CN101868071A - Line heat source - Google Patents

Line heat source Download PDF

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Publication number
CN101868071A
CN101868071A CN200910106807A CN200910106807A CN101868071A CN 101868071 A CN101868071 A CN 101868071A CN 200910106807 A CN200910106807 A CN 200910106807A CN 200910106807 A CN200910106807 A CN 200910106807A CN 101868071 A CN101868071 A CN 101868071A
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CN
China
Prior art keywords
carbon nano
tube
heat source
line heat
heating element
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Pending
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CN200910106807A
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Chinese (zh)
Inventor
刘长洪
王佳平
范守善
姜开利
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
Original Assignee
Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Filing date
Publication date
Application filed by Tsinghua University, Hongfujin Precision Industry Shenzhen Co Ltd filed Critical Tsinghua University
Priority to CN200910106807A priority Critical patent/CN101868071A/en
Priority to US12/655,507 priority patent/US20100122980A1/en
Priority to US12/658,184 priority patent/US20100147828A1/en
Priority to US12/658,193 priority patent/US20100147829A1/en
Priority to US12/658,182 priority patent/US20100147827A1/en
Priority to US12/658,198 priority patent/US20100147830A1/en
Priority to US12/658,237 priority patent/US20100154975A1/en
Priority to US12/660,356 priority patent/US20110024410A1/en
Priority to US12/660,820 priority patent/US20100163547A1/en
Priority to US12/661,165 priority patent/US20100170891A1/en
Priority to US12/661,133 priority patent/US20100200568A1/en
Priority to US12/661,150 priority patent/US20100170890A1/en
Priority to US12/661,110 priority patent/US20100218367A1/en
Priority to US12/661,115 priority patent/US20100200567A1/en
Priority to US12/661,926 priority patent/US20100187221A1/en
Priority to US12/750,186 priority patent/US20100180429A1/en
Priority to JP2010097277A priority patent/JP5448999B2/en
Publication of CN101868071A publication Critical patent/CN101868071A/en
Priority to JP2013018268A priority patent/JP5608767B2/en
Priority to JP2013018267A priority patent/JP5560354B2/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2214/00—Aspects relating to resistive heating, induction heating and heating using microwaves, covered by groups H05B3/00, H05B6/00
    • H05B2214/04—Heating means manufactured by using nanotechnology

Abstract

The invention relates to a line heat source comprising a line-shaped supporting structure, a heating element arranged at the surface of the line-shaped supporting structure and two electrodes, wherein the two electrodes are arranged at intervals and are electrically connected with the heating element, the heating element comprises at least one carbon nano pipe composite structure, the carbon nano pipe composite structure comprises a basal body and a carbon nano pipe membrane structure compounded in the basal body, and the carbon nano pipe membrane structure comprises a plurality of carbon nano pipes which are optimally orientated and arranged along a fixed direction or different directions. The line heat source can be used for manufacturing heating clothes, heating gloves or heating shoes with spontaneous heating, an electric heater, an infrared therapeutic apparatus, an electric room heater and the like and has extensive application range.

Description

Line heat source
Technical field
The present invention relates to a kind of line heat source, relate in particular to a kind of line heat source based on carbon nano-tube.
Background technology
Thermal source plays an important role in people's production, life, scientific research.Line heat source is a kind of of thermal source, has a wide range of applications at industrial circle, scientific research field or sphere of life etc., as electrothermal tube, electric blanket, infrared therapeutic apparatus and electric heater etc.
Existing line heat source generally includes a linear heating element (as resistance wire etc.) and two electrodes, these two electrode gap settings, and be electrically connected with these linear heating element two ends.When by described two electrodes when this linear heating element applies a voltage or feed electric current, this linear heating element produces Joule heat, and heat is to external radiation with common wavelength.Usually, the heating wire of making for employing metal, alloy or carbon fiber as the linear heating element of line heat source.
Yet, the heating wire that adopts metal, alloy or carbon fiber to make has following deficiency: first, the heat that this heating wire produced all with common wavelength to external radiation, its electric conversion efficiency is not high, be unfavorable for saving the energy, need to add the sticking cotton thread of far ultrared paint that scribbles to improve electric conversion efficiency.The second, the carbon fiber size is inadequately little, is unfavorable for being applied to miniature thermal source, and wire diameter is very little the time, and intensity is very low, fractures easily, also is unfavorable for being applied to miniature thermal source.The 3rd, the quality of this heating wire is all bigger, is unfavorable for the lightness of thermal source.In addition, metal electric heating silk and heating alloy are oxidized easily, and repeatedly crooked or easily produce tiredly when being converted into certain angle, and therefore, its application is restricted.
