CN101868067B - Plane heat source - Google Patents

Plane heat source Download PDF

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Publication number
CN101868067B
CN101868067B CN200910106804.9A CN200910106804A CN101868067B CN 101868067 B CN101868067 B CN 101868067B CN 200910106804 A CN200910106804 A CN 200910106804A CN 101868067 B CN101868067 B CN 101868067B
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China
Prior art keywords
carbon nano
cnt
nano tube
tube structure
heating element
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CN200910106804.9A
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CN101868067A (en
Inventor
刘长洪
王佳平
范守善
姜开利
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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 CN200910106804.9A priority Critical patent/CN101868067B/en
Priority to US12/655,507 priority patent/US20100122980A1/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 US12/658,237 priority patent/US20100154975A1/en
Priority to US12/658,182 priority patent/US20100147827A1/en
Priority to US12/660,356 priority patent/US20110024410A1/en
Priority to US12/660,820 priority patent/US20100163547A1/en
Priority to US12/661,150 priority patent/US20100170890A1/en
Priority to US12/661,133 priority patent/US20100200568A1/en
Priority to US12/661,165 priority patent/US20100170891A1/en
Priority to US12/661,115 priority patent/US20100200567A1/en
Priority to US12/661,110 priority patent/US20100218367A1/en
Priority to US12/661,926 priority patent/US20100187221A1/en
Priority to US12/750,186 priority patent/US20100180429A1/en
Priority to JP2010097282A priority patent/JP5281035B2/en
Publication of CN101868067A publication Critical patent/CN101868067A/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 comprises a substrate and a plurality of carbon nano tubes distributed in the substrate; the carbon nano tubes in the heating element form at least a self-supporting carbon nano tube structure; and the carbon nano tubes in the carbon nano tube structure are arranged out of order or arranged by preferred orientation along the same direction or arranged by preferred orientation along different directions. 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 CNT.
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 two-dimensional structure, and heat object the top that heated material is placed in to this two-dimensional structure, and therefore, plane heat source can heat each position of heated material simultaneously, heating surface is large, homogeneous heating and efficiency higher.Plane heat source is successfully for industrial circle, scientific research field or sphere of life etc., as electric heater, electric blanket, infrared therapeutic apparatus and electric heater etc.
Existing plane heat source generally comprises a heating element heater and at least two electrodes, and these at least two electrodes are arranged at the surface of this heating element heater, and is electrically connected to this heating element heater.When passing into voltage or electric current by electrode to heating element heater, because heating element heater has larger resistance, pass into the electric energy energy transform into heat energy of heating element heater, and discharge from heating element heater.Commercially available plane heat source adopts the heating wire that wire or carbon fiber are made to carry out electric heating conversion as heating element heater conventionally now.
Yet wire or carbon fiber all have the shortcoming that intensity is not high, electric conversion efficiency is lower and quality is larger.Wire is easy to fracture, and particularly repeatedly crooked or when being converted into certain angle, easily produce tiredly, therefore application is restricted.In addition, the heat that heating wire was produced made from wire or carbon fiber is to extraradial with common wavelength, its electric conversion efficiency is not high is unfavorable for saving the energy, need add snearing to have the cotton thread of far ultrared paint to improve electric conversion efficiency, is unfavorable for energy-conserving and environment-protective.Carbon fiber and quality wiry are all larger, are unfavorable for making thermal source lightness.Meanwhile, carbon fiber size is not little, is unfavorable for being applied to miniature thermal source.
Since the early 1990s, with CNT, (refer to Helical microtubules of graphitic carbon, Nature, Sumio Iijima, vol 354, p56 (1991)) with its unique structure and character, caused that people pay close attention to greatly for the nano material of representative.In recent years, along with deepening continuously of CNT and nano materials research, its wide application prospect constantly displayed.The people such as Fan Shoushan disclose a kind of nanometer flexible electric heating material on December 19th, 2007 in No. CN101090586Ath, a disclosed Chinese patent application.This thermo electric material comprises a flexible substrate and is dispersed in a plurality of CNTs in described flexible substrate.The plurality of CNT exists with powdered form, and adhesion is very weak to each other, cannot form a self supporting structure with given shape.When the CNT of this powdered form is mixed with polymer solution, the CNT of this powdered form is very easily reunited, thereby it is inhomogeneous to cause CNT to disperse in matrix.Agglomeration while disperseing in polymer solution for fear of CNT, on the one hand, the mixture that needs to process by supersonic oscillations this CNT and polymer solution in the process of disperseing, on the other hand, in this thermo electric material, the quality percentage composition of CNT can not be too high, is only 0.1～4%.
And CNT is through after above-mentioned dispersion treatment, even if CNT can be in contact with one another to each other, its adhesion also a little less than, cannot form the carbon nano tube structure of a self-supporting.Because content of carbon nanotubes is few, the thermal response speed of thermoelectric material is fast not, and electric conversion efficiency is not high enough, therefore the heating temp of this thermo electric material is not high enough, has limited its range of application.In addition, for CNT is disperseed in liquid phase, while preparing thermo electric material, its flexible substrate can only selective polymer material, polymeric material heat resisting temperature is lower, and the method for this kind of employing dispersing Nano carbon tubes formation thermo electric material in liquid phase has limited the selection of matrix 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, comprise: a heating element heater, this heating element heater comprises the carbon nano tube structure of the self-supporting of matrix and at least one one, described carbon nano tube structure comprises at least one deck CNT laminate, the mutual part of CNT adjacent in every one deck CNT laminate is overlapping, and attract each other by Van der Waals force, combine closely; And, at least two electrode gap settings are also electrically connected to this heating element heater, the carbon nano tube structure of the self-supporting of described at least one one is embedded in this matrix compound with matrix, and substantially keep the shape before compound, the CNT lack of alignment in this carbon nano tube structure, the CNT in this carbon nano tube structure to be arranged of preferred orient in the same direction or this carbon nano tube structure in CNT along different directions, be arranged of preferred orient.
A kind of plane heat source, comprise: a heating element heater and at least two electrode gap settings are also electrically connected to this heating element heater, this heating element heater comprises the carbon nano tube structure of the self-supporting of at least one one, and matrix material is compound in this carbon nano tube structure, described carbon nano tube structure comprises at least one deck CNT laminate, the mutual part of CNT adjacent in every one deck CNT laminate is overlapping, and attract each other by Van der Waals force, combine closely, in this heating element heater, this carbon nano tube structure keeps compound shape before substantially, CNT lack of alignment in this carbon nano tube structure, CNT in this carbon nano tube structure be arranged of preferred orient in the same direction or this carbon nano tube structure in CNT along different directions, be arranged of preferred orient, described carbon nano tube structure has a plurality of micropores, described matrix material is evenly compound in the micropore of described carbon nano tube structure.
Compared with prior art, described plane heat source is owing to adopting the carbon nano tube structure of self supporting structure, and CNT is uniformly distributed in carbon nano tube structure, by the carbon nano tube structure of this self-supporting and matrix direct combination, without the scattering problem that solves CNT, the content of CNT is unrestricted, can make in the heating element heater of compound rear formation CNT still mutually combine and keep the form of a carbon nano tube structure, makes this thermal source have better heating properties.In addition, the kind of this matrix 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 carbon nano tube structure distributes, therefore there is uniform thickness and resistance, evenly, the electric conversion efficiency of CNT is high in heating, so this plane heat source has the feature rapid, thermo-lag is little, rate of heat exchange is fast, radiation efficiency is high that heats up.
Accompanying drawing explanation
Fig. 1 is the structural representation of the plane heat source of first embodiment of the invention.
Fig. 2 is that Fig. 1 is along the generalized section of II-II line.
Fig. 3 is the structural representation that the embodiment of the present invention comprises the plane heat source of a plurality of cross one another liner structure of carbon nano tube.
Fig. 4 is the structural representation that the embodiment of the present invention comprises the plane heat source of the liner structure of carbon nano tube that a bending is coiled.
Fig. 5 is the structural representation of CNT fragment in the CNT membrane structure in embodiment of the present invention plane heat source.
Fig. 6 is the stereoscan photograph of the CNT membrane structure in embodiment of the present invention plane heat source.
Fig. 7 is the stereoscan photograph of the CNT waddingization membrane structure in embodiment of the present invention plane heat source.
Fig. 8 is the stereoscan photograph that in the CNT laminate structure in embodiment of the present invention plane heat source, CNT is arranged of preferred orient along different directions.
Fig. 9 is the stereoscan photograph that in the CNT laminate structure in embodiment of the present invention plane heat source, CNT is arranged of preferred orient in the same direction.
Figure 10 is the stereoscan photograph of the carbon nano tube line of the non-torsion in embodiment of the present invention plane heat source.
Figure 11 is the stereoscan photograph of the carbon nano tube line of the torsion in embodiment of the present invention plane heat source.
Figure 12 is the truncation surface stereoscan photograph of the heating element heater that is compounded to form of CNT membrane in embodiment of the present invention plane heat source and epoxy resin.
Figure 13 is the structural representation of the plane heat source of the embodiment of the present invention carbon nano tube structure that comprises a plurality of spaces.
Figure 14 is the temperature variation curve of the heating element heater in use Figure 12 under different voltage.
Figure 15 is the structural representation of the plane heat source of second embodiment of the invention.
Figure 16 is that Figure 15 is along the generalized section of XVI-XVI line.
Figure 17 is the structural representation of the plane heat source of third embodiment of the invention.
Figure 18 is embodiment of the present invention plane heat source preparation method's flow chart.
