CN101868066A - Plane heat source - Google Patents

Plane heat source Download PDF

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Publication number
CN101868066A
CN101868066A CN200910106803A CN200910106803A CN101868066A CN 101868066 A CN101868066 A CN 101868066A CN 200910106803 A CN200910106803 A CN 200910106803A CN 200910106803 A CN200910106803 A CN 200910106803A CN 101868066 A CN101868066 A CN 101868066A
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CN
China
Prior art keywords
carbon nano
tube
heat source
heating element
plane heat
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CN200910106803A
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Chinese (zh)
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CN101868066B (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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Application filed by Tsinghua University, Hongfujin Precision Industry Shenzhen Co Ltd filed Critical Tsinghua University
Priority to CN 200910106803 priority Critical patent/CN101868066B/en
Priority to US12/655,507 priority patent/US20100122980A1/en
Priority to US12/658,237 priority patent/US20100154975A1/en
Priority to US12/658,182 priority patent/US20100147827A1/en
Priority to US12/658,198 priority patent/US20100147830A1/en
Priority to US12/658,193 priority patent/US20100147829A1/en
Priority to US12/658,184 priority patent/US20100147828A1/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 US12/661,150 priority patent/US20100170890A1/en
Priority to US12/661,165 priority patent/US20100170891A1/en
Priority to US12/661,926 priority patent/US20100187221A1/en
Priority to US12/750,186 priority patent/US20100180429A1/en
Priority to JP2010097283A priority patent/JP5281036B2/en
Publication of CN101868066A publication Critical patent/CN101868066A/en
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Publication of CN101868066B publication Critical patent/CN101868066B/en
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Abstract

The invention relates to a plane heat source, comprising a heating element and at least two electrodes which are arranged at intervals and electrically connected with the heating element, wherein the heating element is composed of a substrate and an integrated self-supporting carbon nano tube structure formed by a plurality of carbon nano tubes. The plane heat source can be used for producing self-heating clothes, gloves or shoes, electric heaters, infrared therapy apparatuses, electric radiators and the like and has wide application range.

Description

Plane heat source
Technical field
The present invention relates to a kind of plane heat source, relate in particular to a kind of 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 a kind of of thermal source.Plane heat source is a two-dimensional structure, places the top of this two-dimensional structure that object is heated heated material, and therefore, plane heat source can heat simultaneously to each position of heated material, and heating surface is big, homogeneous heating and efficient are higher.Plane heat source successfully is used 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.When by electrode when heating element feeds voltage or electric current because heating element has big resistance, the electric energy that feeds heating element converts heat energy to, and discharges from heating element.The heating wire that present commercially available plane heat source adopts wire or carbon fiber to make usually carries out the electric heating conversion as heating element.
Yet wire or carbon fiber all have the shortcoming that intensity is not high, electric conversion efficiency is lower and quality is bigger.Wire is easy to fracture, and is particularly repeatedly crooked or easily produce tiredly when being converted into certain angle, therefore uses and is restricted.In addition, the heat made from wire or carbon fiber that heating wire was produced is to extraradial with common wavelength, its electric conversion efficiency is not high to be unfavorable for saving the energy, needs to add the sticking cotton thread that scribbles far ultrared paint and improves electric conversion efficiency, is unfavorable for energy-conserving and environment-protective.Carbon fiber and quality wiry are all bigger, are unfavorable for making the thermal source lightness.Simultaneously, the carbon fiber size is inadequately little, is unfavorable for being applied to miniature thermal source.
Since the early 1990s, (see also Helical microtubules of graphiticcarbon, Nature, Sumio Iijima with carbon nano-tube, vol 354, p56 (1991)) caused that with its particular 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.People such as Fan Shoushan disclose a kind of nanometer flexible electric heating material on December 19th, 2007 in disclosed Chinese patent application CN101090586A number.This thermo electric material comprises a flexible substrate and is dispersed in a plurality of carbon nano-tube in the described flexible substrate.These a plurality of carbon nano-tube exist with powdered form, and adhesion is very weak to each other, can't form a self supporting structure with given shape.When the carbon nano-tube of this powdered form was mixed with polymer solution, the carbon nano-tube of this powdered form was very easily reunited, thereby it is inhomogeneous to cause carbon nano-tube to be disperseed in matrix.Agglomeration when in polymer solution, disperseing for fear of carbon nano-tube, on the one hand, the mixture that in the process of disperseing, needs to handle this carbon nano-tube and polymer solution by supersonic oscillations, on the other hand, the quality percentage composition of carbon nano-tube can not be too high in this thermo electric material, only is 0.1～4%.
And carbon nano-tube is through after the above-mentioned dispersion treatment, even carbon nano-tube can be in contact with one another to each other, its adhesion also a little less than, can't 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 inadequately, and electric conversion efficiency is not high enough, so 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, during the preparation thermo electric material, its flexible substrate can only the selective polymer material, the polymeric material heat resisting temperature is lower, and the method for this kind 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 plane heat source of heating temp wider range.
A kind of plane heat source, it comprises: the carbon nano tube structure of the self-supporting of the one that a heating element, this heating element are made up of a matrix and a plurality of carbon nano-tube is composited; And at least two electrode gap setting and be electrically connected with this heating element.
A kind of plane heat source, comprise: a heating element and at least two electrode gap settings also are electrically connected with this heating element, wherein: this heating element comprises the carbon nano tube structure of one, this carbon nano tube structure comprises a plurality of carbon nano-tube that attract each other by the Van der Waals force effect, and this basis material is compound in this carbon nano tube structure.
A kind of plane heat source, it comprises: a two-dimentional heating element, this two dimension heating element comprises a plurality of carbon nano-tube, and a matrix, and these a plurality of carbon nano-tube form the carbon nano tube structure of one by Van der Waals force, and this carbon nano tube structure is mutually compound with matrix; And at least two electrode gap setting and be electrically connected with this heating element.
Compared with prior art, described plane heat source is owing to adopt the carbon nano tube structure of self supporting structure, and carbon nano-tube evenly distributes in carbon nano tube structure, the carbon nano tube structure and the matrix of this self-supporting is directly compound, need not to solve the scattering problem of carbon nano-tube, the content of carbon nano-tube is unrestricted, carbon nano-tube is still mutually combined keep the form of a carbon nano tube structure, makes this thermal source have better heating properties.In addition, the kind of this basis material is not limited to polymer, and temperature range is wide, makes the range of application of this thermal source more extensive.Even carbon nanotube in the carbon nano tube structure distributes, therefore has homogeneous thickness and resistance, heating is even, and the electric conversion efficiency height of carbon nano-tube is so this plane heat source has the characteristics rapid, that thermo-lag is little, rate of heat exchange is fast, radiation efficiency is high that heat up.
Description of 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 the II-II line.
Fig. 3 comprises the structural representation of the plane heat source of a plurality of cross one another liner structure of carbon nano tube for the embodiment of the invention.
Fig. 4 comprises the structural representation of the plane heat source of the liner structure of carbon nano tube that a bending is coiled for the embodiment of the invention.
Fig. 5 is the structural representation of carbon nano-tube fragment in the carbon nano-tube membrane structure in the embodiment of the invention plane heat source.
Fig. 6 is the stereoscan photograph of the carbon nano-tube membrane structure in the embodiment of the invention plane heat source.
Fig. 7 is the stereoscan photograph of the carbon nano-tube waddingization membrane structure in the embodiment of the invention plane heat source.
The stereoscan photograph that Fig. 8 is arranged of preferred orient along different directions for carbon nano-tube in the carbon nano-tube laminate structure in the embodiment of the invention plane heat source.
The stereoscan photograph that Fig. 9 is arranged of preferred orient along same direction for carbon nano-tube in the carbon nano-tube laminate structure in the embodiment of the invention plane heat source.
Figure 10 is the stereoscan photograph of the non-carbon nano tube line that reverses in the embodiment of the invention plane heat source.
Figure 11 is the stereoscan photograph of the carbon nano tube line that reverses in the embodiment of the invention plane heat source.