Since the early 1990s, (see also Helical microtubules of graphiticcarbon, Nature, Sumio Iijima with carbon nano-tube, vol 354, p56 (1991)) caused that with its particular structure and character people pay close attention to greatly for the nano material of representative.In recent years, along with deepening continuously of carbon nano-tube and nano materials research, its wide application prospect constantly displayed.
On October 25th, 2006, disclosed a kind of filament and preparation method thereof in the CN1282216C Chinese patent of bulletins such as Fan Shoushan.This filament comprises a carbon nano-tube filament.This carbon nano-tube filament comprises a plurality of by the end to end carbon nano-tube bundle of Van der Waals force, and each carbon nano-tube bundle comprises a plurality of being arranged in parallel and carbon nano-tube that length equates substantially.The preparation method of this filament comprises the steps: to prepare carbon nano pipe array; From above-mentioned carbon nano pipe array, pull out carbon nano-tube filament; The carbon nano-tube filament that above-mentioned steps is obtained with even external force is wrapped on the lead that uses as electrode, obtains filament.When described carbon nano-tube filament fed electric current, carbon nano-tube filament sent Joule heat, and radiated electromagnetic wave towards periphery.Yet, carbon nano-tube filament in this patent documentation is to be used for luminously, because the mechanical strength and the toughness of the pure nano-carbon tube silk of this direct acquisition are good inadequately, is easier to destroyed during use, thereby limited the scope of application of carbon nano-tube filament, can't be directly used in thermal source.
Summary of the invention
In view of this, necessaryly provide a kind of mechanical strength bigger, be difficult for ruined line heat source during use.
A kind of line heat source, it comprises a wire supporting construction, one heating element is arranged at the surface of wire supporting construction, and two electrodes, this two electrode gap settings and be electrically connected with this heating element, described heating element comprises at least one composite structure of carbon nano tube, and this composite structure of carbon nano tube comprises that a matrix and a carbon nano-tube membrane structure are compound in this matrix, and this carbon nano-tube membrane structure comprises a plurality of carbon nano-tube that are arranged of preferred orient along a fixed-direction or different directions.
A kind of line heat source, it comprises a wire supporting construction, one heating element is arranged at the surface of wire supporting construction, and two electrodes, this two electrode gap settings and be electrically connected with this heating element, described heating element comprises at least one composite structure of carbon nano tube, described composite structure of carbon nano tube comprises a carbon nano-tube membrane structure and a basis material, this carbon nano-tube membrane structure comprises a plurality of carbon nano-tube that are arranged of preferred orient along a fixed-direction or different directions, and described basis material is compound in this carbon nano-tube membrane structure.
A kind of line heat source, it comprises that a wire supports inner core; One heating element supports inner core around coating described wire, described heating element comprises at least one composite structure of carbon nano tube, this composite structure of carbon nano tube comprises that a matrix and a carbon nano-tube membrane structure are compound in this matrix, and this carbon nano-tube membrane structure comprises a plurality of carbon nano-tube that are arranged of preferred orient along along a fixed-direction or different directions; Two electrodes, this two electrode gap settings and be electrically connected with this heating element; And one the insulating protective layer protective layer coat this heating element.
Compared with prior art, because heating element comprises carbon nano-tube membrane structure and the basis material compound with this carbon nano-tube membrane structure in the described line heat source,, be difficult for destroyed during use so this heating element mechanical strength and toughness are bigger.
Description of drawings
The structural representation of the line heat source that Fig. 1 provides for first embodiment of the invention.
Fig. 2 is the generalized section of the line heat source II-II along the line of Fig. 1.
Fig. 3 is the generalized section of the line heat source III-III along the line of Fig. 2.
Fig. 4 comprises that for the line heat source of first embodiment of the invention layered carbon nano pipe composite construction is arranged at the schematic diagram on wire supporting construction surface, and wherein basis material permeates in carbon nano tube structure.
Fig. 5 comprises that for the line heat source of first embodiment of the invention layered carbon nano pipe composite construction is arranged at the schematic diagram on wire supporting construction surface, and wherein carbon nano tube structure is compound in the basis material.
Fig. 6 comprises that for the line heat source of first embodiment of the invention single wire composite structure of carbon nano tube is arranged at the schematic diagram on wire supporting construction surface.
Fig. 7 comprises that for the line heat source of first embodiment of the invention a plurality of wire composite structure of carbon nano tube are arranged at the schematic diagram on wire supporting construction surface.
Fig. 8 is the stereoscan photograph of the carbon nano-tube membrane structure in the line heat source of first embodiment of the invention.
Fig. 9 is the structural representation of the carbon nano-tube fragment in the carbon nano-tube membrane structure among Fig. 8.
The stereoscan photograph that Figure 10 is arranged of preferred orient along same direction for the carbon nano-tube in the carbon nano-tube laminate structure in the line heat source of first embodiment of the invention.