Figure 19 is the photo of embodiment of the present invention plane heat source preparation method's carbon nanotube flocculent structure.
The specific embodiment
Below with reference to drawings and the specific embodiments, describe plane heat source provided by the invention in detail.
Refer to Fig. 1 and Fig. 2, first embodiment of the invention provides a kind of plane heat source 10, and this plane heat source 10 is two-dimensional structure, and this plane heat source 10 is the structures of extending along two-dimensional directional.Even but it should be pointed out that to there is certain thickness two-dimensional structure, in macroscopic view, be still considered as or the approximate embodiment that is considered as two-dimentional structure, for example: tabular, the structure such as membranaceous, also should be considered as the scope of protection of the invention.
This plane heat source 10 comprises a heating element heater 16, one first electrode 12 and one second electrode 14.This heating element heater 16 is electrically connected to the first electrode 12 and the second electrode 14, thereby for making described heating element heater 16 current flowing that switches on power.
Described heating element heater 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 is larger, this carbon nano tube structure 164 is arranged in matrix 162, and completely coated by this matrix 162.This heating element heater 16 is a layer structure, and particularly, this heating element heater 16 can be a planar structure or curved-surface structure.In the present embodiment, this matrix 162 is a tabular cuboid, and this carbon nano tube structure 164 is embedded in this matrix 162 completely.
This carbon nano tube structure 164 is a self supporting structure.So-called " self supporting structure " i.e. this carbon nano tube structure 164, without by a support body supports, also can keep self specific shape.The carbon nano tube structure 164 of this self supporting structure comprises a plurality of CNTs, the plurality of CNT attracts each other by Van der Waals force, thereby form a network structure, and make carbon nano tube structure 164 there is specific shape, to form the carbon nano tube structure of the self-supporting of an one.In the present embodiment, this carbon nano tube structure 164 is the planar or one dimension linear structure of two dimension.Because this carbon nano tube structure 164 has self-supporting, when not supporting by supporting body surface, still can keep planar or linear structure.In this carbon nano tube structure 164, between CNT, have a large amount of gaps, thereby make this carbon nano tube structure 164 have a large amount of holes, these matrix 162 materials infiltrate in this hole.
Described carbon nano tube structure 164 comprises equally distributed a large amount of CNT, between CNT, by Van der Waals force, combines closely.CNT in this carbon nano tube structure 164 is unordered or ordered arrangement.The orientation of the unordered finger CNT is here irregular, and the orientation of at least most CNTs of orderly finger here has certain rule.Particularly, when carbon nano tube structure 164 comprises the CNT of lack of alignment, CNT can further be wound around mutually, carbon nano tube structure 164 isotropism that the CNT of this lack of alignment forms; When carbon nano tube structure 164 comprises the CNT of ordered arrangement, CNT is arranged of preferred orient along a direction or multiple directions.The thickness of this carbon nano tube structure 164 is preferably 0.5 nanometer～1 millimeter.CNT in this carbon nano tube structure 164 comprises one or more in SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes.The diameter of described SWCN is 0.5 nanometer～50 nanometer, and the diameter of described double-walled carbon nano-tube is 1.0 nanometer～50 nanometers, and the diameter of described multi-walled carbon nano-tubes is 1.5 nanometer～50 nanometers.Preferably, described carbon nano tube structure 164 comprises the CNT of ordered arrangement, and CNT is arranged of preferred orient along a fixed-direction.The thermal response speed that is appreciated that carbon nano tube structure 164 is relevant with its thickness.In situation of the same area, the thickness of carbon nano tube structure 164 is larger, and thermal response speed is slower; Otherwise the thickness of carbon nano tube structure 164 is less, thermal response speed is faster.Because this carbon nano tube structure 164 is comprised 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 form.Be appreciated that when described carbon nano tube structure 164 comprises a plurality of carbon nano-tube film, the plurality of carbon nano-tube film can stacked setting or is arranged side by side.Refer to Fig. 3, when described carbon nano tube structure 164 comprises a plurality of liner structure of carbon nano tube, the plurality of liner structure of carbon nano tube can be parallel to each other, side by side or the carbon nano tube structure 164 of one-tenth arranged in a crossed manner one two dimension or be mutually wound around or be woven into the carbon nano tube structure 164 of a two dimension.In addition, refer to Fig. 4, when this carbon nano tube structure 164 can be coiled into by a liner structure of carbon nano tube bending carbon nano tube structure 164 of a two dimension.
This carbon nano-tube film comprises CNT membrane, CNT waddingization film or CNT laminate.This liner structure of carbon nano tube can comprise that at least one carbon nano tube line, a plurality of carbon nano tube line fascicular texture or a plurality of carbon nano tube line forming that be arranged in parallel reverses the twisted wire structure forming.
Described carbon nano tube structure 164 can comprise at least one CNT membrane, and this CNT membrane for directly pulling a kind of carbon nano-tube film with self-supporting of acquisition from carbon nano pipe array.Each CNT membrane comprises a plurality of preferred orientations in the same direction and is parallel to the CNT of CNT membrane surface alignment.Described CNT joins end to end by Van der Waals force, to form the CNT membrane of the self-supporting of an one.Refer to Fig. 5 and Fig. 6, particularly, each CNT membrane comprise a plurality of continuously and the CNT fragment 143 aligning.The plurality of CNT fragment 143 joins end to end by Van der Waals force.Each CNT fragment 143 comprises a plurality of CNTs that are parallel to each other 145, and the plurality of CNT being parallel to each other 145 is combined closely by Van der Waals force.This CNT fragment 143 has width, thickness, uniformity and shape arbitrarily.The thickness of described CNT membrane is 0.5 nanometer～100 micron, and width is relevant with the size of carbon nano pipe array that pulls this CNT membrane, and length is not limit.When this carbon nano tube structure 164 is comprised of CNT membrane, and the Thickness Ratio of carbon nano tube structure 164 hour, for example, be less than 10 microns, and this carbon nano tube structure 164 has good transparency, its light transmittance can reach 90%, can be for the manufacture of a transparent thermal source.
When described carbon nano tube structure 164 comprises the multilayer carbon nanotube membrane of stacked setting, between the CNT being arranged of preferred orient in adjacent two layers CNT membrane, form an intersecting angle α, α is more than or equal to 0 degree and is less than or equal to 90 degree (0 °≤α≤90 °).Between adjacent CNT between described a plurality of CNT membrane or among a CNT membrane, have certain interval, 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 CNT membrane and preparation method thereof refers to the people such as Fan Shoushan on February 9th, 2007 application, in disclosed CN101239712A China's Mainland publication application (CNT membrane structure and preparation method thereof Augusts 13 in 2008, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd.).For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
The carbon nano tube structure 164 of the embodiment of the present invention comprises a plurality of CNT membranes along the stacked setting of equidirectional, thereby CNT in carbon nano tube structure 164 is all arranged of preferred orient in the same direction.
Described carbon nano tube structure 164 can comprise at least one CNT waddingization film, and this CNT waddingization film comprises mutual winding and equally distributed CNT.The length of CNT is greater than 10 microns, is preferably 200～900 microns, thereby CNT is intertwined mutually.Between described CNT, by Van der Waals force, attract each other, be wound around, form network-like structure, to form the CNT waddingization film of the self-supporting of an one.Described CNT waddingization film isotropism.CNT in described CNT waddingization film is for being uniformly distributed, and random arrangement, forms a large amount of pore structures, and hole aperture is approximately less than 10 microns.Length and the width of described CNT waddingization film are not limit.Refer to Fig. 7, due in CNT waddingization film, CNT is wound around mutually, so this CNT waddingization film has good pliability, and is a self supporting structure, can become arbitrary shape and not break by bending fold.Area and the thickness of described CNT waddingization film are not all limit, and thickness is 1 micron～1 millimeter, are preferably 100 microns.Concrete structure of described CNT waddingization film and preparation method thereof refers to the people such as Fan Shoushan in No. 200710074027.5 China's Mainland patent application (preparation method of carbon nano-tube film of application on April 13rd, 2007, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd.).For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Described carbon nano tube structure 164 can comprise at least one CNT laminate, and this CNT laminate comprises equally distributed CNT.Described CNT is unordered, in the same direction or different directions be arranged of preferred orient.The mutual part of CNT in described CNT laminate is overlapping, and attracts each other by Van der Waals force, combines closely, and makes this carbon nano tube structure have good pliability, can become arbitrary shape and not break by bending fold.And owing to attracting each other by Van der Waals force between the CNT in CNT laminate, combine closely, making CNT laminate is the structure of the self-supporting of an one.Described CNT laminate can obtain by rolling a carbon nano pipe array.CNT in described CNT laminate and the surperficial shape that forms the growth substrate of the carbon nano pipe array β that has angle, wherein, β is more than or equal to 0 degree and is less than or equal to 15 degree (0≤β≤15 °), this angle β is with to be applied to the pressure that carbon nano-pipe array lists relevant, pressure is larger, this angle is less, and preferably, the CNT in this CNT laminate is parallel to this growth substrate and arranges.This CNT laminate is for to obtain by rolling a carbon nano pipe array, and different according to the mode rolling, the CNT in this CNT laminate has different spread patterns.Refer to Fig. 8, when rolling along different directions, CNT is arranged of preferred orient along different directions.Refer to Fig. 9, when rolling in the same direction, CNT is arranged of preferred orient along a fixed-direction.In addition, when rolling direction for vertical this carbon nano pipe array surface, this CNT can lack of alignment.In this CNT laminate, the length of CNT is greater than 50 microns.