The truncation surface stereoscan photograph of the heating element that Figure 12 is compounded to form for the carbon nano-tube membrane in the embodiment of the invention plane heat source and epoxy resin.
Figure 13 comprises the structural representation of plane heat source of the carbon nano tube structure of a plurality of spaces for the embodiment of the invention.
Figure 14 is for using the temperature variation curve of heating element under different voltages among Figure 12.
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 the 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 invention plane heat source preparation method's a flow chart.
Figure 19 is the photo of embodiment of the 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.
See also 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 a two-dimensional structure, and promptly this plane heat source 10 is the structures of extending along two-dimensional directional.Even but should be pointed out that to have certain thickness two-dimensional structure, and still be considered as on the macroscopic view or the approximate embodiment that is considered as the structure of two dimension, for example: tabular, 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 first electrode 12 and second electrode 14, thereby is used to make described heating element 16 energized to flow through electric current.
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 a plurality of holes, and the material of this matrix 162 infiltrates through in a plurality of holes of this carbon nano tube structure 164, thereby forms a composite structure of carbon nano tube.When the volume of this matrix 162 was big, this carbon nano tube structure 164 was arranged in the matrix 162, and is coated fully by this matrix 162.This heating element 16 is a stratiform 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 fully.
This carbon nano tube structure 164 is a self supporting structure.So-called " self supporting structure " i.e. this carbon nano tube structure 164 need not by a support body supports, also can keep self specific shape.The carbon nano tube structure 164 of this self supporting structure comprises a plurality of carbon nano-tube, these a plurality of carbon nano-tube attract each other by Van der Waals force, thereby form a network configuration, and make carbon nano tube structure 164 have specific shape, with the carbon nano tube structure of the self-supporting that forms 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, still can keep planar or linear structure when not supporting by supporting body surface.Have a large amount of gaps between the carbon nano-tube in this carbon nano tube structure 164, 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, combines closely by Van der Waals force between the carbon nano-tube.Carbon nano-tube in this carbon nano tube structure 164 is unordered or orderly arrangement.The orientation of the unordered finger carbon nano-tube here is irregular, and the orientation of the most at least carbon nano-tube of orderly finger here has certain rule.Particularly, when carbon nano tube structure 164 comprised the carbon nano-tube of lack of alignment, carbon nano-tube can further be twined mutually, carbon nano tube structure 164 isotropism that the carbon nano-tube of this lack of alignment forms; When carbon nano tube structure 164 comprised orderly carbon nanotubes arranged, carbon nano-tube was arranged of preferred orient along a direction or a plurality of direction.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 the multi-walled carbon nano-tubes.The diameter of described Single Walled Carbon Nanotube is 0.5 nanometer～50 nanometers, and the diameter of described double-walled carbon nano-tube is 1.0 nanometers～50 nanometers, and the diameter of described multi-walled carbon nano-tubes is 1.5 nanometers～50 nanometers.Preferably, described carbon nano tube structure 164 comprises orderly carbon nanotubes arranged, 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.Under situation of the same area, the thickness of carbon nano tube structure 164 is big more, and thermal response speed is slow more; Otherwise the thickness of carbon nano tube structure 164 is more little, and thermal response speed is fast more.Because this carbon nano tube structure 164 is made up of pure nano-carbon tube, so 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 that 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 are formed.Be appreciated that when described carbon nano tube structure 164 comprises a plurality of carbon nano-tube film these a plurality of carbon nano-tube films can stacked settings or are arranged side by side.See also Fig. 3, when described carbon nano tube structure 164 comprised a plurality of liner structure of carbon nano tube, these a 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 twine or be woven into the carbon nano tube structure 164 of a two dimension mutually.In addition, see also Fig. 4, can be coiled into the carbon nano tube structure 164 of a two dimension when this carbon nano tube structure 164 by liner structure of carbon nano tube bending.
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 the twisted wire structure that is arranged in parallel at least one carbon nano tube line, a plurality of carbon nano tube line the fascicular texture formed or a plurality of carbon nano tube line reverse composition.
Described carbon nano tube structure 164 can comprise at least one carbon nano-tube membrane, and this carbon nano-tube membrane is for directly pulling a kind of carbon nano-tube film with self-supporting of acquisition from carbon nano pipe array.Each carbon nano-tube membrane comprises a plurality of along same direction preferred orientation and be parallel to carbon nano-tube membrane surface carbon nanotubes arranged.Described carbon nano-tube joins end to end by Van der Waals force, with the carbon nano-tube membrane of the self-supporting that forms an one.See also Fig. 5 and Fig. 6, particularly, each carbon nano-tube membrane comprise a plurality of continuously and the carbon nano-tube fragment 143 that aligns.This a plurality of carbon nano-tube fragment 143 joins end to end by Van der Waals force.Each carbon nano-tube fragment 143 comprises a plurality of carbon nano-tube that are parallel to each other 145, and this a plurality of carbon nano-tube that is 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 the 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 the carbon nano-tube membrane, and when the thickness of carbon nano tube structure 164 was smaller, for example less than 10 microns, this carbon nano tube structure 164 had good transparency, its light transmittance can reach 90%, can be used to make a transparent thermal source.
When described carbon nano tube structure 164 comprises the multilayer carbon nanotube membrane of stacked setting, form an intersecting angle α between the carbon nano-tube that is arranged of preferred orient in the adjacent two layers carbon nano-tube membrane, α spends (0 °≤α≤90 °) more than or equal to 0 degree smaller or equal to 90.Have certain interval between described a plurality of carbon nano-tube membrane or between the adjacent carbon nano-tube among carbon nano-tube membrane, thereby form a plurality of 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 sees also people such as Fan Shoushan in application on February 9th, 2007, 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, only be 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 invention comprises a plurality of carbon nano-tube membranes along the stacked setting of equidirectional, and carbon nano-tube all is arranged of preferred orient along same direction in the carbon nano tube structure 164 thereby make.
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 preferably 200～900 microns greater than 10 microns, thereby carbon nano-tube is intertwined mutually.Attract each other, twine by Van der Waals force between the described carbon nano-tube, form network-like structure, with the carbon nano-tube waddingization film of the self-supporting that forms an one.Described carbon nano-tube waddingization film isotropism.Carbon nano-tube in the described carbon nano-tube waddingization film is evenly to distribute, and random arrangement forms a large amount of pore structures, and the hole aperture is approximately less than 10 microns.The length and the width of described carbon nano-tube waddingization film are not limit.See also Fig. 7, because in carbon nano-tube waddingization film, carbon nano-tube is twined mutually, so this carbon nano-tube waddingization film has good flexible, and is a self supporting structure, can bending fold becomes arbitrary shape and does not break.The 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 sees also No. 200710074027.5 China's Mainland patent application (preparation method of carbon nano-tube film of people such as Fan Shoushan in application on April 13rd, 2007, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd.).For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be 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, is arranged of preferred orient along same direction or different directions.Carbon nano-tube in the described carbon nano-tube laminate mutually part overlaps, and attracts each other by Van der Waals force, combines closely, and makes this carbon nano tube structure have good flexible, can bending fold becomes arbitrary shape and does not break.And owing to attract each other by Van der Waals force between the carbon nano-tube in the carbon nano-tube laminate, combine closely, making the 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 the described carbon nano-tube laminate forms an angle β with the surface of the growth substrate that forms carbon nano pipe array, wherein, β is more than or equal to 0 degree and smaller 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 big more, this angle is more little, 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 to obtain by rolling a carbon nano pipe array, and according to the mode difference that rolls, the carbon nano-tube in this carbon nano-tube laminate has different spread patterns.See also Fig. 8, when when different directions rolls, carbon nano-tube is arranged of preferred orient along different directions.See also Fig. 9, when when same direction rolls, carbon nano-tube is arranged of preferred orient along a fixed-direction.In addition, be that this carbon nano-tube can lack of alignment when vertically this carbon nano pipe array was surperficial when rolling direction.The length of carbon nano-tube is greater than 50 microns in this carbon nano-tube laminate.
