selected P type or the substrate of N-type silicon growth, or select the silicon growth substrate that is formed with oxide layer, the embodiment of the present invention to be preferably the silicon growth substrate that adopts 4 inches; (b) form a catalyst layer at growth substrate surface uniform, this catalyst layer material can be selected one of alloy of iron (Fe), cobalt (Co), nickel (Ni) or its combination in any; (c) the above-mentioned growth substrate that is formed with catalyst layer is annealed approximately 30 minutes～90 minutes in the air of 700 DEG C～900 DEG C; (d) growth substrate of processing is placed in to reacting furnace, is heated to 500 DEG C～740 DEG C under protective gas environment, then pass into carbon-source gas and react approximately 5 minutes～30 minutes, growth obtains carbon nano pipe array.This carbon nano-pipe array is classified multiple pure nano-carbon tube arrays parallel to each other and that form perpendicular to the carbon nano-tube of growth substrate growth as.By above-mentioned control growth conditions, in this carbon nano pipe array aligning, substantially do not conform to and have impurity, as agraphitic carbon or residual catalyst metal particles etc.
The carbon nano-pipe array that the embodiment of the present invention provides is classified the one in single-wall carbon nanotube array, double-walled carbon nano-tube array and array of multi-walled carbon nanotubes as.The diameter of described carbon nano-tube is 1～50 nanometer, and length is 50 nanometer～5 millimeter.In the present embodiment, the length of carbon nano-tube is preferably 100～900 microns.
In the embodiment of the present invention, carbon source gas can be selected the more active hydrocarbons of chemical property such as acetylene, ethene, methane, and the preferred carbon source gas of the embodiment of the present invention is acetylene; Protective gas is nitrogen or inert gas, and the preferred protective gas of the embodiment of the present invention is argon gas.
Be appreciated that the carbon nano pipe array that the embodiment of the present invention provides is not limited to above-mentioned preparation method, also can be graphite electrode Constant Electric Current arc discharge sedimentation, laser evaporation sedimentation etc.
Secondly, adopt a stretching tool from carbon nano pipe array, to pull carbon nano-tube and obtain at least one carbon nano-tube membrane, it specifically comprises the following steps: (a) from described super in-line arrangement carbon nano pipe array selected one or have multiple carbon nano-tube of certain width, the present embodiment is preferably and adopts adhesive tape, tweezers or the clip contact carbon nano pipe array with certain width to select one or have multiple carbon nano-tube of certain width; (b) with certain speed this selected carbon nano-tube that stretches, thereby form end to end multiple carbon nano-tube fragment, and then form a continuous carbon nano-tube film.This pulls direction along the direction of growth that is basically perpendicular to carbon nano pipe array.
In above-mentioned drawing process, in the plurality of carbon nano-tube fragment departs from growth substrate gradually along draw direction under pulling force effect, due to van der Waals interaction, these selected multiple carbon nano-tube fragments are drawn out end to end continuously with other carbon nano-tube fragment respectively, thereby form one continuously, evenly and have a carbon nano-tube film of certain width.This carbon nano-tube film comprises multiple end to end carbon nano-tube, and this carbon nano-tube is arranged along draw direction substantially.Refer to Fig. 5 and Fig. 6, this carbon nano-tube film comprises multiple carbon nano-tube that are arranged of preferred orient 145.Further, described carbon nano-tube film comprises multiple carbon nano-tube fragments 143 that join end to end and align, and carbon nano-tube fragment 143 two ends interconnect by Van der Waals force.This carbon nano-tube fragment 143 comprises multiple carbon nano-tube that are arranged parallel to each other 145.The method of this acquisition carbon nano-tube film that directly stretches is simple and quick, the suitable industrial applications of carrying out.
The width of this carbon nano-tube film is relevant with the size of carbon nano pipe array, and the length of this carbon nano-tube film is not limit, and can make according to the actual requirements.In the time that the area of this carbon nano pipe array is 4 inches, the width of this carbon nano-tube film is 0.5 nanometer～10 centimetre, and the thickness of this carbon nano-tube film is 0.5 nanometer～100 micron.
Finally, utilize above-mentioned carbon nano-tube membrane to prepare carbon nano tube structure 164.
This carbon nano-tube membrane can be used as a carbon nano tube structure 164 and uses.Further, can also be by least two parallel gaplesss of carbon nano-tube membrane or/and stacked laying obtains a carbon nano tube structure 164.Because this carbon nano-tube membrane has larger specific area, therefore this carbon nano-tube membrane has larger viscosity, forms a carbon nano tube structure 164 therefore multilayer carbon nanotube film can be combined closely mutually.In this carbon nano tube structure 164, the number of plies of carbon nano-tube membrane is not limit, and has an intersecting angle α between adjacent two layers carbon nano-tube membrane, 0 °≤α≤90 °, specifically can prepare according to actual demand.Described carbon nano-tube film can be laid along an electrode to another electrode direction, thereby carbon nano-tube in carbon nano-tube film is extended along an electrode to another electrode direction
In the present embodiment, further comprise the step of processing carbon nano tube structure 164 with organic solvent, this organic solvent is volatile organic solvent, can select in ethanol, methyl alcohol, acetone, dichloroethanes kind chloroform one or several mixing, and the organic solvent in the present embodiment adopts ethanol.This step of with an organic solvent processing is specially: this carbon nano tube structure 164 is arranged in a substrate surface or a frame structure, by test tube, organic solvent is dropped in to the whole carbon nano tube structure 164 of carbon nano tube structure 164 surface infiltration, or, also above-mentioned carbon nano tube structure 164 can be immersed in the container that fills organic solvent and infiltrates.Described carbon nano tube structure 164 is after organic solvent infiltrates and processes, and in the time that the number of plies of carbon nano-tube film is less, under capillary effect, carbon nano-tube adjacent in carbon nano-tube film can be shrunk to carbon nano tube line spaced apart.And in the time that the number of plies of carbon nano-tube film is more, organic solvent multilayer carbon nanotube film after treatment is a uniform membrane structure.After organic solvent is processed, the viscosity of carbon nano tube structure 164 reduces, and is more convenient for using.