Area and the thickness of this CNT laminate are not limit, and can select according to actual needs.The area of this CNT laminate and the size of carbon nano pipe array are basic identical.The height of this CNT laminate thickness and carbon nano pipe array and the pressure rolling are relevant, can be 1 micron～1 millimeter.The height that is appreciated that carbon nano pipe array is larger and applied pressure is less, and the thickness of the CNT laminate of preparation is larger; Otherwise the height of carbon nano pipe array is less and applied pressure is larger, the thickness of the CNT laminate of preparation is less.Between adjacent CNT among described CNT laminate, have certain interval, thereby form a plurality of holes in CNT laminate, the aperture of hole is approximately less than 10 microns.Concrete structure of described CNT laminate and preparation method thereof refers to the people such as Fan Shoushan in No. 200710074699.6 China's Mainland patent application (preparation method of carbon nano-tube film of application on June 1st, 2007, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd.).For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Described carbon nano tube structure 164 can comprise at least one carbon nano tube line.This carbon nano tube line can be the carbon nano tube line of non-torsion or the carbon nano tube line of torsion.The carbon nano tube line of this non-torsion is for to process CNT membrane to obtain by organic solvent.Refer to Figure 10, the carbon nano tube line of this non-torsion comprises a plurality of CNTs of arranging along carbon nano tube line length direction.Preferably, this CNT joins end to end.Particularly, the carbon nano tube line of this non-torsion comprises a plurality of CNT fragments, and the plurality of CNT fragment joins end to end by Van der Waals force, and each CNT fragment comprises a plurality of CNTs that are parallel to each other and combine closely by Van der Waals force.This CNT fragment has length, thickness, uniformity and shape arbitrarily.The CNT line length of this non-torsion is not limit, and diameter is 0.5 nanometer-100 micron.The concrete structure of described carbon nano tube line and preparation method refer to the people such as Fan Shoushan on September 16th, 2002 application, in No. CN100411979Cth, the Chinese patent of on August 20th, 2008 bulletin, and on December 16th, 2005 application, in No. CN1982209Ath, disclosed Chinese patent application on June 20th, 2007.For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
The carbon nano tube line of this torsion is for adopting a mechanical force that described CNT membrane two ends are reversed to acquisition in opposite direction.Refer to Figure 11, the carbon nano tube line of this torsion comprises a plurality of CNTs of arranging around carbon nano tube line axial screw.Particularly, the carbon nano tube line of this torsion comprises a plurality of CNT fragments, and the plurality of CNT fragment joins end to end by Van der Waals force, and each CNT fragment comprises a plurality of CNTs that are parallel to each other and combine closely by Van der Waals force.This CNT fragment has length, thickness, uniformity and shape arbitrarily.The CNT line length of this torsion is not limit, and diameter is 0.5 nanometer-100 micron.
Further, can adopt a volatile organic solvent to process the carbon nano tube line of this torsion.Under the capillary effect producing when volatile organic solvent volatilizees, CNT adjacent in the carbon nano tube line of the torsion after processing is combined closely by Van der Waals force, diameter and the specific area of the carbon nano tube line of torsion are reduced, and density and intensity increase.
Because this carbon nano tube line obtains for adopting organic solvent or mechanical force to process above-mentioned CNT membrane, this CNT membrane is self supporting structure, therefore this carbon nano tube line is self supporting structure.This carbon nano tube line and CNT membrane are similar, are joined end to end, to form the carbon nano tube line of the self-supporting of an one by a plurality of CNTs by Van der Waals force.In addition, in this carbon nano tube line, between adjacent carbons nanotube, have gap, therefore this carbon nano tube line has a large amount of holes, the aperture of hole is approximately less than 10 microns.
The material of described matrix 162 can be chosen as macromolecular material or Inorganic Non-metallic Materials etc.This matrix 162 or the presoma that forms this matrix 162 are liquid state or gaseous state at a certain temperature, thereby the presoma of this matrix 162 or this matrix 162 can be penetrated in the gap or hole of this carbon nano tube structure 164 in the preparation process of the heating element heater 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 operating temperature of this plane heat source 10 be subject to heat damage, distortion, fusing, gasification or decomposition.
Particularly, this macromolecular material can comprise one or more of thermoplastic polymer or thermosetting polymer, as one or more in cellulose, polyethylene terephthalate, acryl resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, phenolic resins, epoxy resin, silica gel and polyester etc.This Inorganic Non-metallic Materials can comprise one or more in glass, pottery and semi-conducting material.In the embodiment of the present invention, the material of this matrix 162 is epoxy resin.
Refer to Figure 12, owing to thering is gap between CNT 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 it is inner to make this matrix 162 and these carbon nano tube structure 164 compound tenses can infiltrate the hole of this carbon nano tube structure 164.Figure 12 stretches this heating element heater 16 to these heating element heater 16 fractures along the orientation that is parallel to CNT in CNT membrane, the truncation surface photo of this heating element heater 16 obtaining, can find, after compound with epoxy resin, this carbon nano tube structure 164 still can keep compound front form substantially, and CNT is arranged of preferred orient substantially in the same direction in epoxy resin.
This matrix 162 can only be filled in the hole of described carbon nano tube structure 164, also can further be coated as shown in Figure 2 whole carbon nano tube structure 164 completely.Refer to Figure 13, when this heating element heater 16 comprises a plurality of carbon nano tube structure 164, what the plurality of carbon nano tube structure 164 can space (or being in contact with one another) is arranged in this matrix 162.When this carbon nano tube structure 164 is two-dimensional structure, this two-dimensional structure can space or being arranged side by side or stacked being arranged in matrix 162 of being in contact with one another; When this carbon nano tube structure 164 is linear structure, this linear structure can space or being arranged in matrix 162 of being in contact with one another.When this carbon nano tube structure 164 is arranged at intervals in matrix 162, can save the consumption of the required carbon nano tube structure 164 of this heating element heater 16 of preparation.In addition, visual actual needs is arranged on carbon nano tube structure 164 ad-hoc location of matrix 162, thereby makes this heating element heater 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 CNT in this carbon nano tube structure 164, make the not reason external force friction or scratch and come off of CNT in 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 heater 16 and exterior insulation simultaneously.In addition, the object that this matrix 162 can further play heat conduction and make uniform heat distribution.Further, when this carbon nano tube structure 164 steep temperature rise, this matrix 162 can play the effect of buffering heat, makes the variations in temperature of this heating element heater 16 comparatively soft.The material of this matrix 162 can adopt flexible high molecular material, thereby can strengthen flexibility and the toughness of whole plane heat source 10.
Be appreciated that, because this CNT is uniformly distributed in carbon nano tube structure 164, by matrix 162 and carbon nano tube structure 164 direct combinations of self-supporting are formed to heating element heater 16, can make CNT be uniformly distributed in heating element heater 16, and the content of CNT reaches 99%, improved the heating temp of thermal source 10.Because this carbon nano tube structure 164 is a self supporting structure, and CNT is uniformly distributed in carbon nano tube structure 164, by the carbon nano tube structure of this self-supporting 164 and matrix 162 direct combinations, can make in the heating element heater 16 of compound rear formation CNT still mutually combine and keep the form of a carbon nano tube structure 164, thereby make CNT in heating element heater 16 can be uniformly distributed formation conductive network, be not subject to again CNT in solution, to disperse the restriction of concentration, make the quality percentage composition of CNT in heating element heater 16 can reach 99%.
Described the first electrode 12 and the second electrode 14 are comprised of conductive material, and the shape of this first electrode 12 and the second electrode 14 is not limit, and can be conducting film, sheet metal or metal lead wire.Preferably, the first electrode 12 and the second electrode 14 are one deck conducting film.When for micro face thermal source 10, the thickness of this conducting film is 0.5 nanometer～100 micron.The material of this conducting film can be metal, alloy, indium tin oxide (ITO), antimony tin oxide (ATO), conductive silver glue, conducting polymer or conductive carbon nanotube etc.This metal or alloy material can be the alloy of aluminium, copper, tungsten, molybdenum, gold, titanium, neodymium, palladium, caesium or its any combination.In the present embodiment, the material of described the first electrode 12 and the second electrode 14 is Metal Palladium film, and thickness is 5 nanometers.Described Metal Palladium and CNT have good wetting effect, are conducive to form good electrically contacting between described the first electrode 12 and the second electrode 14 and described heating element heater 16, reduce ohmic contact resistance.
The first described electrode 12 and the second electrode 14 are directly electrically connected to the carbon nano tube structure 164 in heating element heater 16.Wherein, the first electrode 12 and the second electrode 14 intervals arrange, so that heating element heater 16 accesses certain resistance while being applied to plane heat source 10, avoid short circuit phenomenon to produce.
Particularly, when 162 of the matrixes of this heating element heater 16 are filled in the hole of this carbon nano tube structure 164, because part CNT in this carbon nano tube structure 164 is partly exposed to heating element heater 16 surfaces, this first electrode 12 and the second electrode 14 can be arranged on the surface of heating element heater 16, thereby this first electrode 12 and the second electrode 14 are electrically connected to carbon nano tube structure 164.The same surface that this first electrode 12 and the second electrode 14 can be arranged on heating element heater 16 also can be arranged on the different surfaces of heating element heater 16.In addition, when the matrix 162 of this heating element heater 16 is coated whole carbon nano tube structure 164, for this first electrode 12 and the second electrode 14 are electrically connected to this carbon nano tube structure 164, this first electrode 12 and the second electrode 14 can be arranged in the matrix 162 of heating element heater 16, and directly contact with carbon nano tube structure 164.Now, for making this first electrode 12 and the second electrode 14 and external power source conducting, this first electrode 12 and the second electrode 14 can partly be exposed to outside heating element heater 16; Or this thermal source 10 can further comprise two lead-in wires, be electrically connected to this first electrode 12 and the second electrode 14 respectively, and draw from these matrix 162 inside.