The stereoscan photograph that Figure 11 is arranged of preferred orient along different directions for the carbon nano-tube in the carbon nano-tube laminate structure in the line heat source of first embodiment of the invention.
Figure 12 is the stereoscan photograph of the carbon nano-tube waddingization membrane structure in the line heat source of first embodiment of the invention.
Figure 13 is the stereoscan photograph of the non-carbon nano tube line that reverses in the line heat source of first embodiment of the invention.
Figure 14 is the stereoscan photograph of the carbon nano tube line that reverses in the line heat source of first embodiment of the invention.
Figure 15 is the profile scanning electromicroscopic photograph of carbon nano-tube membrane and epoxy resin composite construction in the line heat source of first embodiment of the invention.
Figure 16 is a kind of preparation method's of first embodiment of the invention line heat source a flow chart.
Figure 17 is the photo of carbon nanotube flocculent structure of the line heat source of the embodiment of the invention.
Figure 18 will be arranged at the carbon nano tube structure on wire supporting construction surface and the flow chart of macromolecular material composite methods for first embodiment of the invention.
Figure 19 is the another kind of preparation method's of first embodiment of the invention line heat source a flow chart.
The structural representation of the line heat source that Figure 20 provides for second embodiment of the invention.
Embodiment
Describe line heat source provided by the invention and preparation method thereof in detail below with reference to drawings and the specific embodiments.
See also Fig. 1 to Fig. 3, first embodiment of the invention provides a kind of line heat source 20, and this line heat source 20 is an one-dimentional structure.This line heat source 20 comprises a wire supporting construction 202; One heat-reflecting layer 210 is arranged at the surface of this wire supporting construction 202; One heating element 204 is arranged at described heat-reflecting layer 210 surfaces; Two electrodes 206 are arranged at intervals at the surface of this heating element 204, and are electrically connected with this heating element 204; And one insulating protective layer 208 be arranged at the surface of this heating element 204.The length and the diameter of described line heat source 20 are not limit.Preferably, the diameter of described line heat source 20 is 1.1 millimeters～1.1 centimetres.This electrode 206 is used for being electrically connected with the external heat power supply.
Described wire supporting construction 202 is an one-dimentional structure, is used to support heating element 204.The material of described wire supporting construction 202 can be hard material, as: one or more in pottery, glass, resin and the quartz etc., can also select flexible material, as in plastics and the flexible fiber etc. one or more, with so that this line heat source 20 is bent into arbitrary shape in use as required.Preferably, the material of described wire supporting construction 202 is an insulating material.The length of described wire supporting construction 202, diameter and shape are not limit, and can select according to actual needs.Preferably, the diameter of described wire supporting construction 202 is 1 millimeter～1 centimetre.In the present embodiment, this wire supporting construction 202 is a ceramic bar, and its diameter is 1 millimeter.
The material of described heat-reflecting layer 210 is the insulating material that a pair of thermal radiation has better reflecting effect, as: one or more in metal oxide, slaine and the pottery etc.The thickness of described heat-reflecting layer 210 is that the material of heat-reflecting layer 210 is preferably alundum (Al in 100 microns～0.5 millimeter present embodiment, and its thickness is 100 microns.This heat-reflecting layer 210 is deposited on this wire supporting construction 202 surfaces by the method for sputter.Described heat-reflecting layer 210 can be used to further reflect the heat that heating element 204 is sent, and it effectively is dispersed in the extraneous space goes.But this heat-reflecting layer 210 is a choice structure.
Described heating element 204 comprises a composite structure of carbon nano tube.Described composite structure of carbon nano tube comprises a carbon nano tube structure and basis material.This carbon nano tube structure is a self supporting structure.So-called " self supporting structure " i.e. this carbon nano tube structure need not by a support body supports, also can keep self specific shape.The carbon nano tube structure of this self supporting structure comprises a plurality of carbon nano-tube, and these a plurality of carbon nano-tube attract each other by Van der Waals force, thereby makes carbon nano tube structure have specific shape.Carbon nano-tube in the described carbon nano tube structure comprises one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube and the multi-walled carbon nano-tubes.The diameter of described Single Walled Carbon Nanotube is 0.5 nanometer～50 nanometers, and the diameter of described double-walled carbon nano-tube is 1.0 nanometers～50 nanometers, and the diameter of described multi-walled carbon nano-tubes is 1.5 nanometers～50 nanometers.Among the present invention, this carbon nano tube structure is stratiform or linear structure.Because this carbon nano tube structure has self-supporting, still can keep stratiform or linear structure not by support body supports the time.Have a large amount of gaps in this carbon nano tube structure between the carbon nano-tube, thereby make this carbon nano tube structure have a large amount of micropores, described basis material infiltrates in this micropore, combines closely with described carbon nano tube structure.The unit are thermal capacitance of described carbon nano tube structure is less than 2 * 10 -4Every square centimeter of Kelvin of joule.Preferably, the unit are thermal capacitance of described carbon nano tube structure can be smaller or equal to 1.7 * 10 -6Every square centimeter of Kelvin of joule.Particularly, described carbon nano tube structure can comprise at least one carbon nano-tube film, at least one liner structure of carbon nano tube or its combination.