(2) when this carbon nano tube structure 164 comprises at least one carbon nano-tube waddingization film, the preparation method of this carbon nano tube structure 164 comprises the following steps:
First, provide a carbon nanometer tube material.
Described carbon nanometer tube material can be the carbon nano-tube of preparing by the whole bag of tricks such as chemical vapour deposition technique, graphite electrode Constant Electric Current arc discharge sedimentation or laser evaporation sedimentations.
In the present embodiment, adopt blade or other instruments that the above-mentioned carbon nano pipe array aligning is scraped from substrate, obtain a carbon nanometer tube material.Preferably, in described carbon nanometer tube material, the length of carbon nano-tube is greater than 100 microns.
Secondly, above-mentioned carbon nanometer tube material is added in a solvent and wad a quilt with cottonization processing acquisition one carbon nanotube flocculent structure, above-mentioned carbon nanotube flocculent structure is separated from solvent, and to this carbon nanotube flocculent structure heat treatment to obtain a carbon nano-tube film.
In the embodiment of the present invention, the optional water of solvent, volatile organic solvent etc.Waddingization is processed can be by adopting the methods such as ultrasonic wave dispersion treatment or high strength stirring.Preferably, the embodiment of the present invention adopts ultrasonic wave to disperse 10 minutes～30 minutes.Because carbon nano-tube has great specific area, between the carbon nano-tube being mutually wound around, there is larger Van der Waals force.Above-mentioned wadding processing can't be dispersed in the carbon nano-tube in this carbon nanometer tube material in solvent completely, between carbon nano-tube, is attracted each other, is wound around by Van der Waals force, forms network-like structure.
In the embodiment of the present invention, the method for described separating carbon nano-tube flocculent structure specifically comprises the following steps: pour the above-mentioned solvent that contains carbon nanotube flocculent structure into one and be placed with in the funnel of filter paper; Thereby standing and drying a period of time obtains a carbon nanotube flocculent structure separating, the photo that Figure 19 is this carbon nanotube flocculent structure.
In the embodiment of the present invention, the heat treatment process of described carbon nanotube flocculent structure specifically comprises the following steps: above-mentioned carbon nanotube flocculent structure is placed in to a container; This carbon nanotube flocculent structure is spread out according to reservation shape; Apply certain pressure in the carbon nanotube flocculent structure of spreading out; And, solvent residual in this carbon nanotube flocculent structure to be dried or the equal solvent acquisition one carbon nano-tube waddingization film afterwards that naturally volatilize, Fig. 7 is the stereoscan photograph of this carbon nano-tube waddingization film.
Be appreciated that the embodiment of the present invention can control by controlling area that this carbon nanotube flocculent structure spreads out thickness and the surface density of this carbon nano-tube waddingization film.The area that carbon nanotube flocculent structure is spread out is larger, and the thickness of this carbon nano-tube waddingization film and surface density are just less.The carbon nano-tube waddingization film obtaining in the embodiment of the present invention, the thickness of this carbon nano-tube waddingization film is 1 micron-2 millimeters.
In addition, the step of above-mentioned separation and heat treatment carbon nanotube flocculent structure also can directly realize by the mode of suction filtration, specifically comprises the following steps: an a miillpore filter and funnel of bleeding is provided; Pouring the above-mentioned solvent that contains carbon nanotube flocculent structure into this through this miillpore filter bleeds in funnel; Suction filtration the dry rear carbon nano-tube waddingization film that obtains.This miillpore filter is that a smooth surface, aperture are the filter membrane of 0.22 micron.Because suction filtration mode itself will provide a larger gas pressure in this carbon nanotube flocculent structure, this carbon nanotube flocculent structure is through directly formation one uniform carbon nano-tube waddingization film of suction filtration.And because microporous membrane surface is smooth, this carbon nano-tube waddingization film is easily peeled off, and obtains the carbon nano-tube waddingization film of a self-supporting.
Refer to Fig. 7, above-mentioned carbon nano-tube waddingization film comprises the carbon nano-tube of mutual winding, between described carbon nano-tube, is attracted each other, is wound around by Van der Waals force, forms network-like structure, and therefore this carbon nano-tube waddingization film has good toughness.In this carbon nano-tube waddingization film, carbon nano-tube is for being uniformly distributed and random arrangement.
Be appreciated that certain thickness that has of this carbon nano-tube waddingization film, and can control its thickness by controlling area and the pressure size that this carbon nanotube flocculent structure spreads out.So this carbon nano-tube waddingization film can directly use as a carbon nano tube structure 164.In addition, can or be arranged side by side at least two-layer carbon nano-tube waddingization film-stack setting and form a carbon nano tube structure 164.