In this carbon nano tube structure 164, during CNT ordered arrangement, preferably, the orientation of this CNT is extended along the first electrode 12 to second electrodes 14.Particularly, when this carbon nano tube structure 164 comprises at least one CNT membrane, described the first electrode 12 and the second electrode 14 are arranged at the two ends of this CNT membrane, make in CNT membrane CNT join end to end and extend to the second electrode 14 from the first electrode 12.When this carbon nano tube structure 164 comprises a plurality of liner structure of carbon nano tube being arranged in parallel, similar to resistance wire, these liner structure of carbon nano tube two ends are electrically connected to the second electrode 14 with this first electrode 12 respectively.
The first described electrode 12 and the second electrode 14 can be arranged at this heating element heater 16 or carbon nano tube structure 164 surfaces by a conductive adhesive (not shown), conductive adhesive, when realizing the first electrode 12 and the second electrode 14 and electrically contacting with carbon nano tube structure 164, can also be fixed on described the first electrode 12 and the second electrode 14 on the surface of carbon nano tube structure 164 better.Particularly, this conductive adhesive can be elargol.
The structure and material that is appreciated that the first electrode 12 and the second electrode 14 is not all limit, and it arranges object is in order to make carbon nano tube structure 164 current flowings in described heating element heater 16.Therefore, 14 needs of described the first electrode 12 and the second electrode conduction, and and the carbon nano tube structure 164 of described heating element heater 16 between form and electrically contact all in protection scope of the present invention.
The plane heat source 10 of the embodiment of the present invention in use, accesses power supply after can first the first electrode 12 of plane heat source 10 being connected to wire with the second electrode 14.Carbon nano tube structure 164 after access power supply in thermal source 10 can give off the electromagnetic wave of certain wave-length coverage.Described plane heat source 10 can directly contact with the surface of heated material.Or described plane heat source 10 can at intervals arrange with heated material.
Plane heat source 10 in the embodiment of the present invention, in size one timing of carbon nano tube structure 164, by the thickness of regulating power source voltage size and carbon nano tube structure 164, can give off the electromagnetic wave of different wavelength range.Particularly, this carbon nano tube structure 164 can produce an infrared heat radiation.Regularly, the variation tendency that the thickness of carbon nano tube structure 164 and plane heat source 10 give off electromagnetic wavelength is contrary for the size one of supply voltage.When one timing of supply voltage size, the thickness of carbon nano tube structure 164 is thicker, and it is shorter that plane heat source 10 gives off electromagnetic wavelength; The thickness of carbon nano tube structure 164 is thinner, and it is longer that plane heat source 10 gives off electromagnetic wavelength.Regularly, the size of supply voltage and plane heat source 10 give off electromagnetic wavelength and are inversely proportional to the thickness one of carbon nano tube structure 164.When thickness one timing of carbon nano tube structure 164, supply voltage is larger, and it is shorter that plane heat source 10 spokes go out electromagnetic wavelength; Supply voltage is less, and it is longer that plane heat source 10 gives off electromagnetic wavelength.Be appreciated that, this plane heat source 10 should be applied to the voltage swing at the first electrode 12 and the second electrode 14 two ends when application by a circuit limitations according to the material of matrix 162, the heating temp of carbon nano tube structure 164 is controlled in the tolerant temperature range of this matrix 162.For example, when the material of this matrix 162 is organic high molecular polymer, this voltage range is 0～10 volt, and the heating temp of this plane heat source 10 is below 120 ℃, and lower than the fusing point of this high molecular polymer.When the material of this matrix 162 is pottery, this voltage range is 10 volts～30 volts, and the heating temp of this plane heat source 10 is 120 ℃～500 ℃.Refer to Figure 14, the embodiment of the present invention is by measuring the carbon nano tube structure 164 of the mutual stacked formation of 100 layers of CNT membrane and the plane heat source 10 of the heating element heater 16 that epoxy resin-base 162 is compounded to form, can find that this plane heat source 10 is applied to voltage higher, this plane heat source 10 heats up faster, and heating temp is higher.
CNT has good electric conductivity and heat endurance, and as a desirable black matrix structure, has higher radiation efficiency.In another embodiment, when matrix 162 adopts heat proof material, this plane heat source 10 is exposed in the environment of oxidizing gas or atmosphere, wherein the thickness of carbon nano tube structure 164 is 5 millimeters, by at 10 volts～30 volts regulating power source voltages, this plane heat source 10 can give off the longer electromagnetic wave of wavelength.By temperature measuring set, find that the temperature of this plane heat source 10 is 50 ℃～500 ℃.For the object with black matrix structure, when being 200 ℃～450 ℃, its corresponding temperature just can send heat radiation invisible to the human eye (infrared ray), and heat radiation is now the most stable, most effective.Apply the plane heat source 10 that this carbon nano tube structure 164 is made, can be applicable to the fields such as electric heater, infrared therapeutic apparatus, electric blanket, electric heater.
In addition, in the heating element heater 16 of this plane heat source 10, the thickness of carbon nano tube structure 164 is less, is a transparent carbon nano tube structure 164, and the material of this matrix 162 is while 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 heater 16 of this plane heat source 10 is made by flexible polymeric material, this plane heat source 10 is a flexible face thermal source 10.Further, because the matrix 162 of this polymeric material can form various shapes by die pressing, and this carbon nano tube line can be woven into difformity, and this flexible plane heat source 10 can be for the manufacture of garment with heating element, Warming gloves or the heating shoes etc. of spontaneous heating.
Refer to Figure 15 and Figure 16, second embodiment of the invention provides a kind of plane heat source 20, and this plane heat source 20 comprises a heating element heater 26, one first electrode 22 and one second electrode 24.This heating element heater 26 comprises that a matrix 262 and at least one carbon nano tube structure 264 are arranged in matrix 262.This heating element heater 26 is a class two-dimensional structure, is one and has certain thickness two-dimensional structure.Particularly, this heating element heater 26 can be a planar structure or curved-surface structure.The carbon nano tube structure 264 of this heating element heater 26 is electrically connected to the first electrode 22 and the second electrode 24, thereby for making described heating element heater 26 current flowing that switches on power.
The plane heat source 10 of the structure of this plane heat source 20 and the first embodiment is basic identical, and its difference is, this plane heat source 20 further comprises a supporter 28, a heat-reflecting layer 27 and a protective layer 25.Described heat-reflecting layer 27 is arranged at the surface of supporter 28.Described heating element heater 26 is arranged at the surface of described heat-reflecting layer 27.Described the first electrode 22 and the second electrode 24 are arranged at intervals at the surface of described heating element heater 26, and electrically contact with this heating element heater 26, for making described heating element heater 26 current flowings.Described protective layer 25 is arranged at the surface of described heating element heater 26, for avoiding described heating element heater 26 absorption introduced contaminantses.Described supporter 28, heat-reflecting layer 27 and protective layer 25 are optional structure.Further, this plane heat source 20 comprises two electrical leads 29, is connected respectively with described the first electrode 22 with the second electrode 24, from the first electrode 22 and the second electrode 24 that are embedded in matrix 262, leads to outside matrix 262.
Described supporter 28 shapes are not limit, and it has a surface for supporting heating element heater 16 or heat-reflecting layer 27.This surface can be plane or curved surface.Preferably, described supporter 28 is a platy structure, and its material can be hard material, as: pottery, glass, resin, quartz etc., can also select flexible material, as: plastics or resin etc.Wherein, the size of supporter 28 is not limit, and can change according to actual needs.The preferred supporter 28 of the present embodiment is a ceramic substrate.
The setting of described heat-reflecting layer 27 is used for reflecting the heat that heating element heater 26 is sent out, thereby controls the direction of heating, for single-side heating, and further improves the efficiency of heating.The material of described heat-reflecting layer 27 is a white insulating materials, as: metal oxide, slaine or pottery etc.In the present embodiment, heat-reflecting layer 27 is alundum (Al2O3) layer, and its thickness is 100 microns～0.5 millimeter.This heat-reflecting layer 27 can be formed at this supporter 28 surfaces by sputter or additive method.Be appreciated that described heat-reflecting layer 27 also can be arranged on supporter 28 away from the surface of heating element heater 26, described supporter 28 is arranged between described heating element heater 26 and described heat-reflecting layer 27.Described heat-reflecting layer 27 is a selectable structure.Described heating element heater 26 can be set directly at the surface of supporter 28, and now the heating direction of plane heat source 10 is not limit, and can be used for Double-side Heating.
Described protective layer 25 is an optional structure, and its material is an insulating materials, as: plastics, rubber or resin etc.Described protective layer 25 thickness are not limit, and can select according to actual conditions.Described protective layer 25 is covered on described the first electrode 22, the second electrode 24 and heating element heater 26, and in the present embodiment, the material of this insulating protective layer 25 is heat resistant rubber, and its thickness is 0.5～2 millimeter.Described protective layer 25 can be protected heating element heater 26; when especially in this heating element heater 26, matrix 262 is only filled in the hole of carbon nano tube structure 264; this protective layer 25 can prevent that the CNT that is exposed to heating element heater 26 surfaces is subject to external force friction and damages; in addition, can guarantee this heating element heater 26 except described the first electrode 22 and the second electrode 24 and exterior insulation.