Described composite structure of carbon nano tube can comprise that a stratiform composite structure of carbon nano tube or at least one wire composite structure of carbon nano tube are arranged on the surface of wire supporting construction 202.
Layered composite structure of carbon nano tube is a two-dimensional structure.This layered carbon nano pipe composite construction can wrap up or be wrapped in the surface of wire supporting construction 202.Different according to the complex method of carbon nano tube structure and basis material, the concrete structure of this layered carbon nano pipe composite construction comprises following two kinds of situations: first kind of situation, see also Fig. 4, layered composite structure of carbon nano tube comprises that the carbon nano tube structure 2044 of a stratiform and a basis material 2042 permeate in the carbon nano tube structure 2044 of this stratiform.Have a large amount of micropores in the carbon nano tube structure 2044 of this stratiform, this basis material 2042 permeates in the micropore of the carbon nano tube structure 2044 of this stratiform.Also can be understood as, at this moment, carbon nano tube structure 2044 is as parent, and basis material 2042 is filled to as in the hole in the carbon nano tube structure 2044 of parent as packing material.When the carbon nano tube structure 2044 of this stratiform comprised a plurality of carbon nano-tube film, these a plurality of carbon nano-tube films can stackedly be provided with.When the carbon nano tube structure 2044 of this stratiform comprised single liner structure of carbon nano tube, this single liner structure of carbon nano tube folded or is coiled into a stratiform self supporting structure.When the carbon nano tube structure 2044 of this stratiform comprised a plurality of liner structure of carbon nano tube, these a plurality of liner structure of carbon nano tube can parallel tight setting, arranged in a crossed manner or be woven into a stratiform self supporting structure.When the carbon nano tube structure 2044 of this stratiform comprised carbon nano-tube film and liner structure of carbon nano tube simultaneously, described liner structure of carbon nano tube was arranged at least one surface of at least one carbon nano-tube film.
Second kind of situation sees also Fig. 5, and layered composite structure of carbon nano tube comprises that a matrix 2046 and a carbon nano tube structure 2044 are compound in this matrix 2046.This matrix 2046 is a layer structure, and this carbon nano tube structure 2044 is distributed in this matrix 2046, and preferably, this carbon nano tube structure 2044 evenly distributes in matrix 2046.This matrix 2046 can coat this carbon nano tube structure 2044 fully, and being partially submerged at least in this carbon nano tube structure 2044 of this matrix 2046.When this carbon nano tube structure 2044 was a plurality of parallel and liner structure of carbon nano tube that be provided with at interval, this liner structure of carbon nano tube extended to the other end by an end of wire supporting construction 202.
Described wire composite structure of carbon nano tube is an one dimension structure.Described wire composite structure of carbon nano tube comprises two kinds of situations.First kind, described wire composite structure of carbon nano tube comprises that a liner structure of carbon nano tube and a basis material permeate in this liner structure of carbon nano tube.Have a large amount of micropores in this liner structure of carbon nano tube, and basis material permeates in the micropore of this liner structure of carbon nano tube.Second kind, described wire composite structure of carbon nano tube comprises that a matrix and at least one liner structure of carbon nano tube are compound in this matrix.See also Fig. 6, when this heating element 204 was single wire composite structure of carbon nano tube, this single wire composite structure of carbon nano tube can directly be wound in the surface of described wire supporting construction 202.See also Fig. 7, when this heating element 204 comprised a plurality of wire composite structure of carbon nano tube, these a plurality of wire composite structure of carbon nano tube can be arranged in a crossed manner or be woven into a stratiform structure, twine or be wrapped in described wire supporting construction 202 surfaces then.
Described carbon nano-tube film can comprise carbon nano-tube membrane, carbon nano-tube waddingization film or carbon nano-tube laminate.Described liner structure of carbon nano tube can comprise the twisted wire structure that is arranged in parallel at least one carbon nano tube line, a plurality of carbon nano tube line the fascicular texture formed or a plurality of carbon nano tube line reverse composition mutually.