(3) when this carbon nano tube structure 164 comprises at least one carbon nano-tube laminate, the preparation method of this carbon nano tube structure 164 comprises the following steps:
First, provide a carbon nano pipe array to be formed at a growth substrate, this array is the carbon nano pipe array aligning.
Described carbon nano pipe array is preferably the carbon nano pipe array that surpasses in-line arrangement.Described carbon nano pipe array is identical with the preparation method of above-mentioned carbon nano pipe array.
Secondly, adopt a device for exerting, push above-mentioned carbon nano pipe array and obtain a carbon nano-tube laminate, its detailed process is:
This device for exerting applies certain pressure and lists in above-mentioned carbon nano-pipe array.In the process of exerting pressure, carbon nano-pipe array is listed under the effect of pressure and can separates with growth substrate, thereby form the carbon nano-tube laminate with self supporting structure being formed by multiple carbon nano-tube, and described multiple carbon nano-tube go up substantially parallel with the surface of carbon nano-tube laminate.
In the embodiment of the present invention, device for exerting is a pressure head, pressure head smooth surface, the arrangement mode of carbon nano-tube in the carbon nano-tube laminate that the shape of pressure head and the direction of extrusion determine to prepare.Particularly, in the time adopting plane pressure head to push along the direction perpendicular to above-mentioned carbon nano pipe array growth substrate, can obtain carbon nano-tube is isotropic carbon nano-tube laminate of lack of alignment; In the time adopting roller bearing shape pressure head to roll along a certain fixed-direction that is parallel to substrate, can obtain the carbon nano-tube laminate of carbon nano-tube along this fixed-direction orientations; In the time adopting roller bearing shape pressure head to roll along different directions, can obtain the carbon nano-tube laminate of carbon nano-tube along different directions orientations.
Be appreciated that, in the time adopting above-mentioned different modes to push above-mentioned carbon nano pipe array, carbon nano-tube can be toppled under the effect of pressure, and attracts each other, is connected to form by Van der Waals force the carbon nano-tube laminate with self supporting structure being made up of multiple carbon nano-tube with adjacent carbon nano-tube.Described multiple carbon nano-tube and the surface of this growth substrate β that has angle, wherein, β is more than or equal to zero degree and is less than or equal to 15 degree (0 °≤β≤15 °).According to the mode difference rolling, as shown in Figure 9, the carbon nano-tube in this carbon nano-tube laminate can be arranged of preferred orient along a fixed-direction; Or as shown in Figure 8, be arranged of preferred orient along different directions.In addition, under the effect of pressure, carbon nano pipe array can separate with the substrate of growth, thereby this carbon nano-tube laminate is easily departed from substrate, thus the carbon nano-tube laminate of formation one self-supporting.
Those skilled in the art of the present technique should understand, above-mentioned carbon nano pipe array to topple over degree (inclination angle) relevant with the size of pressure, pressure is larger, inclination angle is larger.The angle that described inclination angle is for the carbon nano-tube in carbon nano pipe array and the substrate of this carbon nano pipe array of growth.The thickness of the carbon nano-tube laminate of preparation depends on height and the pressure size of carbon nano pipe array.The height of carbon nano pipe array is larger and applied pressure is less, and the thickness of the carbon nano-tube laminate of preparation is larger; Otherwise the height of carbon nano pipe array is less and applied pressure is larger, the thickness of the carbon nano-tube laminate of preparation is less.The size of the substrate that the width of this carbon nano-tube laminate is grown with carbon nano pipe array is relevant, and the length of this carbon nano-tube laminate is not limit, and can make according to the actual requirements.The carbon nano-tube laminate obtaining in the embodiment of the present invention, the thickness of this carbon nano-tube laminate is 1 micron～2 millimeters.
Finally, this carbon nano-tube laminate is uncovered from described growth substrate, thereby obtained the carbon nano-tube laminate of a self-supporting.
Above-mentioned carbon nano-tube laminate comprises carbon nano-tube in the same direction multiple or that be arranged of preferred orient, between described carbon nano-tube, attracts each other by Van der Waals force, and therefore this carbon nano-tube laminate has good toughness.In this carbon nano-tube laminate, even carbon nanotube distributes, regularly arranged.
Be appreciated that this carbon nano-tube laminate has certain thickness, and can control its thickness by height and the pressure size of carbon nano pipe array.So this carbon nano-tube laminate can directly be used as a carbon nano tube structure 164.In addition, can or be arranged side by side the stacked setting of at least two-layer carbon nano-tube laminate and form a carbon nano tube structure 164.
(4) in the time that this carbon nano tube structure 164 comprises at least one liner structure of carbon nano tube, the preparation method of this carbon nano tube structure 164 comprises the following steps:
First, provide at least one carbon nano-tube membrane.
The formation method of this carbon nano-tube membrane is identical with the formation method of carbon nano-tube membrane in ().
Secondly, process this carbon nano-tube membrane, form at least one carbon nano tube line.
The step of this processing carbon nano-tube membrane can be processed this carbon nano-tube membrane for employing organic solvent, thereby obtains the carbon nano tube line of a non-torsion, or for adopting mechanical external force to reverse this carbon nano-tube membrane, thereby obtain the carbon nano tube line of a torsion.