Refer to Figure 17, third embodiment of the invention provides a kind of plane heat source 30, and this plane heat source 30 comprises a heating element heater 36, one first electrode 32 and one second electrode 34.This heating element heater 36 is a two-dimensional structure, has certain thickness two-dimensional structure.Particularly, this heating element heater 36 can be a planar structure or curved-surface structure.This heating element heater 36 is electrically connected to the first electrode 32 and the second electrode 34, thereby for making the CNT of described heating element heater 36 current flowing that switches on power.
The plane heat source 10 of the structure of this plane heat source 30 and the first embodiment is basic identical, and its difference is, this heating element heater 36 comprises a plurality of CNT wire composite constructions 366.The plurality of CNT wire composite construction 366 mutually braiding forms two-dimentional heating element heater 36.This CNT wire composite construction 366 is by a liner structure of carbon nano tube and a matrix material is compound obtains.This matrix material is filled in the hole of this liner structure of carbon nano tube.This carbon nano tube compound linear structure 366 can directly be woven into the heating element heater 36 of various shapes easily.This matrix material is preferably flexible polymer.
Refer to Figure 18, the embodiment of the present invention provides a kind of preparation method of plane heat source 10, and it comprises the following steps:
Step 1, provides a carbon nano tube structure 164, and this carbon nano tube structure 164 comprises 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 be also 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) when this carbon nano tube structure 164 comprises at least one CNT membrane, the preparation method of this carbon nano tube structure 164 specifically comprises the following steps:
First, provide a carbon nano pipe array to be formed at a growth substrate, the carbon nano pipe array that this array is super in-line arrangement.
The preparation method of this carbon nano pipe array adopts chemical vapour deposition technique, its concrete steps comprise: a smooth growth substrate (a) is provided, this growth substrate can be selected P type or the substrate of N-type silicon growth, or select the silicon growth substrate that is formed with oxide layer, the embodiment of the present invention to be preferably the silicon growth substrate that adopts 4 inches; (b) at growth substrate surface uniform, form a catalyst layer, this catalyst layer material can be selected one of alloy of iron (Fe), cobalt (Co), nickel (Ni) or its any combination; (c) the above-mentioned growth substrate that is formed with catalyst layer is annealed approximately 30 minutes～90 minutes in the air of 700 ℃～900 ℃; (d) growth substrate of processing is placed in to reacting furnace, is heated to 500 ℃～740 ℃ under protective gas environment, then pass into carbon-source gas and react approximately 5 minutes～30 minutes, growth obtains carbon nano pipe array.This carbon nano-pipe array is classified the pure nano-carbon tube array that a plurality of CNTs parallel to each other and that grow perpendicular to growth substrate form as.By above-mentioned control growth conditions, in this carbon nano pipe array aligning, substantially do not contain impurity, as agraphitic carbon or residual catalyst metal particles etc.
The carbon nano-pipe array that the embodiment of the present invention provides is classified a kind of in single-wall carbon nanotube array, double-walled carbon nano-tube array and array of multi-walled carbon nanotubes as.The diameter of described CNT is 1～50 nanometer, and length is 50 nanometer～5 millimeter.In the present embodiment, the length of CNT is preferably 100～900 microns.
In the embodiment of the present invention, carbon source gas can be selected the more active hydrocarbons of chemical property such as acetylene, ethene, methane, and the preferred carbon source gas of the embodiment of the present invention is acetylene; Protective gas is nitrogen or inert gas, and the preferred protective gas of the embodiment of the present invention is argon gas.
Be appreciated that the carbon nano pipe array that the embodiment of the present invention provides is not limited to above-mentioned preparation method, also can be graphite electrode Constant Electric Current arc discharge sedimentation, laser evaporation sedimentation etc.
Secondly, adopt a stretching tool from carbon nano pipe array, to pull CNT and obtain at least one CNT membrane, it specifically comprises the following steps: (a) from described super in-line arrangement carbon nano pipe array selected one or have a plurality of CNTs of certain width, the present embodiment is preferably and adopts adhesive tape, tweezers or the clip contact carbon nano pipe array with certain width to select one or have a plurality of CNTs of certain width; (b) with certain speed this selected CNT that stretches, thereby form end to end a plurality of CNT 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, when the plurality of CNT fragment departs from growth substrate gradually along draw direction under pulling force effect, due to van der Waals interaction, these selected a plurality of CNT fragments are drawn out end to end continuously with other CNT 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 CNTs, and this CNT is arranged along draw direction substantially.Refer to Fig. 5 and Fig. 6, this carbon nano-tube film comprises a plurality of CNTs that are arranged of preferred orient 145.Further, described carbon nano-tube film comprises a plurality of CNT fragments 143 that join end to end and align, and CNT fragment 143 two ends interconnect by Van der Waals force.This CNT fragment 143 comprises a plurality of CNTs that are arranged parallel to each other 145.The method of this acquisition carbon nano-tube film that directly stretches is simple and quick, the suitable industrial applications of carrying out.
The width of this carbon nano-tube film is relevant with the size of carbon nano pipe array, and the length of this carbon nano-tube film is not limit, and can make according to the actual requirements.When the area of this carbon nano pipe array is 4 inches, the width of this carbon nano-tube film is 0.5 nanometer～10 centimetre, and the thickness of this carbon nano-tube film is 0.5 nanometer～100 micron.
Finally, utilize above-mentioned CNT membrane to prepare carbon nano tube structure 164.
This CNT membrane can be used as a carbon nano tube structure 164 and uses.Further, can also be by least two parallel gaplesss of CNT membrane or/and stacked laying obtains a carbon nano tube structure 164.Because this CNT membrane has larger specific area, so this CNT membrane has larger viscosity, formation one carbon nano tube structure 164 therefore multilayer carbon nanotube film can be combined closely mutually.In this carbon nano tube structure 164, the number of plies of CNT membrane is not limit, and has an intersecting angle α between adjacent two layers CNT 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 CNT in carbon nano-tube film is extended along an electrode to another electrode direction
In the present embodiment, further comprise the step of processing carbon nano tube structure 164 with organic solvent, this organic solvent is volatile organic solvent, can select in ethanol, methyl alcohol, acetone, dichloroethanes and chloroform one or several mixing, and the organic solvent in the present embodiment adopts ethanol.This step of with an organic solvent processing is specially: this carbon nano tube structure 164 is arranged in a substrate surface or a frame structure, by test tube, organic solvent is dropped in to carbon nano tube structure 164 surfaces and infiltrates whole carbon nano tube structure 164, or, also above-mentioned carbon nano tube structure 164 can be immersed in the container that fills organic solvent and infiltrates.Described carbon nano tube structure 164 is after organic solvent infiltrate to be processed, and when the number of plies of carbon nano-tube film is less, under capillary effect, CNT adjacent in 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 is more, the multilayer carbon nanotube film after organic solvent is processed is a uniform membrane structure.After organic solvent is processed, the viscosity of carbon nano tube structure 164 reduces, and is more convenient for using.
(2) when this carbon nano tube structure 164 comprises at least one CNT waddingization film, the preparation method of this carbon nano tube structure 164 comprises the following steps:
First, provide a carbon nanometer tube material.
Described carbon nanometer tube material can be the CNT of preparing by the whole bag of tricks such as chemical vapour deposition technique, graphite electrode Constant Electric Current arc discharge sedimentation or laser evaporation sedimentations.
In the present embodiment, adopt blade or other instruments that the above-mentioned carbon nano pipe array aligning is scraped from substrate, obtain a carbon nanometer tube material.Preferably, in described carbon nanometer tube material, the length of CNT is greater than 100 microns.
Secondly, above-mentioned carbon nanometer tube material is added in a solvent and wad a quilt with cottonization is processed acquisition one carbon nanotube flocculent structure, by the separation from solvent of above-mentioned carbon nanotube flocculent structure, and to this carbon nanotube flocculent structure heat treatment to obtain a carbon nano-tube film.
In the embodiment of the present invention, the optional water of solvent, volatile organic solvent etc.Waddingization is processed can be by adopting the methods such as ultrasonic wave dispersion treatment or high strength stirring.Preferably, the embodiment of the present invention adopts ultrasonic wave to disperse 10 minutes～30 minutes.Because CNT has great specific area, between the CNT being mutually wound around, there is larger Van der Waals force.Above-mentioned waddingization is processed and the CNT in this carbon nanometer tube material can't be dispersed in solvent completely, between CNT, by Van der Waals force, is attracted each other, is wound around, and forms network-like structure.
In the embodiment of the present invention, the method for described separating carbon nano-tube flocculent structure specifically comprises the following steps: pour the above-mentioned solvent that contains carbon nanotube flocculent structure into one and be placed with in the funnel of filter paper; Thereby standing and drying a period of time obtains the carbon nanotube flocculent structure of a separation, the photo that Figure 19 is this carbon nanotube flocculent structure.
In the embodiment of the present invention, the heat treatment process of described carbon nanotube flocculent structure specifically comprises the following steps: above-mentioned carbon nanotube flocculent structure is placed in to a container; This carbon nanotube flocculent structure is spread out according to reservation shape; Apply certain pressure in the carbon nanotube flocculent structure of spreading out; And, solvent residual in this carbon nanotube flocculent structure to be dried or the equal solvent acquisition one CNT waddingization film afterwards that naturally volatilize, Fig. 7 is the stereoscan photograph of this CNT waddingization film.