Described carbon nano-tube film comprises equally distributed carbon nano-tube, combines closely by Van der Waals force between the carbon nano-tube.Carbon nano-tube in this carbon nano-tube film is unordered or orderly arrangement.The arrangement of the unordered finger carbon nano-tube here is random, and the orientation of the most at least carbon nano-tube of orderly finger here has certain rule.Particularly, when carbon nano-tube film comprised the carbon nano-tube of lack of alignment, carbon nano-tube was twined mutually or isotropism is arranged; When carbon nano tube structure comprised orderly carbon nanotubes arranged, carbon nano-tube was arranged of preferred orient along a direction or a plurality of direction.In the present embodiment, preferably, described carbon nano tube structure comprises the carbon nano-tube film of a plurality of stacked settings, and the thickness of this carbon nano tube structure is preferably 0.5 nanometer～1 millimeter.The thermal response speed that is appreciated that carbon nano tube structure is relevant with its thickness.Under situation of the same area, the thickness of carbon nano tube structure is big more, and thermal response speed is slow more; Otherwise the thickness of carbon nano tube structure is more little, and thermal response speed is fast more.When the thickness of described carbon nano tube structure is 1 micron～1 millimeter, carbon nano tube structure just can reach maximum temperature in less than 1 second time.And the carbon nano-tube monofilm just can reach maximum temperature in 0.1 millisecond of time.So this line heat source 20 is applicable to the object Fast Heating.
Described carbon nano-tube membrane is for directly pulling a kind of carbon nano-tube film with self-supporting of acquisition from carbon nano pipe array.Each carbon nano-tube membrane comprises a plurality of along same direction preferred orientation and be parallel to carbon nano-tube membrane surface carbon nanotubes arranged.Described carbon nano-tube joins end to end by Van der Waals force.See also Fig. 8 and Fig. 9, particularly, each carbon nano-tube membrane comprise a plurality of continuously and the carbon nano-tube fragment 143 that aligns.This a plurality of carbon nano-tube fragment 143 joins end to end by Van der Waals force.Each carbon nano-tube fragment 143 comprises a plurality of carbon nano-tube that are parallel to each other 145, and this a plurality of carbon nano-tube that is parallel to each other 145 is combined closely by Van der Waals force.This carbon nano-tube fragment 143 has width, thickness, uniformity and shape arbitrarily.The thickness of described carbon nano-tube membrane is 0.5 nanometer～100 micron, and width is relevant with the size of the carbon nano pipe array that pulls this carbon nano-tube membrane, and length is not limit.Described carbon nano-tube membrane and preparation method thereof specifically sees also the CN101239712A number Chinese publication application " carbon nano-tube membrane structure and preparation method thereof " of people such as Fan Shoushan in application on February 9th, 2007.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.When this carbon nano tube structure is made up of the carbon nano-tube membrane, and the thickness of carbon nano tube structure is when smaller, and for example less than 10 microns, this carbon nano tube structure has good transparency, and its light transmittance can reach 96%, can be used to make a transparent thermal source.
When described carbon nano tube structure comprises the multilayer carbon nanotube membrane of stacked setting, form an intersecting angle α between the carbon nano-tube that is arranged of preferred orient in the adjacent two layers carbon nano-tube membrane, and α spends (0 °≤α≤90 °) more than or equal to 0 degree smaller or equal to 90.Have certain interval between described a plurality of carbon nano-tube membrane or between the adjacent carbon nano-tube among carbon nano-tube membrane, thereby form a plurality of micropores in carbon nano tube structure, the aperture of micropore is approximately less than 10 microns.
The carbon nano tube structure of the embodiment of the invention comprises a plurality of carbon nano-tube membranes along the stacked setting of equidirectional, thereby the carbon nano-tube in the carbon nano tube structure all is arranged of preferred orient along same direction.