The step that adopts organic solvent to process this carbon nano-tube membrane is specially: the whole surface that organic solvent is infiltrated to described carbon nano-tube membrane, under the capillary effect producing in the time that volatile organic solvent volatilizees, the multiple carbon nano-tube that are parallel to each other in carbon nano-tube membrane are combined closely by Van der Waals force, thereby make carbon nano-tube membrane be punctured into the carbon nano tube line of a non-torsion.This organic solvent is volatile organic solvent, as ethanol, methyl alcohol, acetone, dichloroethanes or chloroform, adopts ethanol in the present embodiment.By the non-torsion carbon nano tube line of organic solvent processing, compared with carbon nano-tube membrane without organic solvent processing, specific area reduces, and viscosity reduces.Be appreciated that, this employing organic solvent process carbon nano-tube membrane form non-torsion carbon nano tube line method with in (one), adopt the method for viscosity of organic solvent reduction carbon nano-tube membrane similar, its difference is, in the time need to forming the carbon nano tube line of non-torsion, the two ends of carbon nano-tube membrane are unfixing, carbon nano-tube membrane are not arranged in substrate surface or frame structure.
The step that adopts mechanical external force to reverse this carbon nano-tube membrane is to adopt a mechanical force that described carbon nano-tube film two ends are reversed in opposite direction.In the embodiment of the present invention, specifically can provide an afterbody can cling the spinning axle of carbon nano-tube membrane.After the afterbody of this spinning axle is combined with carbon nano-tube membrane, this spinning axle is rotated to this carbon nano-tube membrane in rotary manner, form a carbon nano tube line reversing.The rotation mode that is appreciated that above-mentioned spinning axle is not limit, can forward, and also can reverse, or rotate and reverse and combine.
Further, can adopt a volatile organic solvent to process the carbon nano tube line of this torsion.Under the capillary effect producing in the time that volatile organic solvent volatilizees, carbon nano-tube adjacent in the carbon nano tube line of torsion after treatment is combined closely by Van der Waals force, the specific area of the carbon nano tube line reversing is reduced, viscosity reduces, and all increases with carbon nano tube line phase specific density and the intensity of the torsion without organic solvent processing.
Again, utilize above-mentioned carbon nano tube line to prepare at least one liner structure of carbon nano tube, and obtain a carbon nano tube structure 164.
The carbon nano tube line of above-mentioned torsion or the carbon nano tube line of non-torsion are a self supporting structure, can directly use as a carbon nano tube structure 164.In addition, multiple carbon nano tube lines can be arranged in parallel into the liner structure of carbon nano tube of a fascicular texture, or these multiple carbon nano tube lines that are arranged in parallel be obtained to the liner structure of carbon nano tube of hank line structure through a torsion step.Further, the plurality of carbon nano tube line or liner structure of carbon nano tube can be arranged parallel to each other, cross arrangement or braiding, obtain the carbon nano tube structure 164 of a two dimension.
Step 2, interval formation one first electrode 12 and one second electrode 14 are in the two ends of this carbon nano tube structure 164, and this first electrode 12 and one second electrode 14 form and are electrically connected with this carbon nano tube structure 164.
The first described electrode 12 and the set-up mode of one second electrode 14 are relevant with carbon nano tube structure 164.When in carbon nano tube structure 164 when at least part of ordered arrangement of carbon nano-tube, as this carbon nano tube structure 164 comprise a carbon nano-tube membrane, while rolling the carbon nano-tube laminate that obtains or a carbon nano tube line along a fixed-direction, when in this carbon nano tube structure 164, most of carbon nano-tube are arranged of preferred orient in the same direction, preferably, should ensure that part carbon nano-tube in carbon nano tube structure 164 extends along the first electrode 12 to 1 second electrode 14 directions, the first electrode 12 and the second electrode 14 are arranged on the bearing of trend of this carbon nano-tube.This kind of set-up mode can ensure that carbon nano tube structure 164 has best conductivity, thereby makes heating element 16 have best heating effect.
The first described electrode 12 and one second electrode 14 can be arranged on the same surface of carbon nano tube structure 164 or on different surfaces, or this first electrode 12 and one second electrode 14 are around the surface that is arranged at carbon nano tube structure 164.Wherein, the setting of being separated by between the first electrode 12 and one second electrode 14, avoids short circuit phenomenon to produce so that carbon nano tube structure 164 accesses certain resistance while being applied to line heat source 10.Carbon nano tube structure 164 itself has good adhesiveness and conductivity, thus the first electrode 12 and one second electrode 14 can and carbon nano tube structure 164 between form and well electrically contact.
Described the first electrode 12 and one second electrode 14 are conducting film, sheet metal or metal lead wire.This conducting film can be by plating, chemical plating, sputter, vacuum evaporation, physical vaporous deposition, chemical vapour deposition technique, directly apply or silk screen printing electrocondution slurry or other method are formed at carbon nano tube structure 164 surfaces.This sheet metal can be copper sheet or aluminium flake etc.This sheet metal or metal lead wire can be fixed on carbon nano tube structure 164 surfaces by conductive adhesive, or are fixed on carbon nano tube structure by screw, clamping plate etc.In the embodiment of the present invention, adopt vacuum vapour deposition to form two palladium films at carbon nano tube structure 164 two ends, as the first electrode 12 and the second electrode 14.