Be appreciated that the embodiment of the present invention can control by controlling area that this carbon nanotube flocculent structure spreads out thickness and the surface density of this CNT waddingization film.The area that carbon nanotube flocculent structure is spread out is larger, and the thickness of this CNT waddingization film and surface density are just less.The CNT waddingization film obtaining in the embodiment of the present invention, the thickness of this CNT waddingization film is 1 micron-2 millimeters.
In addition, the step of above-mentioned separation and heat treatment carbon nanotube flocculent structure also can be directly mode by suction filtration realize, specifically comprise the following steps: an a miillpore filter and funnel of bleeding is provided; Through this miillpore filter, pouring the above-mentioned solvent that contains carbon nanotube flocculent structure into this bleeds in funnel; Suction filtration the dry rear CNT waddingization film that obtains.This miillpore filter is that a smooth surface, aperture are the filter membrane of 0.22 micron.Because suction filtration mode itself will provide a larger gas pressure in this carbon nanotube flocculent structure, this carbon nanotube flocculent structure is through the direct formation one uniform CNT waddingization film of suction filtration.And because microporous membrane surface is smooth, this CNT waddingization film is easily peeled off, and obtains the CNT waddingization film of a self-supporting.
Refer to Fig. 7, above-mentioned CNT waddingization film comprises the CNT of mutual winding, between described CNT, by Van der Waals force, is attracted each other, is wound around, and form network-like structure, so this CNT waddingization film has good toughness.In this CNT waddingization film, CNT is for being uniformly distributed and random arrangement.
Be appreciated that certain thickness that has of this CNT waddingization film, and can control its thickness by controlling area and the pressure size that this carbon nanotube flocculent structure spreads out.So this CNT waddingization film can directly be used as a carbon nano tube structure 164.In addition, can or be arranged side by side at least two-layer CNT waddingization film-stack setting and form a carbon nano tube structure 164.
(3) when this carbon nano tube structure 164 comprises at least one CNT laminate, the preparation method of this carbon nano tube structure 164 comprises the following steps:
First, provide a carbon nano pipe array to be formed at a growth substrate, this array is the carbon nano pipe array aligning.
Described carbon nano pipe array is preferably the carbon nano pipe array that surpasses in-line arrangement.Described carbon nano pipe array is identical with the preparation method of above-mentioned carbon nano pipe array.
Secondly, adopt a device for exerting, push above-mentioned carbon nano pipe array and obtain a CNT laminate, its detailed process is:
This device for exerting applies certain pressure and lists in above-mentioned carbon nano-pipe array.In the process of exerting pressure, carbon nano-pipe array is listed in can be separated with growth substrate under the effect of pressure, thereby form the CNT laminate with self supporting structure being formed by a plurality of CNTs, and described a plurality of CNTs are gone up substantially parallel with the surface of CNT laminate.
In the embodiment of the present invention, device for exerting is a pressure head, pressure head smooth surface, the arrangement mode of CNT in the CNT laminate that the shape of pressure head and the direction of extrusion determine to prepare.Particularly, when adopting plane pressure head to push along the direction perpendicular to above-mentioned carbon nano pipe array growth substrate, can obtain CNT is isotropic CNT laminate of lack of alignment; When adopting roller bearing shape pressure head to roll along a certain fixed-direction that is parallel to substrate, can obtain CNT along the CNT laminate of this fixed-direction orientations; When adopting roller bearing shape pressure head to roll along different directions, can obtain CNT along the CNT laminate of different directions orientations.
Be appreciated that, when adopting above-mentioned different modes to push above-mentioned carbon nano pipe array, CNT can be toppled under the effect of pressure, and by Van der Waals force, attracts each other, is connected to form the CNT laminate with self supporting structure being comprised of a plurality of CNTs with adjacent CNT.Described a plurality of CNTs and the surface of this growth substrate β that has angle, wherein, β is more than or equal to zero degree and is less than or equal to 15 degree (0 °≤β≤15 °).Different according to the mode rolling, as shown in Figure 9, the CNT in this CNT laminate can be arranged of preferred orient along a fixed-direction; Or as shown in Figure 8, along different directions, be arranged of preferred orient.In addition, under the effect of pressure, carbon nano pipe array can be separated with the substrate of growth, thus make this CNT laminate easily with substrate disengaging, thereby form the CNT 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 larger, inclination angle is larger.Described inclination angle is the angle that the substrate of the CNT in carbon nano pipe array and this carbon nano pipe array of growing is.The thickness of the CNT laminate of preparation depends on height and the pressure size of carbon nano pipe array.The height of carbon nano pipe array is larger and applied pressure is less, and the thickness of the CNT laminate of preparation is larger; Otherwise the height of carbon nano pipe array is less and applied pressure is larger, the thickness of the CNT laminate of preparation is less.The size of the substrate that the width of this CNT laminate is grown with carbon nano pipe array is relevant, and the length of this CNT laminate is not limit, and can make according to the actual requirements.The CNT laminate obtaining in the embodiment of the present invention, the thickness of this CNT laminate is 1 micron～2 millimeters.
Finally, this CNT laminate is uncovered from described growth substrate, thereby obtained the CNT laminate of a self-supporting.
Above-mentioned CNT laminate comprises CNT in the same direction a plurality of or that be arranged of preferred orient, attract each other, so this CNT laminate has good toughness between described CNT by Van der Waals force.In this CNT laminate, even carbon nanotube distributes, regularly arranged.
Be appreciated that this CNT laminate has certain thickness, and can control its thickness by height and the pressure size of carbon nano pipe array.So this CNT laminate can directly be used as a carbon nano tube structure 164.In addition, can or be arranged side by side the stacked setting of at least two-layer CNT laminate and form a carbon nano tube structure 164.
(4) when this carbon nano tube structure 164 comprises at least one liner structure of carbon nano tube, the preparation method of this carbon nano tube structure 164 comprises the following steps:
First, provide at least one CNT membrane.
The formation method of this CNT membrane is identical with the formation method of CNT membrane in ().
Secondly, process this CNT membrane, form at least one carbon nano tube line.
The step of this processing CNT membrane can be processed this CNT membrane for employing organic solvent, thereby obtains the carbon nano tube line of a non-torsion, or for adopting mechanical external force to reverse this CNT membrane, thereby obtain the carbon nano tube line of a torsion.
The step that adopts organic solvent to process this CNT membrane is specially: the whole surface that organic solvent is infiltrated to described CNT membrane, under the capillary effect producing when volatile organic solvent volatilizees, a plurality of CNTs that are parallel to each other in CNT membrane are combined closely by Van der Waals force, thereby make CNT membrane be punctured into the carbon nano tube line of a non-torsion.This organic solvent is volatile organic solvent, as ethanol, methyl alcohol, acetone, dichloroethanes or chloroform, adopts ethanol in the present embodiment.The non-torsion carbon nano tube line of processing by organic solvent is compared with the CNT membrane of processing without organic solvent, and specific area reduces, and viscosity reduces.Be appreciated that, this employing organic solvent process CNT membrane form non-torsion carbon nano tube line method with in (one), adopt the method for viscosity of organic solvent reduction CNT membrane similar, its difference is, in the time need to forming the carbon nano tube line of non-torsion, the two ends of CNT membrane are unfixing, CNT membrane are not arranged in substrate surface or frame structure.
The step that adopts mechanical external force to reverse this CNT membrane is to adopt a mechanical force that described carbon nano-tube film two ends are reversed in opposite direction.In the embodiment of the present invention, specifically can provide an afterbody can cling the spinning axle of CNT membrane.After the afterbody of this spinning axle is combined with CNT membrane, this spinning axle is rotated to this CNT membrane in rotary manner, form the carbon nano tube line of a torsion.The rotation mode that is appreciated that above-mentioned spinning axle is not limit, can forward, and also can reverse, or rotate and reverse and combine.
Further, can adopt a volatile organic solvent to process the carbon nano tube line of this torsion.Under the capillary effect producing when volatile organic solvent volatilizees, CNT adjacent in the carbon nano tube line of the torsion after processing is combined closely by Van der Waals force, the specific area of the carbon nano tube line of torsion is reduced, viscosity reduces, and all increases with carbon nano tube line phase specific density and the intensity of the torsion of processing without organic solvent.
Again, utilize above-mentioned carbon nano tube line to prepare at least one liner structure of carbon nano tube, and obtain a carbon nano tube structure 164.
The carbon nano tube line of above-mentioned torsion or the carbon nano tube line of non-torsion are a self supporting structure, can directly as a carbon nano tube structure 164, use.In addition, a plurality of carbon nano tube lines can be arranged in parallel into the liner structure of carbon nano tube of a fascicular texture, or a plurality of carbon nano tube lines that this is arranged in parallel obtain the liner structure of carbon nano tube of hank line structure through a torsion step.Further, the plurality of carbon nano tube line or liner structure of carbon nano tube can be arranged parallel to each other, cross arrangement or braiding, obtain the carbon nano tube structure 164 of a two dimension.
Step 2, interval formation one first electrode 12 and one second electrode 14 are in the two ends of this carbon nano tube structure 164, and this first electrode 12 and one second electrode 14 form and are electrically connected to this carbon nano tube structure 164.