The 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 that rolls are relevant, can be 1 micron～1 millimeter.The height that is appreciated that carbon nano pipe array is big more and applied pressure is more little, and then the thickness of Zhi Bei carbon nano-tube laminate is big more; Otherwise the height of carbon nano pipe array is more little and applied pressure is big more, and then the thickness of Zhi Bei carbon nano-tube laminate is more little.Have certain interval between the adjacent carbon nano-tube among the described carbon nano-tube laminate, thereby form a plurality of holes in the 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 sees also No. 200710074699.6 China's Mainland patent application (preparation method of carbon nano-tube film of people such as Fan Shoushan in application on June 1st, 2007, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd.).For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be 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 non-carbon nano tube line that reverses or the carbon nano tube line that reverses.This non-carbon nano tube line that reverses obtains for the carbon nano-tube membrane is handled by organic solvent.See also Figure 10, this non-carbon nano tube line that reverses comprises a plurality of along carbon nano tube line length direction carbon nanotubes arranged.Preferably, this carbon nano-tube joins end to end.Particularly, this non-carbon nano tube line that reverses comprises a plurality of carbon nano-tube fragments, and these a plurality of carbon nano-tube fragments join end to end by Van der Waals force, and each carbon nano-tube fragment comprises a plurality of 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.This non-carbon nano-tube line length of reversing is not limit, and diameter is 0.5 nanometer-100 micron.The concrete structure of described carbon nano tube line and preparation method see also people such as Fan Shoushan in application on September 16th, 2002, in the Chinese patent of on August 20th, 2008 bulletin CN100411979C number, and on December 16th, 2005 application, in disclosed Chinese patent application CN1982209A number on June 20th, 2007.For saving space, only be 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.
This carbon nano tube line that reverses reverses acquisition for adopting a mechanical force in opposite direction with described carbon nano-tube membrane two ends.See also Figure 11, this carbon nano tube line that reverses comprises a plurality of around carbon nano tube line axial screw carbon nanotubes arranged.Particularly, this carbon nano tube line that reverses comprises a plurality of carbon nano-tube fragments, and these a plurality of carbon nano-tube fragments join end to end by Van der Waals force, and each carbon nano-tube fragment comprises a plurality of 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 that this reverses is not limit, and diameter is 0.5 nanometer-100 micron.
Further, can adopt a volatile organic solvent to handle the carbon nano tube line that this reverses.Under the capillary effect that when volatile organic solvent volatilizees, produces, adjacent carbon nano-tube is combined closely by Van der Waals force in the carbon nano tube line that reverses after the processing, the diameter and the specific area of the carbon nano tube line that reverses are reduced, and density and intensity increase.
Because this carbon nano tube line obtains for adopting organic solvent or mechanical force to handle above-mentioned carbon nano-tube membrane, this carbon nano-tube membrane is a self supporting structure, so this carbon nano tube line is a self supporting structure.This carbon nano tube line and carbon nano-tube membrane are similar, are joined end to end by Van der Waals force by a plurality of carbon nano-tube, with the carbon nano tube line of the self-supporting that forms an one.In addition, have the gap between the adjacent carbons nanotube in this carbon nano tube line, so 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 subjected to heat damage, distortion, fusing, gasification or decomposition.
Particularly, this macromolecular material can comprise one or more of thermoplastic polymer or thermosetting polymer, as in cellulose, polyethylene terephthalate, acryl resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, phenolic resins, epoxy resin, silica gel and the polyester etc. one or more.This Inorganic Non-metallic Materials can comprise one or more in glass, pottery and the semi-conducting material.In the embodiment of the invention, the material of this matrix 162 is an epoxy resin.
See also Figure 12, owing to have the gap between carbon nano-tube in this carbon nano tube structure 164, thereby in carbon nano tube structure 164, form a plurality of 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 is for stretching this heating element 16 to these heating element 16 fractures along the orientation that is parallel to carbon nano-tube in the carbon nano-tube membrane, the truncation surface photo of this heating element 16 that obtains, can find, with epoxy resin compound after, this carbon nano tube structure 164 still can keep compound preceding form substantially, and carbon nano-tube is arranged of preferred orient along same direction in epoxy resin substantially.
This matrix 162 can only be filled in the hole of described carbon nano tube structure 164, also can further coat whole carbon nano tube structure 164 as shown in Figure 2 fully.See also Figure 13, when this heating element 16 comprises a plurality of carbon nano tube structure 164, but being arranged in this matrix 162 of this a plurality of carbon nano tube structures 164 spaces (or being in contact with one another).When this carbon nano tube structure 164 is two-dimensional structure, but this two-dimensional structure space or being arranged side by side or stacked being arranged in the matrix 162 of being in contact with one another; When this carbon nano tube structure 164 is linear structure, but this linear structure space or being arranged in the matrix 162 of being in contact with one another.When this carbon nano tube structure 164 is arranged at intervals in the matrix 162, can save the consumption of the required carbon nano tube structure 164 of this heating element of preparation 16.In addition, visual actual needs is arranged on the ad-hoc location of matrix 162 with carbon nano tube structure 164, 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 the carbon nano tube structure 164 in use.When described matrix 162 coated whole carbon nano tube structure 164, this matrix 162 can further be protected this carbon nano tube structure 164.When this matrix 162 high-molecular organic material that is insulating properties or Inorganic Non-metallic Materials, this matrix 162 guarantees this heating element 16 and exterior insulation simultaneously.In addition, this matrix 162 purpose that can further play heat conduction and make uniform heat distribution.Further, when this carbon nano tube structure 164 sharply heated up, 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 the flexibility and the toughness of whole plane heat source 10.
Be appreciated that, because this carbon nano-tube evenly distributes in carbon nano tube structure 164, directly be compounded to form heating element 16 by carbon nano tube structure 164 with matrix 162 and self-supporting, carbon nano-tube is evenly distributed in heating element 16, and the content of carbon nano-tube reaches 99%, has improved the heating temp of thermal source 10.Because this carbon nano tube structure 164 is a self supporting structure, and carbon nano-tube evenly distributes in carbon nano tube structure 164, the carbon nano tube structure 164 of this self-supporting is directly compound with matrix 162, carbon nano-tube is still mutually combined keep the form of a carbon nano tube structure 164, thereby make in the heating element 16 the carbon nano-tube formation conductive network that can evenly distribute, be not subjected to carbon nano-tube in solution, to disperse the restriction of concentration again, make the quality percentage composition of carbon nano-tube in heating element 16 can reach 99%.
Described first electrode 12 and second electrode 14 are made up of electric conducting material, and the shape of this first electrode 12 and second electrode 14 is not limit, and can be conducting film, sheet metal or metal lead wire.Preferably, first electrode 12 and second electrode 14 are one deck conducting film.When being used for miniature plane heat 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 first electrode 12 and second electrode 14 is the Metal Palladium film, and thickness is 5 nanometers.Described Metal Palladium and carbon nano-tube have wetting effect preferably, help forming good electrical contact between described first electrode 12 and second electrode 14 and the described heating element 16, reduce ohmic contact resistance.
Described first electrode 12 and second electrode, 14 carbon nano tube structures 164 direct and in the heating element 16 are electrically connected.Wherein, first electrode 12 and second electrode 14 are provided with at interval, avoid short circuit phenomenon to produce so that heating element 16 inserts certain resistance when being applied to plane heat source 10.
Particularly, when 162 of the matrixes of this heating element 16 are filled in the hole of this carbon nano tube structure 164, because the part carbon nano-tube partly is exposed to heating element 16 surfaces in this carbon nano tube structure 164, this first electrode 12 and second electrode 14 can be arranged on the surface of heating element 16, thereby this first electrode 12 and second electrode 14 are electrically connected with carbon nano tube structure 164.The same surface that this first electrode 12 and second electrode 14 can be arranged on heating element 16 also can be arranged on the different surfaces of heating element 16.In addition, when the matrix 162 of this heating element 16 coats whole carbon nano tube structure 164, for this first electrode 12 and second electrode 14 are electrically connected with this carbon nano tube structure 164, this first electrode 12 and second electrode 14 can be arranged in the matrix 162 of heating element 16, and directly contact with carbon nano tube structure 164.At this moment, for making this first electrode 12 and second electrode 14 and external power source conducting, this first electrode 12 and second electrode 14 can partly be exposed to outside the heating element 16; Perhaps, this thermal source 10 can further comprise two lead-in wires, is electrically connected with this first electrode 12 and second electrode 14 respectively, and draws from these matrix 162 inside.