Described carbon nano-tube laminate comprises equally distributed carbon nano-tube, and carbon nano-tube is arranged of preferred orient along same direction or different directions.Carbon nano-tube in the described carbon nano-tube laminate mutually part overlaps, and attracts each other by Van der Waals force, combines closely, and makes this carbon nano tube structure have good flexible, can bending fold becomes arbitrary shape and does not break.And owing to attract each other by Van der Waals force between the carbon nano-tube in the carbon nano-tube laminate, combine closely, making the carbon nano-tube laminate is the structure of a self-supporting.Described carbon nano-tube laminate can obtain by rolling a carbon nano pipe array.Carbon nano-tube in the described carbon nano-tube laminate forms an angle β with the surface of the growth substrate that forms carbon nano pipe array, wherein, β is more than or equal to 0 degree and smaller or equal to 15 degree (0≤β≤15 °), this angle β is with to be applied to the pressure that carbon nano-pipe array lists relevant, pressure is big more, this angle is more little, and preferably, the carbon nano-tube in this carbon nano-tube laminate is parallel to this growth substrate and arranges.This carbon nano-tube laminate is to obtain by rolling a carbon nano pipe array, and according to the mode difference that rolls, the carbon nano-tube in this carbon nano-tube laminate has different spread patterns.Particularly, see also Figure 10, when when same direction rolls, carbon nano-tube is arranged of preferred orient along a fixed-direction; See also Figure 11, when when different directions rolls, carbon nano-tube is arranged of preferred orient along different directions; When rolling along direction perpendicular to carbon nano pipe array, the carbon nano-tube film isotropism.The length of carbon nano-tube is greater than 50 microns in this carbon nano-tube laminate.Described carbon nano-tube laminate and preparation method thereof specifically saw also people such as Fan Shoushan in application on June 1st, 2007, in disclosed CN101314464A Chinese patent application on December 3 " preparation method of carbon nano-tube film " in 2008.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
The area and the thickness of this carbon nano-tube laminate are not limit, and can select according to actual needs.The area of this carbon nano-tube laminate and the size of carbon nano pipe array are basic identical.The height of this carbon nano-tube laminate thickness and carbon nano pipe array and the pressure that rolls are relevant, can be 1 micron～1 millimeter.The height that is appreciated that carbon nano pipe array is big more and applied pressure is more little, and then the thickness of Zhi Bei carbon nano-tube laminate is big more; Otherwise the height of carbon nano pipe array is more little and applied pressure is big more, and then the thickness of Zhi Bei carbon nano-tube laminate is more little.Have certain interval between the adjacent carbon nano-tube among the described carbon nano-tube laminate, thereby form a plurality of micropores in the carbon nano-tube laminate, the aperture of micropore is approximately less than 10 microns.
Described carbon nano tube structure can comprise at least one carbon nano-tube waddingization film, and this carbon nano-tube waddingization film comprises mutual winding and equally distributed carbon nano-tube.The length of carbon nano-tube is greater than 10 microns, and preferably, the length of carbon nano-tube is more than or equal to 200 microns and smaller or equal to 900 microns.Attract each other, twine by Van der Waals force between the described carbon nano-tube, form network-like structure.Carbon nano-tube in the described carbon nano-tube waddingization film is evenly to distribute, and random arrangement makes this carbon nano-tube waddingization film isotropism.Carbon nano-tube in the described carbon nano-tube waddingization film forms a large amount of microcellular structures, and micropore size is approximately less than 10 microns.The length and the width of described carbon nano-tube waddingization film are not limit.See also Figure 12, because in carbon nano-tube waddingization film, carbon nano-tube is twined mutually, so this carbon nano-tube waddingization film has good flexible, and is a self supporting structure, can bending fold becomes arbitrary shape and does not break.The area and the thickness of described carbon nano-tube waddingization film are not all limit, and thickness is 1 micron～1 millimeter, are preferably 100 microns.Described carbon nano-tube waddingization film and preparation method thereof specifically saw also people such as Fan Shoushan in application on April 13rd, 2007, in disclosed CN101284662A Chinese patent application on October 15 " preparation method of carbon nano-tube film " in 2008.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Described carbon nano tube line comprises a plurality of along carbon nano tube line axial orientation carbon nanotubes arranged.Described carbon nano tube line can be non-carbon nano tube line that reverses or the carbon nano tube line that reverses.This non-carbon nano tube line that reverses obtains for the carbon nano-tube membrane is handled by organic solvent.See also Figure 13, this non-carbon nano tube line that reverses comprises a plurality of along carbon nano tube line length direction carbon nanotubes arranged.This carbon nano tube line that reverses reverses acquisition for adopting a mechanical force in opposite direction with described carbon nano-tube membrane two ends.See also Figure 14, this carbon nano tube line that reverses comprises a plurality of around carbon nano tube line axial screw carbon nanotubes arranged.This non-carbon nano tube line that reverses and the carbon nano-tube line length of reversing are not limit, and diameter is 0.5 nanometer～100 micron.Described carbon nano tube line and preparation method thereof specifically sees also people such as Fan Shoushan in application on September 16th, 2002, in CN100411979C number China's bulletin patent " a kind of carbon nano-tube rope and manufacture method thereof " of bulletin on August 20th, 2008, and in disclosed CN1982209A number Chinese publication application " carbon nano-tube filament and preparation method thereof " on June 20 in 2007.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Further, can adopt a volatile organic solvent to handle the carbon nano tube line that this reverses.Under the capillary effect that when volatile organic solvent volatilizees, produces, adjacent carbon nano-tube is combined closely by Van der Waals force in the carbon nano tube line that reverses after the processing, the diameter and the specific area of the carbon nano tube line that reverses are reduced, and density and intensity increase.
Because this carbon nano tube line obtains for adopting organic solvent or mechanical force to handle above-mentioned carbon nano-tube membrane, this carbon nano-tube membrane is a self supporting structure, so this carbon nano tube line is a self supporting structure.In addition, have the gap between the adjacent carbons nanotube in this carbon nano tube line, so this carbon nano tube line has a large amount of micropores, and the aperture of micropore is approximately less than 10 microns.