The first described electrode 12 and the set-up mode of one second electrode 14 are relevant with carbon nano tube structure 164.In carbon nano tube structure 164 during at least part of ordered arrangement of CNT, as this carbon nano tube structure 164 comprise a CNT membrane, while rolling the CNT laminate that obtains or a carbon nano tube line along a fixed-direction, when in this carbon nano tube structure 164, most of CNTs are arranged of preferred orient in the same direction, preferably, should guarantee that the part CNT in carbon nano tube structure 164 extends along the first electrode 12 to 1 second electrode 14 directions, is arranged on the bearing of trend of this CNT the first electrode 12 and the second electrode 14.This kind of set-up mode can guarantee that carbon nano tube structure 164 has best electric conductivity, thereby makes heating element heater 16 have best heating effect.
The first described electrode 12 and one second electrode 14 can be arranged on the same surface of carbon nano tube structure 164 or on different surfaces, or this first electrode 12 and one second electrode 14 are around the surface that is arranged at carbon nano tube structure 164.Wherein, the setting of being separated by between the first electrode 12 and one second electrode 14, avoids short circuit phenomenon to produce so that carbon nano tube structure 164 accesses certain resistance while being applied to line heat source 10.Carbon nano tube structure 164 itself has good adhesiveness and electric conductivity, thus the first electrode 12 and one second electrode 14 can and carbon nano tube structure 164 between form and well electrically contact.
Described the first electrode 12 and one second electrode 14 are conducting film, sheet metal or metal lead wire.This conducting film can be by plating, chemical plating, sputter, vacuum evaporation, physical vaporous deposition, chemical vapour deposition technique, directly apply or serigraphy electrocondution slurry or other method are formed at carbon nano tube structure 164 surfaces.This sheet metal can be copper sheet or aluminium flake etc.This sheet metal or metal lead wire can be fixed on carbon nano tube structure 164 surfaces by conductive adhesive, or are fixed on carbon nano tube structure by screw, clamping plate etc.In the embodiment of the present invention, adopt vacuum vapour deposition to form two palladium films at carbon nano tube structure 164 two ends, as the first electrode 12 and the second electrode 14.
Described the first electrode 12 and one second electrode 14 can also be a metallic carbon nanotubes layer.This carbon nanotube layer is arranged at the surface of carbon nano tube structure 164.This carbon nanotube layer can be by himself viscosity or the conductive adhesive surface of being fixed on carbon nano tube structure 164.This carbon nanotube layer comprises and aligning and equally distributed metallic carbon nanotubes.Particularly, this carbon nanotube layer comprises at least one carbon nano-tube film or at least one carbon nano tube line.Preferably, in described metallic carbon nanotubes layer, carbon nano tube surface is coated a metal level at least partly, thereby improves the electric 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 the first electrode 12 and one second electrode 14, can further form two conductive lead wires, be electrically connected to the end of the first electrode 12 and the second electrode 14 respectively, from the first electrode 12 and one second electrode 14, lead to external power source.
Step 3, provides a matrix precursor, and matrix precursor and carbon nano tube structure 164 is compound, forms a heating element heater 16.
The material of described matrix precursor is material, the formed solution of this matrix material of this matrix or forerunner's reactant of preparing this matrix material.This matrix precursor should be liquid state or gaseous state at a certain temperature.
The material of described matrix 162 comprises macromolecular material or Inorganic Non-metallic Materials etc.Particularly, this high-molecular organic material can comprise one or more in thermoplastic polymer or thermosetting polymer, therefore the material of this matrix precursor can be for generating the polymer monomer solution of this thermoplastic polymer or thermosetting polymer, or the mixed liquor that forms after dissolving in volatile organic solvent of this thermoplastic polymer or thermosetting polymer.This carbon nano tube structure 164 is directly soaked in after this liquid matrix precursor, and this matrix precursor is solidified, and forms matrix 162 compound with this carbon nano tube structure 164.
This Inorganic Non-metallic Materials can comprise one or more in glass, pottery and semi-conducting material, therefore the slurry that this matrix precursor can be made for Inorganic Non-metallic Materials particle, prepare the reacting gas of this Inorganic Non-metallic Materials or be this Inorganic Non-metallic Materials of gaseous state.Particularly, can adopt the method for vacuum evaporation, sputter, chemical 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 matrix presoma is infiltrated to this carbon nano tube structure 164 and solidifies this matrix precursor, thereby this matrix 162 is infiltrated in the hole of this carbon nano tube structure 164, forms a heating element heater 16; When this matrix precursor is gaseous state, this step 3 specifically comprises that this matrix precursor of deposition is in the step of the carbon nano tube surface of carbon nano tube structure 164, thereby this matrix 162 is full of in the hole of this carbon nano tube structure 164, forms a heating element heater 16.
The present embodiment adopts injecting glue method that epoxy resin-base material and carbon nano tube structure 164 is compound, forms a heating element heater 16, specifically comprises the following steps:
Step (one): a liquid thermosetting macromolecular material is provided.
The viscosity of described liquid thermosetting macromolecular material is lower than 5 handkerchief seconds, and can at room temperature keep this viscosity more than 30 minutes.The embodiment of the present invention is preferably prepared liquid thermosetting macromolecular material with epoxy resin, and it specifically comprises the following steps:
First, the mixture of glycidol ether type epoxy and glycidyl ester type epoxy is placed in to a container, be heated to 30 ℃～60 ℃, and the mixture of the type epoxy of glycidol ether described in container and glycidyl ester type epoxy is stirred 10 minutes, until the mixture of described glycidol ether type epoxy and glycidyl ester type epoxy mixes.
Secondly, in the glycidol ether type epoxy stirring described in fatty amine and diglycidyl ether are joined and the mixture of glycidyl ester type epoxy, carry out chemical reaction.
Finally, the mixture of described glycidol ether type epoxy and glycidyl ester type epoxy is heated to 30 ℃～60 ℃, thereby obtains a liquid thermosetting macromolecular material containing epoxy resin.
Step (two): adopt described liquid thermosetting macromolecular material to infiltrate described carbon nano tube structure 162.
The method that adopts described liquid thermosetting macromolecular material to infiltrate described carbon nano tube structure 162 in the present embodiment comprises the following steps:
First, carbon nano tube structure 162 is positioned in a mould.
Secondly, described liquid thermosetting macromolecular material is injected in described mould, infiltrates described carbon nano tube structure 162.In order to allow liquid thermosetting macromolecular material fully infiltrate described carbon nano tube structure 162, the time that infiltrates described carbon nano tube structure 162 can not be less than 10 minutes.
Be appreciated that, the method that described liquid thermosetting macromolecular material is infiltrated to described carbon nano tube structure 162 is not limit the method for injection, described liquid thermosetting macromolecular material can also be inhaled in described carbon nano tube structure 162 by capillarity, infiltrate described carbon nano tube structure 162, or described carbon nano tube structure 162 is immersed in described liquid thermosetting macromolecular material.
Step (three): solidify the above-mentioned carbon nano tube structure being infiltrated by liquid thermosetting macromolecular material 162, obtain a composite structure of carbon nano tube.
The present embodiment specifically comprises the following steps containing the curing of the thermoset macromolecule material of epoxy resin:
First, by a heater, by this mold heated to 50 ℃～70 ℃, the thermoset macromolecule material containing epoxy resin at this temperature be liquid, maintains this temperature 1 hour～3 hours, makes this thermoset macromolecule material continue to absorb heat to increase its curing degree.
Secondly, continue this mould to 80 of heating ℃～100 ℃, at this temperature, maintain 1 hour～3 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.
Again, continue this mould to 110 of heating ℃～150 ℃, at this temperature, maintain 2 hours～20 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.
Finally, stop heating, until this mould, be cooled to after room temperature, the demoulding can obtain a composite structure of carbon nano tube.
The China's Mainland patent application " preparation method of carbon nano tube compound material " that the application number that the above-mentioned concrete steps of preparing composite structure of carbon nano tube can be applied on December 14th, 2007 referring to people such as Fan Shoushan is 200710125109.8.For saving space, be only incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
The curing that is appreciated that the above-mentioned thermoset macromolecule material containing epoxy resin also can adopt the method once heating up, and directly temperature is risen to 150 ℃, and thermoset macromolecule material heat absorption is solidified.
Be appreciated that the step that forms the first electrode 12 and one second electrode 14 in above-mentioned steps two can carry out after forming this heating element heater 16.When this matrix 162 is only filled in the hole of this carbon nano tube structure 164, thereby while making CNT partly be exposed to heating element heater 16 surface, can adopt the method identical with step 2 that this first electrode 12 and one second electrode 14 are directly formed to this heating element heater 16 surfaces.When this matrix 162 all coated this carbon nano tube structure 164, further comprise that the described carbon nano tube structure 164 of an exposure is in the step on heating element heater 16 surfaces, this first electrode 12 and the second electrode 14 are electrically connected to the carbon nano tube structure 164 exposing respectively.Particularly, can adopt the step of a cutting to cut this heating element heater 16, to form a cut surface, thereby make this carbon nano tube structure 164 be exposed to the cut surface of heating element heater 16, and then the employing method identical with step 2 be formed at this first electrode 12 and one second electrode 14 cut surface of this heating element heater 16, thereby the carbon nano tube structure 164 coming out with this is electrically connected to.
Be appreciated that when this carbon nano tube structure is wire, the formation method of the heating element heater 36 of the 3rd embodiment can comprise the following steps:
First, this liner structure of carbon nano tube and described matrix precursor is compound, form a CNT wire composite construction 366;
Secondly, one or more these CNT wire composite constructions 366 are arranged, formed the heating element heater 36 of a two dimension.