Described the first electrode 12 and one second electrode 14 can also be a metallic carbon nanotubes layer.This carbon nanotube layer is arranged at the surface of carbon nano tube structure 164.This carbon nanotube layer can be fixed on by the viscosity of himself or conductive adhesive the surface of carbon nano tube structure 164.This carbon nanotube layer comprises and aligning and equally distributed metallic carbon nanotubes.Particularly, this carbon nanotube layer comprises at least one carbon nano-tube film or at least one carbon nano tube line.Preferably, in described metallic carbon nanotubes layer, carbon nano tube surface is coated a metal level at least partly, thereby improves the conductivity of this metallic carbon nanotubes layer.Should in carbon nanotube layer, the method for carbon nano tube surface covered with metal layer can be vacuum evaporation, plasma sputtering or physical gas-phase deposite method etc.
Be appreciated that forming after the first electrode 12 and one second electrode 14, can further form two conductive lead wires, be electrically connected with the end of the first electrode 12 and the second electrode 14 respectively, lead to external power source from the first electrode 12 and one second electrode 14.
Step 3, provides a matrix precursor, by compound to matrix precursor and carbon nano tube structure 154, forms a heating element 16.
The material that the material of described matrix precursor is this matrix, the solution that this basis material forms or forerunner's reactant of preparing this basis material.This matrix precursor should be liquid state or gaseous state at a certain temperature.
The material of described matrix 162 comprises macromolecular material or Inorganic Non-metallic Materials etc.Particularly, this high-molecular organic material can comprise one or more in thermoplastic polymer or thermosetting polymer, therefore the material of this matrix precursor can be for generating the polymer monomer solution of this thermoplastic polymer or thermosetting polymer, or this thermoplastic polymer or thermosetting polymer in volatile organic solvent, dissolves after the mixed liquor of formation.This carbon nano tube structure 164 is directly soaked in after this liquid matrix precursor, and this matrix precursor is solidified, and forms matrix 162 compound with this carbon nano tube structure 164.
This Inorganic Non-metallic Materials can comprise one or more in glass, pottery and semi-conducting material, therefore the slurry that this matrix precursor can be made for Inorganic Non-metallic Materials particle, prepare the reacting gas of this Inorganic Non-metallic Materials or be this Inorganic Non-metallic Materials of gaseous state.Particularly, can adopt the method for vacuum evaporation, sputter, chemical vapour deposition (CVD) (CVD) and physical vapour deposition (PVD) (PVD) to form the matrix precursor of gaseous state, and make this matrix precursor be deposited on the carbon nano tube surface of carbon nano tube structure 164.In addition, a large amount of Inorganic Non-metallic Materials particles can be disperseed in solvent, form a slurry as this matrix precursor, and this carbon nano tube structure 164 is soaked in this slurry, and make solvent evaporation, make this matrix 162 compound with this carbon nano tube structure 164.
In a word, in the time that this matrix precursor is liquid state, this step 3 specifically comprises the step that this liquid matrix presoma is infiltrated to this carbon nano tube structure 164 and solidifies this matrix precursor, thereby this matrix 162 is infiltrated in the hole of this carbon nano tube structure 164, forms a heating element 16; In the time that this matrix precursor is gaseous state, this step 3 specifically comprises that this matrix precursor of deposition is in the step of the carbon nano tube surface of carbon nano tube structure 164, thereby this matrix 162 is full of in the hole of this carbon nano tube structure 164, forms a heating element 16.
The present embodiment adopts injecting glue method by compound to epoxy resin-base material and carbon nano tube structure 164, forms a heating element 16, specifically comprises the following steps:
Step (one): a liquid thermosetting macromolecular material is provided.
The viscosity of described liquid thermosetting macromolecular material is lower than 5 handkerchief seconds, and can at room temperature keep this viscosity more than 30 minutes.The embodiment of the present invention is preferably prepared liquid thermosetting macromolecular material with epoxy resin, and it specifically comprises the following steps:
First, the mixture of glycidol ether type epoxy and glycidyl ester type epoxy is placed in to a container, be heated to 30 DEG C～60 DEG C, and the mixture of the type epoxy of glycidol ether described in container and glycidyl ester type epoxy is stirred 10 minutes, until the mixture of described glycidol ether type epoxy and glycidyl ester type epoxy mixes.
Secondly in the glycidol ether type epoxy, stirring described in fatty amine and diglycidyl ether are joined and the mixture of glycidyl ester type epoxy, carry out chemical reaction.
Finally, the mixture of described glycidol ether type epoxy and glycidyl ester type epoxy is heated to 30 DEG C～60 DEG C, thereby obtains a liquid thermosetting macromolecular material containing epoxy resin.
Step (two): adopt described liquid thermosetting macromolecular material to infiltrate described carbon nano tube structure 162.
The method that adopts described liquid thermosetting macromolecular material to infiltrate described carbon nano tube structure 162 in the present embodiment comprises the following steps:
First, carbon nano tube structure 162 is positioned in a mould.
Secondly, described liquid thermosetting macromolecular material is injected in described mould, infiltrates described carbon nano tube structure 162.In order to allow liquid thermosetting macromolecular material fully infiltrate described carbon nano tube structure 162, the time that infiltrates described carbon nano tube structure 162 can not be less than 10 minutes.