When carbon nano-tube was arranged in order in this carbon nano tube structure 164, preferably, the orientation of this carbon nano-tube was extended along first electrode, 12 to second electrodes 14.Particularly, when this carbon nano tube structure 164 comprises at least one carbon nano-tube membrane, described first electrode 12 and second electrode 14 are arranged at the two ends of this carbon nano-tube membrane, carbon nano-tube is joined end to end extend to second electrode 14 from first electrode 12.When this carbon nano tube structure 164 comprised a plurality of liner structure of carbon nano tube that is arranged in parallel, similar to resistance wire, these liner structure of carbon nano tube two ends were electrically connected with second electrode 14 with this first electrode 12 respectively.
Described first electrode 12 and second electrode 14 can be arranged at this heating element 16 or carbon nano tube structure 164 surfaces by a conductive adhesive (figure does not show), conductive adhesive can also be fixed in described first electrode 12 and second electrode 14 on the surface of carbon nano tube structure 164 when realizing that first electrode 12 and second electrode 14 electrically contact with carbon nano tube structure 164 better.Particularly, this conductive adhesive can be elargol.
The structure and material that is appreciated that first electrode 12 and second electrode 14 is not all limit, and it is provided with purpose is that carbon nano tube structure 164 flows through electric current in the described heating element 16 in order to make.Therefore, 14 needs of described first electrode 12 and 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 invention in use, can be earlier with first electrode 12 of plane heat source 10 with insert power supply after second electrode 14 is connected lead.Carbon nano tube structure 164 after inserting power supply in the 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.Perhaps, described plane heat source 10 can at intervals be provided with heated material.
Plane heat source 10 in the embodiment of the invention by regulating the thickness of supply voltage size and carbon nano tube structure 164, can give off the electromagnetic wave of different wavelength range in area size one timing of carbon nano tube structure 164.Particularly, this carbon nano tube structure 164 can produce an infrared heat radiation.Size one timing of supply voltage, it is opposite that the thickness of carbon nano tube structure 164 and plane heat source 10 give off electromagnetic wavelength change trend.Promptly when one timing of supply voltage size, the thickness of carbon nano tube structure 164 is thick more, and it is short more that plane heat source 10 gives off electromagnetic wavelength; The thickness of carbon nano tube structure 164 is thin more, and it is long more 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.Promptly when thickness one timing of carbon nano tube structure 164, supply voltage is big more, and it is short more that plane heat source 10 spokes go out electromagnetic wavelength; Supply voltage is more little, and it is long more that plane heat source 10 gives off electromagnetic wavelength.Be appreciated that, this plane heat source 10 should be applied to the voltage swing at first electrode 12 and second electrode, 14 two ends by a circuit limitations according to the material of matrix 162 when using, the heating temp of carbon nano tube structure 164 is controlled in these matrix 162 tolerant temperature ranges.For example, when the material of this matrix 162 was organic high molecular polymer, this voltage range was 0～10 volt, and the heating temp of this plane heat source 10 is below 120 ℃, and was lower than the fusing point of this high molecular polymer.When the material of this matrix 162 was pottery, this voltage range was 10 volts～30 volts, and the heating temp of this plane heat source 10 is 120 ℃～500 ℃.See also Figure 14, the plane heat source 10 of the heating element 16 that the carbon nano tube structure 164 of the embodiment of the invention by measuring the mutual stacked formation of 100 layers of carbon nano-tube membrane and epoxy resin-base 162 are compounded to form, it is high more to find that this plane heat source 10 is applied voltage, this plane heat source 10 heats up fast more, and heating temp is high more.
Carbon nano-tube has excellent conducting performance and thermal stability, and as a desirable black matrix structure, has than 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 regulating supply voltage at 10 volts～30 volts, this plane heat source 10 can give off the long electromagnetic wave of wavelength.Find that by temperature measuring set the temperature of this plane heat source 10 is 50 ℃～500 ℃.For object with black matrix structure, when being 200 ℃～450 ℃, its pairing temperature just can send thermal radiation invisible to the human eye (infrared ray), and the thermal radiation of this moment is the most stable, most effective.Use the plane heat source 10 that this carbon nano tube structure 164 is made, can be applicable to fields such as electric heater, infrared therapeutic apparatus, electric blanket, electric heater.
In addition, the thickness of carbon nano tube structure 164 is less in the heating element 16 of this plane heat source 10, is a transparent carbon nano tube structure 164, and the material of this matrix 162 is when being transparent organic or inorganic material, and this plane heat source 10 is a transparent area thermal source 10.In addition, when the matrix 162 in the heating element 16 of this plane heat source 10 was made by the polymeric material of flexibility, this plane heat source 10 was a flexible face thermal source 10.Further, because the matrix 162 of this polymeric material can form different shape by die pressing, and this carbon nano tube line can be woven into difformity, and this flexible plane heat source 10 can be used to make heating clothes, Warming gloves or the heating shoes etc. of spontaneous heating.
See also 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 the 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 first electrode 22 and second electrode 24, thereby is used to make described heating element 26 energized to flow through electric current.
The plane heat source 10 of the structure of this plane heat source 20 and first embodiment is basic identical, and its difference is that 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 first electrode 22 and second electrode 24 are arranged at intervals at the surface of described heating element 26, and electrically contact with this heating element 26, are used for making described heating element 26 to flow through electric current.Described protective layer 25 is arranged at the surface of described heating element 26, is used to avoid described heating element 26 absorption introduced contaminantses.But described supporter 28, heat-reflecting layer 27 and protective layer 25 are choice structure.Further, this plane heat source 20 comprises two electrical leads 29, links to each other with second electrode 24 with described first electrode 22 respectively, and first electrode 22 and second electrode 24 from be embedded in matrix 262 lead to outside the matrix 262.
Described supporter 28 shapes are not limit, and it has a surface and is used to support 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 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 the direction of control heating is used for the single face heating, and further improves the efficient 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 the alundum (Al 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, promptly described supporter 28 is arranged between described heating element 26 and the 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 this moment, the heating direction of plane heat source 10 was not limit, and can be used for two-sided heating.
But described protective layer 25 is a choice 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 first electrode 22, second electrode 24 and the heating element 26, and in the present embodiment, the material of this insulating protective layer 25 is a heat resistant rubber, and its thickness is 0.5～2 millimeter.Described protective layer 25 can be protected heating element 26; especially when matrix 262 in this heating element 26 only is filled in the hole of carbon nano tube structure 264; the carbon nano-tube that this protective layer 25 can prevent to be exposed to heating element 26 surfaces is subjected to the external force friction and damages; in addition, can guarantee that this heating element 26 is except that described first electrode 22 and second electrode 24 and exterior insulation.
See also 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, promptly 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 first electrode 32 and second electrode 34, thereby is used for making the carbon nano-tube energized of described heating element 36 to flow through electric current.
The plane heat source 10 of the structure of this plane heat source 30 and first embodiment is basic identical, and its difference is that this heating element 36 comprises a plurality of carbon nano-tube wire composite constructions 366.These a plurality of carbon nano-tube wire composite constructions 366 braiding mutually form two-dimentional heating element 36.This carbon nano-tube wire composite construction 366 is with 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.The compound linear structure 366 of this carbon nano-tube can directly be woven into the heating element 36 of different shape easily.This basis material is preferably flexible polymer.
See also Figure 18, the embodiment of the invention provides a kind of preparation method of plane heat source 10, and it may further comprise the steps:
Step 1 provides a carbon nano tube structure 164, and this carbon nano tube structure 164 comprises a plurality of holes.