This CNT wire composite construction 366 can mutually weave, intersects, side by side or coiling form the heating element heater 36 of a two dimension.When this CNT wire composite construction 366 is mutually during braiding, like dry goods, it is one planar that this heating element heater 36 can keep.This heating element heater 36 that mutually weaves formation can be made into a heating cushion, heating clothing and heated gloves etc.When this CNT wire composite construction 366 intersects, side by side or when coiling mutually, between the plurality of liner structure of carbon nano tube 366, can bond by binding agent, thereby make this heating element heater 36 keep planar.
Described that the liner structure of carbon nano tube mode compound with matrix precursor is identical with above-mentioned steps three.
This first electrode and the second electrode can be formed at by the mode of above-mentioned steps two these heating element heater 36 surfaces.Further, can expose this liner structure of carbon nano tube in described heating element heater 36 surfaces by a cutting step, and then this first electrode and the second electrode are formed to this exposure have on the surface of carbon nano tube structure, thereby being formed, this first electrode and the second electrode and CNT in this composite structure of carbon nano tube be electrically connected to.
Be appreciated that this preparation method can further comprise the following step of selecting, thereby prepare a plane heat source 20 having in the second embodiment:
Step 4, provides a supporter 28, forms a heat-reflecting layer 27 in the surface of supporter 28.
On the surface of supporter 28, forming a heat-reflecting layer 27 can realize by the method for coating or plated film.Particularly, when the material of this heat-reflecting layer 27 is slaine or metal oxide, the particle of this slaine or metal oxide can be scattered in solvent, form a slurry, and by this slurry coating or serigraphy in supporter 28 surfaces, form this heat-reflecting layer 27.According to the difference of slaine or metal oxide, this solvent not should with slaine or metal oxide generation chemical reaction.In addition, this heat-reflecting layer 27 also can form by methods such as plating, chemical plating, sputter, vacuum evaporation, chemical vapour deposition (CVD) or physical vapour deposition (PVD)s.The embodiment of the present invention adopts physical vaporous deposition at ceramic base plate surface deposition one deck alundum (Al2O3) layer, as heat-reflecting layer 27.
Step 5, is arranged at heat-reflecting layer 27 surfaces by heating element heater 26.
This heating element heater 26 can be fixed on heat-reflecting layer 27 surfaces by a binding agent.In addition, also can adopt the fixing method of machinery, as adopted the fixtures such as screw, clamping plate, 26 4 jiaos of heating element heaters or four limits are fixed on to heat-reflecting layer 27 surfaces.
Step 6, forms a protective layer 25 in the outer surface of described heating element heater 26, forms a plane heat source 20.
This protective layer 25 can directly be fixed on heating element heater 26 surfaces by binding agent or the fixing method of machinery.In addition, when the material of this protective layer 25 is a thermoplastic polymer, this thermoplastic polymer at high temperature can be applied or is wrapped in heating element heater 26 surfaces in melting state, when low temperature, solidify to form this protective layer 25.In addition, when this protective layer 25 is a flexible polymer, during as a PETG (PET) film, a heat-press step be can pass through, by this protective layer 25 and these heating element heater 26 stack hot pressing, protective layer 25 and heating element heater 26 strong bonded made.
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 CNT is uniformly distributed in carbon nano tube structure, by the carbon nano tube structure of this self-supporting and matrix direct combination, can make in the heating element heater of compound rear formation CNT still mutually combine and keep the form of a carbon nano tube structure, thereby make CNT in heating element heater can be uniformly distributed formation conductive network, be not subject to again CNT in solution, to disperse the restriction of concentration, make the quality percentage composition of CNT in heating element heater can reach 99%, make this thermal source there is higher heating properties.In addition, the kind of this matrix material is not limited to polymer, makes the range of application of this thermal source more extensive.Second, because CNT has good intensity and toughness, the intensity of carbon nano tube structure is larger, better flexible, be difficult for breaking, make it there is longer service life, especially, when this carbon nano tube structure and flexible substrate are compounded to form heating element heater, can prepare a flexible thermal source, make this thermal source there is wider range of application.The 3rd, even carbon nanotube in carbon nano tube structure distributes, therefore there is uniform thickness and resistance, heating evenly, the electric conversion efficiency of CNT is high, and the unit are thermal capacitance of this carbon nano tube structure is less than every square centimeter of Kelvin of 2 * 10-4 joule, so this plane heat source has the feature rapid, thermo-lag is little, thermal response speed is fast, rate of heat exchange is fast and radiation efficiency is high that heats up.The 4th, the diameter of CNT is less, makes carbon nano tube structure can have less thickness, can prepare micro face thermal source, is applied to the heating of microdevice.The 5th, when carbon nano tube structure comprises CNT membrane, this CNT membrane can be by pulling and obtain from carbon nano pipe array, and method is simple and be conducive to the making of large area plane heat source, and in this CNT membrane, CNT is arranged of preferred orient in the same direction, there is good electric conductivity, make this thermal source there is good heating properties, in addition, this CNT membrane has certain transparency, can be used for preparing a transparent thermal source.The 6th, this carbon nano tube line can be used for the heating element heater that braiding forms various shapes, thereby prepares the plane heat source of various shapes.The 7th, this CNT waddingization film and CNT laminate have good toughness, and preparation method is simple.The 8th, this forms the carbon nano tube structure of self-supporting, and the method for this carbon nano tube structure and matrix direct combination formation heating element heater is simple, and the content of CNT in heating element heater can be controlled easily.After compound with matrix, this carbon nano tube structure still can keep original form, has the heating property suitable with pure nano-carbon tube structure.The 9th, this carbon nano tube structure can selectively be arranged at an a certain position having in the matrix of given shape, thereby realizes local selective heating, adapts to the demand of different field.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention, within all should being included in the present invention's scope required for protection.

Claims (13)

1. a plane heat source, comprising:
One heating element heater, this heating element heater comprises the carbon nano tube structure of the self-supporting of matrix and at least one one, described carbon nano tube structure comprises at least one deck CNT laminate, the mutual part of CNT adjacent in every one deck CNT laminate is overlapping, and attract each other by Van der Waals force, combine closely; And at least two electrode gap settings are also electrically connected to this heating element heater,
It is characterized in that, the carbon nano tube structure of the self-supporting of described at least one one is embedded in this matrix compound with matrix, and substantially keep the shape before compound, the CNT lack of alignment in this carbon nano tube structure, the CNT in this carbon nano tube structure to be arranged of preferred orient in the same direction or this carbon nano tube structure in CNT along different directions, be arranged of preferred orient.
2. plane heat source as claimed in claim 1, is characterized in that, described carbon nano tube structure comprises that the stacked setting of a plurality of CNT laminate or a plurality of CNT laminate are arranged side by side.
3. plane heat source as claimed in claim 1, it is characterized in that, described CNT laminate is for to obtain by rolling a carbon nano pipe array, CNT in described CNT laminate and the surperficial shape that forms the growth substrate of the carbon nano pipe array β that has angle, wherein, β is more than or equal to 0 degree and is less than or equal to 15 degree.
4. plane heat source as claimed in claim 1, is characterized in that, in described CNT laminate, CNT is arranged of preferred orient in the same direction, and in CNT laminate described in this plane heat source, CNT extends to another electrode along an electrode.
5. plane heat source as claimed in claim 1, is characterized in that, the thickness of described CNT laminate is 1 micron to 1 millimeter.
6. 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.
7. plane heat source as claimed in claim 1, is characterized in that, described at least two electrodes are electrically connected to described carbon nano tube structure respectively.
8. plane heat source as claimed in claim 1, is characterized in that, described heating element heater comprises a plurality of carbon nano tube structures space or being arranged in described matrix of being in contact with one another.
9. 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.
10. plane heat source as claimed in claim 1, is characterized in that, described plane heat source further comprises a supporter, and described heating element heater is at least partly by this support body supports, and the material of this supporter is flexible material or hard material.
11. plane heat sources as claimed in claim 10, 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 heater and supporter or is arranged on described supporter away from the surface of heating element heater.
12. 1 kinds of plane heat sources, comprising:
One heating element heater and at least two electrode gap settings are also electrically connected to this heating element heater, it is characterized in that: this heating element heater comprises the carbon nano tube structure of the self-supporting of at least one one, and matrix material is compound in this carbon nano tube structure, described carbon nano tube structure comprises at least one deck CNT laminate, the mutual part of CNT adjacent in every one deck CNT laminate is overlapping, and attract each other by Van der Waals force, combine closely, in this heating element heater, this carbon nano tube structure keeps compound shape before substantially, CNT lack of alignment in this carbon nano tube structure, CNT in this carbon nano tube structure be arranged of preferred orient in the same direction or this carbon nano tube structure in CNT along different directions, be arranged of preferred orient, described carbon nano tube structure has a plurality of micropores, described matrix material is evenly compound in the micropore of described carbon nano tube structure.
13. plane heat sources as claimed in claim 12, is characterized in that, described micropore size is less than 10 microns.
CN200910106804.9A 2008-06-07 2009-04-20 Plane heat source Active CN101868067B (en)

Priority Applications (17)

Application Number Priority Date Filing Date Title
CN200910106804.9A CN101868067B (en) 2009-04-20 2009-04-20 Plane heat source
US12/655,507 US20100122980A1 (en) 2008-06-13 2009-12-31 Carbon nanotube heater
US12/658,198 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
US12/658,237 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
US12/660,356 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
US12/661,133 US20100200568A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,165 US20100170891A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,115 US20100200567A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,110 US20100218367A1 (en) 2008-06-13 2010-03-11 Method for making carbon nanotube heater
US12/661,150 US20100170890A1 (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
JP2010097282A JP5281035B2 (en) 2009-04-20 2010-04-20 Surface heat source

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