Be appreciated that, the method that described liquid thermosetting macromolecular material is infiltrated to described carbon nano tube structure 162 is not limit the method for injection, described liquid thermosetting macromolecular material can also be inhaled in described carbon nano tube structure 162 by capillarity, infiltrate described carbon nano tube structure 162, or described carbon nano tube structure 162 is immersed in described liquid thermosetting macromolecular material.
Step (three): solidify the above-mentioned carbon nano tube structure being infiltrated by liquid thermosetting macromolecular material 162, obtain a composite structure of carbon nano tube.
The present embodiment specifically comprises the following steps containing the curing of the thermoset macromolecule material of epoxy resin:
First, by this mold heated to 50 DEG C～70 DEG C, at this temperature, be liquid containing the thermoset macromolecule material of epoxy resin by a heater, maintain this temperature 1 hour～3 hours, make this thermoset macromolecule material continue to absorb heat to increase its curing degree.
Secondly, continue this mould to 80 of heating DEG C～100 DEG C, at this temperature, maintain 1 hour～3 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.
Again, continue heating this mould to 110 DEG C～150 DEG C, at this temperature, maintain 2 hours～20 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.
Finally, stop heating, be cooled to after room temperature until this mould, the demoulding can obtain a composite structure of carbon nano tube.
The China's Mainland patent application " preparation method of carbon nano tube compound material " that the above-mentioned concrete steps of preparing composite structure of carbon nano tube can be 200710125109.8 in the application number of application on December 14th, 2007 referring to people such as Fan Shoushan.For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
The curing that is appreciated that the above-mentioned thermoset macromolecule material containing epoxy resin also can adopt the method once heating up, and directly temperature is risen to 150 DEG C, and thermoset macromolecule material heat absorption is solidified.
Be appreciated that the step that forms the first electrode 12 and one second electrode 14 in above-mentioned steps two can carry out forming after this heating element 16.When this matrix 162 is only filled in the hole of this carbon nano tube structure 164, thereby while making carbon nano-tube part be exposed to heating element 16 surface, can adopt the method identical with step 2 that this first electrode 12 and one second electrode 14 are directly formed to this heating element 16 surfaces.In the time of this matrix 162 all coated this carbon nano tube structure 164, further comprise that the described carbon nano tube structure 164 of an exposure is in the step on heating element 16 surfaces, this first electrode 12 and the second electrode 14 are electrically connected with the carbon nano tube structure 164 exposing respectively.Particularly, can adopt the step of a cutting to cut this heating element 16, to form a cut surface, thereby make this carbon nano tube structure 164 be exposed to the cut surface of heating element 16, and then the employing method identical with step 2 be formed at this first electrode 12 and one second electrode 14 cut surface of this heating element 16, thereby the carbon nano tube structure 164 coming out with this is electrically connected.
Be appreciated that in the time that this carbon nano tube structure is wire, the formation method of the heating element 36 of the 3rd embodiment can comprise the following steps:
First,, by compound to this liner structure of carbon nano tube and described matrix precursor, form a carbon nano-tube wire composite construction 366;
Secondly, one or more these carbon nano-tube wire composite constructions 366 are arranged, formed the heating element 36 of a two dimension.
This carbon nano-tube wire composite construction 366 can mutually weave, intersects, side by side or coiling form the heating element 36 of a two dimension.When this carbon nano-tube wire composite construction 366 is mutually when braiding, like dry goods, it is one planar that this heating element 36 can keep.This heating element 36 that mutually weaves formation can be made into a heating resistance pad, heating clothing and heated gloves etc.When this carbon nano-tube wire composite construction 366 intersects, side by side or when coiling mutually, between the plurality of liner structure of carbon nano tube 366, can bond by binding agent, thereby make this heating element 36 keep planar.
Described by identical with above-mentioned steps three mode compound with matrix precursor liner structure of carbon nano tube.
This first electrode and the second electrode can be formed at this heating element 36 surfaces by the mode of above-mentioned steps two.Further, can expose this liner structure of carbon nano tube in described heating element 36 surfaces by a cutting step, and then this first electrode and the second electrode are formed to this exposure have on the surface of carbon nano tube structure, thereby make this first electrode and the second electrode form and be electrically connected with the carbon nano-tube in this composite structure of carbon nano tube.
Be appreciated that this preparation method can further comprise the following step of selecting, thus preparation one plane heat source 20 having in the second embodiment:
Step 4, provides a supporter 28, forms a heat-reflecting layer 27 in the surface of supporter 28.
Forming a heat-reflecting layer 27 can realize by the method for coating or plated film on the surface of supporter 28.Particularly, in the time that the material of this heat-reflecting layer 27 is slaine or metal oxide, the particle of this slaine or metal oxide can be scattered in solvent, form a slurry, and by this slurry coating or silk screen printing in supporter 28 surfaces, form this heat-reflecting layer 27.According to the difference of slaine or metal oxide, this solvent not should with slaine or metal oxide generation chemical reaction.In addition, this heat-reflecting layer 27 also can form by methods such as plating, chemical plating, sputter, vacuum evaporation, chemical vapour deposition (CVD) or physical vapour deposition (PVD)s.The embodiment of the present invention adopts physical vaporous deposition at ceramic base plate surface deposition one deck alundum (Al2O3) layer, as heat-reflecting layer 27.
Step 5, is arranged at heat-reflecting layer 27 surfaces by heating element 26.