According to the difference of carbon nano tube structure 164, the preparation method of described carbon nano tube structure 164 comprises: direct membrane method, rolled-on method, wadding method etc.In the present embodiment, this carbon nano tube structure 164 can also can be two-dimensional structure for one-dimentional structure.To the preparation method of above-mentioned several carbon nano tube structures 164 be narrated respectively below.
(1) comprise at least one carbon nano-tube membrane when this carbon nano tube structure 164, the preparation method of this carbon nano tube structure 164 specifically may further comprise the steps:
At first, provide a carbon nano pipe array to be formed at a growth substrate, this array is the carbon nano pipe array of 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 for use, or select for use the silicon growth substrate that is formed with oxide layer, the embodiment of the invention to be preferably and adopt 4 inches silicon growth substrate; (b) evenly form a catalyst layer on the growth substrate surface, this catalyst layer material can be selected one of alloy of iron (Fe), cobalt (Co), nickel (Ni) or its combination in any for use; (c) the above-mentioned growth substrate that is formed with catalyst layer was annealed in 700 ℃～900 ℃ air about 30 minutes～90 minutes; (d) growth substrate that will handle places reacting furnace, is heated to 500 ℃～740 ℃ under the protective gas environment, feeds carbon-source gas then and reacts about 5 minutes～30 minutes, and growth obtains carbon nano pipe array.This carbon nano-pipe array is classified a plurality of pure nano-carbon tube arrays parallel to each other and that form perpendicular to the growth substrate carbon nanotubes grown as.By above-mentioned control growing condition, do not contain impurity in this carbon nano pipe array that aligns substantially, as agraphitic carbon or residual catalyst metal particles etc.
The carbon nano-pipe array that the embodiment of the invention provides is classified a kind of in single-wall carbon nanotube array, double-walled carbon nano-tube array and the array of multi-walled carbon nanotubes as.The diameter of described carbon nano-tube is 1～50 nanometer, and length is 50 nanometers～5 millimeter.In the present embodiment, the length of carbon nano-tube is preferably 100～900 microns.
Carbon source gas can be selected the more active hydrocarbons of chemical property such as acetylene, ethene, methane for use in the embodiment of the invention, and the preferred carbon source gas of the embodiment of the invention is acetylene; Protective gas is nitrogen or inert gas, and the preferred protective gas of the embodiment of the invention is an argon gas.
Be appreciated that the carbon nano pipe array that the embodiment of the 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 may further comprise the steps: (a) from described super in-line arrangement carbon nano pipe array selected one or have a plurality of carbon nano-tube of certain width, present embodiment is preferably and adopts adhesive tape, tweezers or clip contact carbon nano pipe array with certain width with selected one or have a plurality of carbon nano-tube of certain width; (b) with certain speed this selected carbon nano-tube that stretches, thereby form end to end a plurality of 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, these a plurality of carbon nano-tube fragments are when tension lower edge draw direction breaks away from growth substrate gradually, because Van der Waals force effect, should selected a plurality of carbon nano-tube fragments be drawn out continuously end to end 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 a plurality of end to end carbon nano-tube, and this carbon nano-tube is arranged along draw direction substantially.See also Fig. 5 and Fig. 6, this carbon nano-tube film comprises a plurality of carbon nano-tube that are arranged of preferred orient 145.Further, described carbon nano-tube film comprises a plurality of 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 a plurality of carbon nano-tube that are arranged parallel to each other 145.Directly the method for stretching acquisition carbon nano-tube film is simply 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.When the area of this carbon nano pipe array was 4 inches, the width of this carbon nano-tube film was 0.5 nanometer～10 centimetre, and the thickness of this carbon nano-tube film is 0.5 nanometer～100 micron.
At last, 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 with at least two parallel no gaps of carbon nano-tube membrane or/and stacked laying obtains a carbon nano tube structure 164.Because this carbon nano-tube membrane has bigger specific area, so this carbon nano-tube membrane has big viscosity, formation one carbon nano tube structure 164 so the 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 the 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 is extended along an electrode to another electrode direction
In the present embodiment, further comprise the step of handling carbon nano tube structure 164 with organic solvent, this organic solvent is a volatile organic solvent, can select in ethanol, methyl alcohol, acetone, dichloroethanes and the chloroform one or several mixing for use, and the organic solvent in the present embodiment adopts ethanol.This step of with an organic solvent handling is specially: this carbon nano tube structure 164 is arranged on a substrate surface or the frame structure, by test tube organic solvent is dropped in the whole carbon nano tube structure 164 of carbon nano tube structure 164 surface infiltrations, perhaps, also above-mentioned carbon nano tube structure 164 can be immersed in the container that fill organic solvent and soak into.Described carbon nano tube structure 164 after organic solvent soak into to be handled, when the number of plies of carbon nano-tube film more after a little while, under capillary effect, carbon nano-tube adjacent in the carbon nano-tube film can be shrunk to carbon nano tube line spaced apart.And when the number of plies of carbon nano-tube film more for a long time, the multilayer carbon nanotube film after organic solvent is handled is a uniform membrane structure.After organic solvent was handled, the viscosity of carbon nano tube structure 164 reduced, and was more convenient for using.
(2) comprise at least one carbon nano-tube waddingization film when this carbon nano tube structure 164, the preparation method of this carbon nano tube structure 164 may further comprise the steps:
At first, provide a carbon nanometer tube material.
Described carbon nanometer tube material can be the carbon nano-tube by prepared in various methods 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 that aligns is scraped from substrate, obtain a carbon nanometer tube material.Preferably, in the described carbon nanometer tube material, the length of carbon nano-tube is greater than 100 microns.
Next adds to above-mentioned carbon nanometer tube material in one solvent and wadding a quilt with cotton processing obtains a carbon nanotube flocculent structure, above-mentioned carbon nanotube flocculent structure is separated from solvent, and this carbon nanotube flocculent structure typing is handled to obtain a carbon nano-tube film.
In the embodiment of the invention, the optional water of solvent, volatile organic solvent etc.The waddingization processing can be by adopting methods such as ultrasonic wave dispersion treatment or high strength stirring.Preferably, the embodiment of the invention adopts ultrasonic wave to disperse 10 minutes～30 minutes.Because carbon nano-tube has great specific area, has bigger Van der Waals force between the carbon nano-tube of twining mutually.Above-mentioned wadding processing can't be dispersed in the carbon nano-tube in this carbon nanometer tube material in the solvent fully, attracts each other, twines by Van der Waals force between the carbon nano-tube, forms network-like structure.
In the embodiment of the invention, the method for described separating carbon nano-tube flocculent structure specifically may further comprise the 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 of separating, and Figure 19 is the photo of this carbon nanotube flocculent structure.
In the embodiment of the invention, the typing processing procedure of described carbon nanotube flocculent structure specifically may further comprise the steps: above-mentioned carbon nanotube flocculent structure is placed 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 with the oven dry of solvent residual in this carbon nanotube flocculent structure or the equal solvent acquisition one carbon nano-tube waddingization film afterwards that volatilize naturally, Fig. 7 is the stereoscan photograph of this carbon nano-tube waddingization film.
Be appreciated that the embodiment of the invention can control the thickness and the surface density of this carbon nano-tube waddingization film by controlling area that this carbon nanotube flocculent structure spreads out.The area that carbon nanotube flocculent structure is spread out is big more, and then the thickness of this carbon nano-tube waddingization film and surface density are just more little.The carbon nano-tube waddingization film that obtains in the embodiment of the invention, the thickness of this carbon nano-tube waddingization film are 1 micron-2 millimeters.
In addition, the step that carbon nanotube flocculent structure is handled in above-mentioned separation and typing also can be directly mode by suction filtration realize, specifically may further comprise the steps: a miillpore filter and a funnel of bleeding is provided; The above-mentioned solvent that contains carbon nanotube flocculent structure is poured in this funnel of bleeding through this miillpore filter; Suction filtration and dry back obtain a carbon nano-tube waddingization film.This miillpore filter is that a smooth surface, aperture are 0.22 micron filter membrane.Because suction filtration mode itself will provide a bigger gas pressure in this carbon nanotube flocculent structure, this carbon nanotube flocculent structure can directly form a uniform carbon nano-tube waddingization film through suction filtration.And because microporous membrane surface is smooth, this carbon nano-tube waddingization film is peeled off easily, obtains the carbon nano-tube waddingization film of a self-supporting.