Described basis material can be chosen as one or more in macromolecular material and the Inorganic Non-metallic Materials etc.This basis material or the presoma that forms this basis material are liquid state or gaseous state at a certain temperature, thereby make the presoma of this basis material or this basis material in the preparation process of the heating element 204 of line heat source 20, can be penetrated in the gap or micropore of this carbon nano tube structure, combine closely with described carbon nano tube structure, solidify the back and form a composite construction.This basis material should have certain heat resistance, makes its unlikely destruction, distortion, fusing, gasification or decomposition in the working temperature of this line heat source 20.
Particularly, this macromolecular material can comprise one or more of thermoplastic polymer and thermosetting polymer, as in cellulose, polyethylene terephthalate, acryl resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, phenolic resins, epoxy resin and the polyester etc. one or more.These nonmetallic materials can comprise one or more in glass, pottery and the semi-conducting material.In the present embodiment, this basis material is an epoxy resin.This basis material can be the flexible macromolecule base material.This flexible macromolecule base material one of can be selected from silicone elastomer, polyurethane and the polymethyl methacrylate or its composition.
Owing to have a plurality of micropores in the described carbon nano tube structure, the basis material of liquid state or gaseous state or the presoma that forms this basis material can infiltrate the micropore inside of this carbon nano tube structure, combine closely with this carbon nano tube structure, solidify the back and form composite structure of carbon nano tube.See also Figure 15, for breaking the section photo that this composite structure of carbon nano tube obtains perpendicular to the orientation of carbon nano-tube in the carbon nano-tube membrane in the edge.Can find, with epoxy resin compound after, this carbon nano tube structure still can keep the form before compound substantially, carbon nano-tube is arranged of preferred orient along same direction in epoxy resin substantially.
Described basis material can only be filled in the micropore of described carbon nano tube structure, also can further coat whole carbon nano tube structure fully.When this heating element 204 comprises a plurality of carbon nano tube structure, but this a plurality of carbon nano tube structures space or being arranged in this basis material of being in contact with one another.When this carbon nano tube structure is a layer structure, as when being carbon nano-tube film, but carbon nano tube structure space or being arranged side by side or stacked being arranged in the basis material of being in contact with one another; When this carbon nano tube structure is a linear structure, as when being carbon nano tube line, but this linear structure space or being arranged side by side in basis material of being in contact with one another.When this carbon nano tube line or carbon nano-tube film are arranged at intervals in the basis material, can save the consumption of the required carbon nano tube structure of this heating element of preparation 204.In addition, visual actual needs is arranged on the ad-hoc location of basis material with carbon nano-tube film or carbon nano tube line, thereby makes this heating element 204 have different heating-up temperatures at diverse location.
Be appreciated that, described basis material permeates in the micropore of carbon nano tube structure, can play the effect of fixing the carbon nano-tube in this carbon nano tube structure, make the not reason external force friction or scratch and come off of the carbon nano-tube in the carbon nano tube structure in use of this line heat source.When described basis material coated whole carbon nano tube structure, this basis material can further be protected this carbon nano tube structure, guaranteed this heating element 204 and exterior insulation simultaneously.In addition, this basis material can further play heat conduction and make the purpose of uniform heat distribution.Further, when this carbon nano tube structure sharply heated up, this basis material can play the effect of buffering heat, makes the variations in temperature of this heating element 204 comparatively soft.This basis material can also strengthen the flexibility and the toughness of whole composite structure of carbon nano tube.
Be appreciated that by carbon nano tube structure directly to be compounded to form heating element 204, carbon nano-tube is evenly distributed in heating element 204, and the content of carbon nano-tube can be 1%～99%, improved the heating temp of thermal source 10 basis material and self-supporting.Because this carbon nano tube structure is a self supporting structure, and carbon nano-tube evenly distributes in carbon nano tube structure, the carbon nano tube structure and the basis material of this self-supporting is directly compound, carbon nano-tube is still mutually combined keep the form of a carbon nano tube structure, thereby make in the heating element 204 the carbon nano-tube formation conductive network that can evenly distribute, be not subjected to carbon nano-tube in solution, to disperse the restriction of concentration again, make the quality percentage composition of carbon nano-tube in heating element can reach 99%.