This heating element 26 can be fixed on heat-reflecting layer 27 surfaces by a binding agent.In addition, also can adopt the fixing method of machinery, as adopted the fixtures such as screw, clamping plate, 26 4 jiaos of heating elements or four limits are fixed on to heat-reflecting layer 27 surfaces.
Step 6, forms a protective layer 25 in the outer surface of described heating element 26, forms a plane heat source 20.
This protective layer 25 can directly be fixed on heating element 26 surfaces by binding agent or the fixing method of machinery.In addition, in the time that the material of this protective layer 25 is a thermoplastic polymer, this thermoplastic polymer at high temperature can be applied or is wrapped in heating element 26 surfaces in melting state, in the time of low temperature, solidify to form this protective layer 25.In addition; when this protective layer 25 is a flexible polymer, as one poly-during to benzenetricarboxylic acid glycol ester (PET) film, can pass through a heat-press step; this protective layer 25 is superposeed and hot pressing with this heating element 26, make protective layer 25 and heating element 26 strong bonded.
Described plane heat source and preparation method thereof has the following advantages: first, because this carbon nano tube structure is a self supporting structure, and carbon nano-tube is uniformly distributed in carbon nano tube structure, by the carbon nano tube structure of this self-supporting and matrix direct combination, can make in the heating element of compound rear formation carbon nano-tube still mutually combine and keep the form of a carbon nano tube structure, thereby make carbon nano-tube in heating element can be uniformly distributed formation conductive network, be not subject to again carbon nano-tube in solution, to disperse the restriction of concentration, make the quality percentage composition of carbon nano-tube in heating element can reach 99%, make this thermal source there is higher heating properties.In addition, the kind of this basis material is not limited to polymer, makes the range of application of this thermal source more extensive.Second, because carbon nano-tube has good intensity and toughness, the intensity of carbon nano tube structure is larger, better flexible, be difficult for breaking, make it have longer useful life, especially, in the time that this carbon nano tube structure and flexible substrate are compounded to form heating element, can prepare a flexible thermal source, make this thermal source there is wider range of application.The 3rd, the even carbon nanotube in carbon nano tube structure distributes, and therefore has uniform thickness and resistance, and evenly, the electric conversion efficiency of carbon nano-tube is high, and the unit are thermal capacitance of this carbon nano tube structure is less than 2 × 10 in heating -4every square centimeter of Kelvin of joule, so this plane heat source has the feature rapid, thermo-lag is little, thermal response speed is fast, rate of heat exchange is fast and radiation efficiency is high that heats up.The 4th, the diameter of carbon nano-tube is less, makes carbon nano tube structure can have less thickness, can prepare micro face thermal source, is applied to the heating of microdevice.The 5th, in the time that carbon nano tube structure comprises carbon nano-tube membrane, this carbon nano-tube membrane can be by pulling and obtain from carbon nano pipe array, and method is simple and be conducive to the making of large area plane heat source, and in this carbon nano-tube membrane, carbon nano-tube is arranged of preferred orient in the same direction, there is good electric conductivity, make this thermal source there is good heating properties, in addition, this carbon nano-tube membrane has certain transparency, can be used for preparing a transparent thermal source.The 6th, this carbon nano tube line can be used for braiding and forms the heating element of various shapes, thereby prepares the plane heat source of various shapes.The 7th, this carbon nano-tube waddingization film and carbon nano-tube laminate have good toughness, and preparation method is simple.The 8th, the carbon nano tube structure of this formation self-supporting, and by simple the method for this carbon nano tube structure and matrix direct combination formation heating element, and the content of carbon nano-tube in heating element can be controlled easily.After compound with matrix, this carbon nano tube structure still can keep original form, has the heating property suitable with pure nano-carbon tube structure.The 9th, this carbon nano tube structure can selectively be arranged at an a certain position having in the matrix of given shape, thereby realizes local selectivity heating, adapts to the demand of different field.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and certainly, the variation that these do according to spirit of the present invention, within all should being included in the present invention's scope required for protection.

Claims (15)

1. a preparation method for plane heat source, it comprises:
The membranaceous carbon nano tube structure of the one of multiple self-supportings is provided, make the setting of multiple membranaceous carbon nano tube structures space, wherein, each membranaceous carbon nano tube structure comprises multiple carbon nano-tube, the plurality of carbon nano-tube attracts each other by Van der Waals force, thereby forms a network configuration;
Interval forms one first electrode and one second electrode on described each carbon nano tube structure surface, and forms and be electrically connected with this carbon nano tube structure, and
One matrix precursor is provided, by the membranaceous carbon nano tube structure direct combination of multiple self-supportings of the setting of matrix precursor and space, form a composite structure of carbon nano tube, each carbon nano tube structure described in this composite structure of carbon nano tube keeps not compound shape before.
2. the preparation method of plane heat source as claimed in claim 1, is characterized in that, described the first electrode and the second electrode form by forming metal film on carbon nano tube structure surface.
3. the preparation method of plane heat source as claimed in claim 2, it is characterized in that, the described method that forms metal film on carbon nano tube structure surface is plating, chemical plating, sputter, vacuum evaporation, physical vapour deposition (PVD), chemical vapour deposition (CVD), direct coated with conductive slurry or silk screen printing electrocondution slurry.
4. the preparation method of plane heat source as claimed in claim 1, is characterized in that, described the first electrode and the second electrode are by forming at carbon nano tube structure surface fixing metal sheet or metal lead wire.