See also Fig. 7, comprise the carbon nano-tube of mutual winding in the above-mentioned carbon nano-tube waddingization film, attract each other, twine by Van der Waals force between the described carbon nano-tube, form network-like structure, so this carbon nano-tube waddingization film has good toughness.In this carbon nano-tube waddingization film, carbon nano-tube is evenly to distribute 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 formation one carbon nano tube structure 164 with two-layer at least carbon nano-tube waddingization film-stack setting.
(3) comprise at least one carbon nano-tube laminate when this carbon nano tube structure 164, the preparation method of this carbon nano tube structure 164 may further comprise the steps:
At first, provide a carbon nano pipe array to be formed at a growth substrate, this array is the carbon nano pipe array that aligns.
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, the effect that carbon nano-pipe array is listed in pressure can separate with growth substrate down, thereby form the carbon nano-tube laminate of forming by a plurality of carbon nano-tube, and described a plurality of carbon nano-tube goes up surperficial parallel with the carbon nano-tube laminate substantially with self supporting structure.
In the embodiment of the 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 of the shape of pressure head and direction of extrusion decision preparation.Particularly, when adopting pressure head edge, plane to push perpendicular to the direction of above-mentioned carbon nano pipe array growth substrate, can obtain carbon nano-tube is isotropic carbon nano-tube laminate of lack of alignment; When adopting roller bearing shape pressure head to roll, can obtain the carbon nano-tube laminate of carbon nano-tube along this fixed-direction orientations along a certain fixed-direction that is parallel to substrate; When adopting roller bearing shape pressure head when different directions rolls, can obtain the carbon nano-tube laminate of carbon nano-tube along the different directions orientations.
Be appreciated that, when 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 the carbon nano-tube laminate of being made up of a plurality of carbon nano-tube with self supporting structure with adjacent carbon nano-tube by Van der Waals force.The surface of described a plurality of carbon nano-tube and this growth substrate β that has angle, wherein, β is more than or equal to zero degree and smaller or equal to 15 degree (0 °≤β≤15 °).According to the mode difference that rolls, 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 makes the easy and substrate disengaging of this carbon nano-tube laminate, thereby forms the carbon nano-tube laminate of a 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 big more, the inclination angle is big more.Described inclination angle is the angle that substrate was of the carbon nano-tube in the carbon nano pipe array and this carbon nano pipe array of growing.The thickness of the carbon nano-tube laminate of preparation depends on the height and the pressure size of carbon nano pipe array.The height of carbon nano pipe array is big more and applied pressure is more little, and then the thickness of Zhi Bei carbon nano-tube laminate is big more; Otherwise the height of carbon nano pipe array is more little and applied pressure is big more, and then the thickness of Zhi Bei carbon nano-tube laminate is more little.The width of this carbon nano-tube laminate is relevant with the size of the substrate that carbon nano pipe array is grown, 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 that obtains in the embodiment of the invention, the thickness of this carbon nano-tube laminate are 1 micron～2 millimeters.
At last, this carbon nano-tube laminate is uncovered from described growth substrate, thereby obtained the carbon nano-tube laminate of a self-supporting.
Comprise a plurality ofly in the above-mentioned carbon nano-tube laminate, attract each other by Van der Waals force between the described carbon nano-tube, so this carbon nano-tube laminate has good toughness along same direction or the carbon nano-tube that is arranged of preferred orient.In this carbon nano-tube laminate, even carbon nanotube distributes, and is regularly arranged.
Be appreciated that this carbon nano-tube laminate has certain thickness, and can control its thickness by the 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 formation one carbon nano tube structure 164 with the stacked setting of two-layer at least carbon nano-tube laminate.
(4) when this carbon nano tube structure 164 comprised at least one liner structure of carbon nano tube, the preparation method of this carbon nano tube structure 164 may further comprise the steps:
At 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, handle this carbon nano-tube membrane, form at least one carbon nano tube line.
The step of this processing carbon nano-tube membrane can be handled this carbon nano-tube membrane for adopting organic solvent, thereby obtains a non-carbon nano tube line that reverses, or for the employing mechanical external force reverses this carbon nano-tube membrane, thereby obtain a carbon nano tube line that reverses.
The step that adopts organic solvent to handle this carbon nano-tube membrane is specially: the whole surface of organic solvent being soaked into described carbon nano-tube membrane, under the capillary effect that when volatile organic solvent volatilizees, produces, the a plurality of carbon nano-tube that are parallel to each other in the carbon nano-tube membrane are combined closely by Van der Waals force, thereby make the carbon nano-tube membrane be punctured into a non-carbon nano tube line that reverses.This organic solvent is a volatile organic solvent, as ethanol, methyl alcohol, acetone, dichloroethanes or chloroform, adopts ethanol in the present embodiment.Compare with the carbon nano-tube membrane of handling without organic solvent by the non-carbon nano tube line that reverses that organic solvent is handled, specific area reduces, and viscosity reduces.Be appreciated that, it is similar that this employing organic solvent is handled the method for the viscosity that adopts organic solvent reduction carbon nano-tube membrane among method that carbon nano-tube membrane forms the non-carbon nano tube line that reverses and (one), its difference is, when needs form the non-carbon nano tube line that reverses, the two ends of carbon nano-tube membrane are unfixing, promptly the carbon nano-tube membrane are not arranged on substrate surface or the frame structure.
The step that adopts mechanical external force to reverse this carbon nano-tube membrane is reversed described carbon nano-tube film two ends in opposite direction for adopting a mechanical force.In the embodiment of the invention, specifically can provide an afterbody can cling the spinning axle of carbon nano-tube membrane.The afterbody of this spinning axle with after the carbon nano-tube membrane combine, should be spinned and spool rotated this carbon nano-tube membrane, formation one carbon nano tube line that reverses in rotary manner.The rotation mode that is appreciated that above-mentioned spinning axle is not limit, and can just change, and can reverse yet, and perhaps rotates and reverse to combine.
Further, can adopt a volatile organic solvent to handle the carbon nano tube line that this reverses.Under the capillary effect that when volatile organic solvent volatilizees, produces, adjacent carbon nano-tube is combined closely by Van der Waals force in the carbon nano tube line that reverses after the processing, the specific area of the carbon nano tube line that reverses is reduced, viscosity reduces, and specific density and intensity all increase mutually with the carbon nano tube line of handling without organic solvent that reverses.
Once more, 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.
Above-mentioned carbon nano tube line that reverses or the non-carbon nano tube line that reverses are a self supporting structure, can directly use as a carbon nano tube structure 164.In addition, a plurality of carbon nano tube lines can be arranged in parallel into the liner structure of carbon nano tube of a pencil structure, perhaps a plurality of carbon nano tube lines that this is arranged in parallel reverse the liner structure of carbon nano tube that step obtains the hank line structure through one.Further, can with these a plurality of carbon nano tube lines or liner structure of carbon nano tube be arranged parallel to each other, cross arrangement or braiding, obtain the carbon nano tube structure 164 of a two dimension.
Step 2 forms one first electrode 12 and one second electrode 14 at interval in the two ends of this carbon nano tube structure 164, and this first electrode 12 and one second electrode 14 form with this carbon nano tube structure 164 and be electrically connected.
The set-up mode of described first electrode 12 and one second electrode 14 is relevant with carbon nano tube structure 164.When carbon nano-tube in the carbon nano tube structure 164 when partial order is arranged at least, as this carbon nano tube structure 164 comprise a carbon nano-tube membrane, when a fixed-direction rolls the carbon nano-tube laminate that obtains or a carbon nano tube line, promptly in this carbon nano tube structure 164 most of carbon nano-tube when same direction is arranged of preferred orient, preferably, should guarantee that the part carbon nano-tube in the carbon nano tube structure 164 extends along first electrode, 12 to 1 second electrode 14 directions, first electrode 12 and second electrode 14 are arranged on the bearing of trend of this carbon nano-tube.This kind set-up mode can guarantee that carbon nano tube structure 164 has best conductivity, thereby makes heating element 16 have best heating effect.
Described first electrode 12 and one second electrode 14 can be arranged on the same surface of carbon nano tube structure 164 or on the different surfaces, perhaps 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 first electrode 12 and one second electrode 14 avoids short circuit phenomenon to produce so that carbon nano tube structure 164 inserts certain resistance when being applied to line heat source 10.Carbon nano tube structure 164 itself has good adhesiveness and conductivity, thus first electrode 12 and one second electrode 14 can and carbon nano tube structure 164 between form and well electrically contact.
Described 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 in carbon nano tube structure 164 surfaces by conductive adhesive, perhaps are fixed on carbon nano tube structure by screw, clamping plate etc.Adopt vacuum vapour deposition to form two palladium films at carbon nano tube structure 164 two ends in the embodiment of the invention, as first electrode 12 and second electrode 14.
Described 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 by viscosity or the conductive adhesive surface of being fixed in carbon nano tube structure 164 of himself.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, coat a metal level to the small part carbon nano tube surface in the described metallic carbon nanotubes layer, thereby improve 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 after forming first electrode 12 and one second electrode 14 can further form two conductive lead wires, the end with first electrode 12 and second electrode 14 is electrically connected respectively, leads to external power source from first electrode 12 and one second electrode 14.
Step 3 provides a matrix precursor, and matrix precursor and carbon nano tube structure 164 is compound, forms a heating element 16.
The material of described matrix precursor is material, the formed solution of this basis material of this matrix or the forerunner's reactant for 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 the thermosetting polymer, so 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 dissolves the mixed liquor of back formation in volatile organic solvent.After this carbon nano tube structure 164 directly is soaked in this liquid matrix precursor, this matrix precursor is solidified, it is compound with this carbon nano tube structure 164 to form matrix 162.
This Inorganic Non-metallic Materials can comprise one or more in glass, pottery and the semi-conducting material, so the slurry that this matrix precursor can be made for the 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 vapor deposition (CVD) and physical vapor deposition (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, when this matrix precursor is liquid state, this step 3 specifically comprises the step that this liquid state matrix precursor is soaked into 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; When this matrix precursor was gaseous state, this step 3 specifically comprised this matrix precursor of deposition 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.
Present embodiment adopts the injecting glue method that epoxy resin-base material and carbon nano tube structure 164 is compound, forms a heating element 16, specifically may further comprise the steps:
Step (one): a liquid thermosetting macromolecular material is provided.
The viscosity of described liquid thermosetting macromolecular material was lower than for 5 handkerchief seconds, and can at room temperature keep this viscosity more than 30 minutes.The embodiment of the invention preferably prepares the liquid thermosetting macromolecular material with epoxy resin, and it specifically may further comprise the steps:
At first, the mixture of glycidol ether type epoxy and glycidyl ester type epoxy is placed a container, be heated to 30 ℃～60 ℃, and the mixture of type epoxy of glycidol ether described in the container and glycidyl ester type epoxy stirred 10 minutes, till the mixture of described glycidol ether type epoxy and glycidyl ester type epoxy mixes.
Secondly, fatty amine and diglycidyl ether are joined in the mixture of described glycidol ether type epoxy that stirs and glycidyl ester type epoxy and carry out chemical reaction.
At last, the mixture of described glycidol ether type epoxy and glycidyl ester type epoxy is heated to 30 ℃～60 ℃, thereby obtains a liquid thermosetting macromolecular material that contains epoxy resin.
Step (two): adopt described liquid thermosetting macromolecular material to soak into described carbon nano tube structure 162.
Adopt the method that described liquid thermosetting macromolecular material soaks into described carbon nano tube structure 162 may further comprise the steps in the present embodiment:
At first, carbon nano tube structure 162 is positioned in the mould.
Secondly, described liquid thermosetting macromolecular material is injected in the described mould, soaks into described carbon nano tube structure 162.In order to allow the liquid thermosetting macromolecular material fully soak into described carbon nano tube structure 162, the time of soaking into 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 soaked into described carbon nano tube structure 162 is not limit the method for injection, described liquid thermosetting macromolecular material can also be inhaled in the described carbon nano tube structure 162 by capillarity, soak into described carbon nano tube structure 162, perhaps described carbon nano tube structure 162 is immersed in the described liquid thermosetting macromolecular material.
Step (three): solidify the above-mentioned carbon nano tube structure 162 that is soaked into by the liquid thermosetting macromolecular material, obtain a composite structure of carbon nano tube.
The curing that present embodiment contains the thermoset macromolecule material of epoxy resin specifically may further comprise the steps:
At first, with this mold heated to 50 ℃～70 ℃, the thermoset macromolecule material that contains epoxy resin under this temperature was kept this temperature 1 hour～3 hours for liquid, made this thermoset macromolecule material continue heat absorption to increase its curing degree by a heater.
Secondly, continue this mould to 80 of heating ℃～100 ℃, under this temperature, kept 1 hour～3 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.
Once more, continue this mould to 110 of heating ℃～150 ℃, under this temperature, kept 2 hours～20 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.
At last, stop the heating, treat that this mould is cooled to room temperature after, the demoulding can get a composite structure of carbon nano tube.
The application number that the concrete steps of above-mentioned preparation composite structure of carbon nano tube can be applied on December 14th, 2007 referring to people such as Fan Shoushan is 200710125109.8 China's Mainland patent application " preparation method of carbon nano tube compound material ".For saving space, only be 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.
Be appreciated that the above-mentioned curing that contains the thermoset macromolecule material of epoxy resin also can adopt the method that once heats up, directly temperature risen to 150 ℃, the thermoset macromolecule material heat absorption is solidified.
Be appreciated that in the above-mentioned steps two that the step that forms first electrode 12 and one second electrode 14 can carry out after forming this heating element 16.When this matrix 162 only is filled in the hole of this carbon nano tube structure 164, thereby when making carbon nano-tube partly be exposed to heating element 16 surfaces, can adopt the method identical that this first electrode 12 and one second electrode 14 directly are formed at this heating element 16 surfaces with step 2.When this matrix 162 all coats this carbon nano tube structure 164, comprise that further one exposes described carbon nano tube structure 164 in the step on heating element 16 surfaces, this first electrode 12 and second electrode 14 are electrically connected with the carbon nano tube structure 164 that exposes respectively.Particularly, can adopt a step of 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 the cut surface of this heating element 16 with this first electrode 12 and one second electrode 14, thereby be electrically connected with this carbon nano tube structure that comes out 164.
Be appreciated that when this carbon nano tube structure is wire the formation method of the heating element 36 of the 3rd embodiment can may further comprise the steps:
At first, this liner structure of carbon nano tube and described matrix precursor is compound, 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 weave mutually, intersects, side by side or coiling form the heating element 36 of a two dimension.When this carbon nano-tube wire composite construction 366 mutually during braiding, like dry goods, it is one planar that this heating element 36 can keep.The heating element 36 of braiding formation can be made into a heating resistance pad, heating clothing and heated gloves etc. mutually.When this carbon nano-tube wire composite construction 366 intersects, side by side or when coiling mutually, can bond by binding agent between these a plurality of liner structure of carbon nano tube 366, thereby make this heating element 36 keep planar.
The described mode that liner structure of carbon nano tube and matrix precursor is compound is identical with above-mentioned steps three.
This first electrode and second electrode can be formed at these 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 second electrode are formed at this exposure have on the surface of carbon nano tube structure, thereby being formed, this first electrode and second electrode and carbon nano-tube in this composite structure of carbon nano tube be electrically connected.