5. the preparation method of plane heat source as claimed in claim 4, is characterized in that, described sheet metal or metal lead wire are fixed on carbon nano tube structure surface by binding agent, screw or clamping plate.
6. the preparation method of plane heat source as claimed in claim 1, is characterized in that, described the first electrode and the second electrode form by the metallic carbon nanotubes layer that bonds at carbon nano tube structure.
7. the preparation method of plane heat source as claimed in claim 1, is characterized in that, described matrix precursor and the compound step of carbon nano tube structure are comprised liquid matrix precursor is infiltrated to described carbon nano tube structure and solidifies this liquid matrix precursor.
8. the preparation method of plane heat source as claimed in claim 7, is characterized in that, this liquid matrix precursor is a thermoset macromolecule material, and the compound method of this thermoset macromolecule material and this carbon nano tube structure specifically comprises the following steps:
One liquid thermosetting macromolecular material is provided;
Multiple carbon nano tube structures of the setting of described space are positioned in a mould;
Described liquid thermosetting macromolecular material is injected in described mould, infiltrates described multiple carbon nano tube structure;
By a heater by this mold heated; And
Stop heating, the demoulding after this mould is cooled to room temperature.
9. the preparation method of plane heat source as claimed in claim 1, is characterized in that, described matrix precursor is gaseous state, and matrix precursor and the compound method of carbon nano tube structure are comprised to vacuum evaporation, sputter, chemical vapour deposition (CVD) or physical vapour deposition (PVD).
10. a preparation method for plane heat source, it comprises:
The membranaceous carbon nano tube structure of the one of multiple self-supportings is provided, make the setting of multiple membranaceous carbon nano tube structures space, wherein, each membranaceous carbon nano tube structure comprises multiple carbon nano-tube, the plurality of carbon nano-tube attracts each other by Van der Waals force, thereby forms a network configuration;
One matrix precursor is provided, by the carbon nano tube structure direct combination of multiple self-supportings of the setting of matrix precursor and space, forms a heating element, each carbon nano tube structure described in this heating element keeps not compound shape before; And,
Interval forms one first electrode and one second electrode on described each carbon nano tube structure surface, and forms and be electrically connected with heating element.
The preparation method of 11. plane heat sources as claimed in claim 10, it is characterized in that, the preparation method of this plane heat source further comprises that the described carbon nano tube structure of an exposure is in the step on heating element surface, and described the first electrode and the second electrode are electrically connected with the carbon nano tube structure exposing respectively.
The preparation method of 12. plane heat sources as claimed in claim 11, is characterized in that, the step of described exposure carbon nano tube structure, for this heating element of cutting is to form a cut surface, makes carbon nano-structured this cut surface that is exposed to.
The preparation method of 13. 1 kinds of plane heat sources, it comprises the following steps:
The membranaceous carbon nano tube structure that the one of one self-supporting is provided, it comprises multiple carbon nano-tube, the plurality of carbon nano-tube attracts each other by Van der Waals force, thereby forms a network configuration;
Interval forms one first electrode and one second electrode on described carbon nano tube structure surface, and forms and be electrically connected with this carbon nano tube structure;
One matrix precursor is provided, by the membranaceous carbon nano tube structure direct combination of matrix precursor and self-supporting, forms a heating element, carbon nano tube structure described in this heating element keeps not compound shape before;
One supporter and a reflector are provided, and reflector is formed at supporting body surface; And
Described heating element is arranged to surface, reflector.
The preparation method of 14. plane heat sources as claimed in claim 13, is characterized in that, described heating element is fixed on this surface, reflector by binding agent or mechanical means.
The preparation method of 15. plane heat sources as claimed in claim 13, is characterized in that, the preparation method of this plane heat source further comprises that formation one protective layer is in the surface of described heating element.
CN200910106600.5A 2008-06-07 2009-04-20 Preparation method of plane heat source Active CN101868065B (en)

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CN200910106600.5A CN101868065B (en) 2009-04-20 2009-04-20 Preparation method of plane heat source
US12/655,507 US20100122980A1 (en) 2008-06-13 2009-12-31 Carbon nanotube heater
US12/658,198 US20100147830A1 (en) 2008-06-07 2010-02-04 Carbon nanotube heater
US12/658,184 US20100147828A1 (en) 2008-06-13 2010-02-04 Carbon nanotube heater
US12/658,193 US20100147829A1 (en) 2008-06-13 2010-02-04 Carbon nanotube heater
US12/658,182 US20100147827A1 (en) 2008-06-13 2010-02-04 Carbon nanotube heater
US12/658,237 US20100154975A1 (en) 2008-06-13 2010-02-04 Carbon Nanotube heater
US12/660,356 US20110024410A1 (en) 2008-06-13 2010-02-25 Carbon nanotube heater
US12/660,820 US20100163547A1 (en) 2008-06-13 2010-03-04 Carbon nanotube heater
US12/661,110 US20100218367A1 (en) 2008-06-13 2010-03-11 Method for making carbon nanotube heater
US12/661,133 US20100200568A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,165 US20100170891A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,150 US20100170890A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,115 US20100200567A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,926 US20100187221A1 (en) 2008-06-13 2010-03-25 Carbon nanotube hearter
US12/750,186 US20100180429A1 (en) 2008-06-13 2010-03-30 Carbon nanotube heater
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