Be appreciated that this preparation method can further comprise the following step of selecting, thereby prepare a plane heat source 20 that has among 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, when the material of this heat-reflecting layer 27 is slaine or metal oxide, can with the Dispersion of Particles of this slaine or metal oxide in solvent, form a slurry, and with 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 invention adopts physical vaporous deposition at ceramic base plate surface deposition one deck alundum (Al layer, as heat-reflecting layer 27.
Step 5 is arranged at heat-reflecting layer 27 surfaces with heating element 26.
This heating element 26 can be fixed in heat-reflecting layer 27 surfaces by a binding agent.In addition, also can adopt the method for mechanical fixation,, 26 4 jiaos of heating elements or four limits are fixed in heat-reflecting layer 27 surfaces as adopting fixtures such as screw, clamping plate.
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 be directly method by binding agent or mechanical fixation be fixed in heating element 26 surfaces.In addition, when the material of this protective layer 25 is a thermoplastic polymer, can be with this thermoplastic polymer at high temperature in melting state coating or be wrapped in heating element 26 surfaces, solidify to form this protective layer 25 when treating low temperature.In addition,, during as a PETG (PET) film, a heat-press step be can pass through,, protective layer 25 and heating element 26 strong bonded made this protective layer 25 and these heating element 26 stack and hot pressing when this protective layer 25 is a flexible polymer.
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 evenly distributes in carbon nano tube structure, the carbon nano tube structure and the matrix of this self-supporting is directly compound, carbon nano-tube is still mutually combined keep the form of a carbon nano tube structure, thereby make in the heating element carbon nano-tube formation conductive network that can evenly distribute, be not subjected to carbon nano-tube in solution, to disperse the restriction of concentration again, make the quality percentage composition of carbon nano-tube in heating element can reach 99%, make this thermal source have 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 intensity and toughness preferably, the intensity of carbon nano tube structure is bigger, better flexible, be difficult for breaking, make it have long useful life, especially, when this carbon nano tube structure and flexible substrate are compounded to form heating element, can prepare a flexible thermal source, make this thermal source have wider range of application.The 3rd, the even carbon nanotube in the carbon nano tube structure distributes, and therefore has homogeneous thickness and resistance, and heating is even, the electric conversion efficiency height of carbon nano-tube, and the unit are thermal capacitance of this carbon nano tube structure is less than 2 * 10 -4Every square centimeter of Kelvin of joule, intensification is rapid, thermo-lag is little, thermal response speed is fast, rate of heat exchange reaches the high characteristics of radiation efficiency soon so this plane heat source has.The 4th, the diameter of carbon nano-tube is less, makes carbon nano tube structure can have less thickness, can prepare miniature plane heat source, is applied to the heating of microdevice.The 5th, when carbon nano tube structure comprises the carbon nano-tube membrane, this carbon nano-tube membrane can obtain by pulling from carbon nano pipe array, and method is simple and help the making of large tracts of land plane heat source, and in this carbon nano-tube membrane, carbon nano-tube is arranged of preferred orient along same direction, have electric conductivity preferably, make this thermal source have heating properties preferably, 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 weaving the heating element that forms different shape, thus the plane heat source of preparation different shape.The 7th, this carbon nano-tube waddingization film and carbon nano-tube laminate have toughness preferably, and the preparation method is simple.The 8th, this forms the carbon nano tube structure of self-supporting, and it is simple that this carbon nano tube structure and matrix directly are compounded to form the method for heating element, and the content of carbon nano-tube in heating element can be controlled easily.With matrix compound after, this carbon nano tube structure still can keep original form, has the heating property suitable with the pure nano-carbon tube structure.The 9th, this carbon nano tube structure can selectively be arranged at an a certain position that has 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 variations in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention all should be included within the present invention's scope required for protection.

Claims (17)

1. a plane heat source is characterized in that, comprising:
The carbon nano tube structure of the self-supporting of the one that one heating element, this heating element are made up of a matrix and a plurality of carbon nano-tube is composited; And
At least two electrode gap settings also are electrically connected with this heating element.
2. plane heat source as claimed in claim 1 is characterized in that described carbon nano tube structure comprises the composite construction of at least one carbon nano-tube film, at least one liner structure of carbon nano tube or its combination.
3. plane heat source as claimed in claim 2 is characterized in that, described carbon nano tube structure comprises that the setting of a plurality of carbon nano-tube film-stack or a plurality of carbon nano-tube film are arranged side by side.
4. plane heat source as claimed in claim 2 is characterized in that, described carbon nano-tube film comprises equally distributed a plurality of carbon nano-tube, and these a plurality of carbon nano-tube are arranged in order.
5. plane heat source as claimed in claim 4 is characterized in that, described carbon nano-tube film comprises that a plurality of carbon nano-tube are arranged of preferred orient along same direction, and these a plurality of carbon nano-tube join end to end by Van der Waals force.
6. plane heat source as claimed in claim 5 is characterized in that, carbon nano-tube is extended to another electrode along an electrode in the described carbon nano-tube film.
7. plane heat source as claimed in claim 2 is characterized in that, the thickness of described carbon nano-tube film is 0.5 nanometer～100 micron.
8. plane heat source as claimed in claim 1 is characterized in that, the unit are thermal capacitance of described carbon nano tube structure is less than 2 * 10 -4Every square centimeter of Kelvin of joule.
9. plane heat source as claimed in claim 1 is characterized in that, described at least two electrodes are electrically connected with described carbon nano tube structure respectively.
10. plane heat source as claimed in claim 1 is characterized in that, attracts each other owing to the Van der Waals force effect between the carbon nano-tube in the carbon nano tube structure of described self-supporting.
11. plane heat source as claimed in claim 1 is characterized in that, the material of described matrix is high-molecular organic material or Inorganic Non-metallic Materials.
12. plane heat source as claimed in claim 1 is characterized in that, described plane heat source further comprises a supporter, and described heating element passes through this support body supports to small part, and the material of this supporter is flexible material or hard material.
13. plane heat source as claimed in claim 12 is characterized in that, described plane heat source further comprises a heat-reflecting layer, and described heat-reflecting layer is arranged between described heating element and the supporter or is arranged on the surface of described supporter away from heating element.
14. a plane heat source comprises:
One heating element and at least two electrode gap settings also are electrically connected with this heating element, it is characterized in that: this heating element comprises the carbon nano tube structure of one, this carbon nano tube structure comprises a plurality of carbon nano-tube that attract each other by the Van der Waals force effect, and this basis material is compound in this carbon nano tube structure.
15. plane heat source as claimed in claim 14 is characterized in that, described carbon nano tube structure has a plurality of holes, and described basis material is compound in the hole of described carbon nano tube structure.
16. plane heat source as claimed in claim 15 is characterized in that, described pore-size is less than 10 microns.
17. a plane heat source is characterized in that it comprises:
One two-dimentional heating element, this two dimension heating element comprises a plurality of carbon nano-tube, and a matrix, and these a plurality of carbon nano-tube form the carbon nano tube structure of one by Van der Waals force, and this carbon nano tube structure is mutually compound with matrix; And
At least two electrode gap settings also are electrically connected with this heating element.
CN 200910106803 2008-06-07 2009-04-20 Plane heat source Active CN101868066B (en)

Priority Applications (17)

Application Number Priority Date Filing Date Title
CN 200910106803 CN101868066B (en) 2009-04-20 2009-04-20 Plane heat source
US12/655,507 US20100122980A1 (en) 2008-06-13 2009-12-31 Carbon nanotube heater
US12/658,237 US20100154975A1 (en) 2008-06-13 2010-02-04 Carbon Nanotube heater
US12/658,182 US20100147827A1 (en) 2008-06-13 2010-02-04 Carbon nanotube heater
US12/658,198 US20100147830A1 (en) 2008-06-07 2010-02-04 Carbon nanotube heater
US12/658,193 US20100147829A1 (en) 2008-06-13 2010-02-04 Carbon nanotube heater
US12/658,184 US20100147828A1 (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
US12/661,150 US20100170890A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,165 US20100170891A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,115 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
JP2010097283A JP5281036B2 (en) 2009-04-20 2010-04-20 Surface heat source

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