The position that is provided with of described electrode 206 is not limit, as long as be electrically connected with described heating element 204.Described electrode 206 can be arranged on the same surface of heating element 204 and also can be arranged on the different surfaces of heating element 204.Described electrode 206 can be arranged on the surface of this heating element 204 by the viscosity or the conductive adhesive (figure does not show) of carbon nano tube structure.Conductive adhesive also can be fixed in electrode 206 on the surface of carbon nano tube structure when realizing that electrode 206 and carbon nano tube structure electrically contact better.Particularly, this conductive adhesive can be elargol.Can apply voltage to heating element 204 by these two electrodes 206.Wherein, the setting of being separated by between two electrodes 206 avoids short circuit phenomenon to produce so that insert certain resistance when adopting heating element 204 heating powers of carbon nano tube structure.Preferably, because wire supporting construction 202 diameters are less, two electrodes 206 are arranged at intervals at the two ends of wire supporting construction 202, and around the surface that is arranged at heating element 204.
Particularly, when the basis material of this heating element 204 only is filled in the micropore of this carbon nano tube structure, because the part of part carbon nano-tube is exposed to this composite structure of carbon nano tube surface in this carbon nano tube structure, this electrode 206 can be arranged on the surface of heating element 204, thereby electrode 206 is electrically connected with carbon nano tube structure.This electrode 206 can be arranged on the same surface of heating element 204 and also can be arranged on the different surfaces of heating element 204.In addition, when the basis material of this composite structure of carbon nano tube coats whole carbon nano tube structure, be electrically connected with this carbon nano tube structure for making this electrode 206, this electrode 206 can be arranged in the composite structure of carbon nano tube, and directly contacts with carbon nano tube structure.At this moment, for making this electrode 206 and external power source conducting, this electrode 206 can partly be exposed to outside the composite structure of carbon nano tube; Perhaps, this line heat source 20 can further comprise two lead-in wires, is electrically connected with these two electrodes 206 respectively, and draws from this composite structure of carbon nano tube inside.
When the carbon nano-tube in this carbon nano tube structure was arranged in order, preferably, the orientation of this carbon nano-tube was along extending from an electrode 206 to another electrode 206 directions.Particularly, when this carbon nano tube structure comprises at least one carbon nano-tube membrane, described two electrodes 206 are arranged at the two ends of this carbon nano-tube membrane respectively, the direction of carbon nano-tube from an electrode 206 to another electrode 206 in the carbon nano-tube membrane joined end to end align.
Described electrode 206 is conductive film, sheet metal or metal lead wire.The material of this conductive film can be metal, alloy, indium tin oxide (ITO), antimony tin oxide (ATO), conductive silver glue, conducting polymer etc.This conductive film can be formed at heating element 204 surfaces by physical vaporous deposition, chemical vapour deposition technique or other method.The material of this sheet metal or metal lead wire can be copper sheet or aluminium flake etc.This sheet metal can be fixed in heating element 204 surfaces by conductive adhesive.
Described electrode 206 can also be a carbon nano tube structure.This carbon nano tube structure can be by viscosity or the conductive adhesive surface of being fixed in heat-reflecting layer 210 or wire supporting construction 202 of himself.This carbon nano tube structure comprises and aligning and equally distributed metallic carbon nanotubes.Particularly, this carbon nano tube structure comprises at least one carbon nano-tube membrane or at least one carbon nano tube line.
In the present embodiment, preferably, two carbon nano-tube membranes are arranged at the two ends of shape supporting construction 202 length directions along the line respectively as electrode 206.These two carbon nano-tube membranes are surrounded on the inner surface of heating element 204, and electrically contact by forming between conductive adhesive and the heating element 204.Described conductive adhesive is preferably elargol.Because the heating element 204 in the present embodiment also adopts carbon nano tube structure, so have less ohmic contact resistance between electrode 206 and the heating element 204, can improve the utilance of 20 pairs of electric energy of line heat source.
The structure and material that is appreciated that electrode 206 is not all limit, if can be in described composite structure of carbon nano tube the mode of input current all in protection scope of the present invention.
The material of described insulating protective layer 208 is an insulating material, as: one or more in rubber and the resin etc.Described insulating protective layer 208 thickness are not limit, and can select according to actual conditions.The thickness of described insulating protective layer 208 is 0.5～2 millimeter.In the present embodiment, the material of this insulating protective layer 208 adopts rubber, and its thickness is 0.5 millimeter.Described insulating protective layer 208 is used for preventing that this line heat source 20 from electrically contacting with external world's formation in use, can also prevent the carbon nano tube structure absorption introduced contaminants in the zone of heating 204 simultaneously.Be appreciated that but this insulating protective layer 208 is a choice structure.
Carbon nano-tube has excellent conducting performance and thermal stability, and as a desirable black matrix structure, has than higher radiation efficiency.Insert power supply after two electrodes 206 of the line heat source 20 of present embodiment are connected leads, apply certain voltage in described composite structure of carbon nano tube, the composite structure of carbon nano tube in the line heat source 20 can give off the electromagnetic wave of certain wave-length coverage.This line heat source 20 by regulating the thickness of supply voltage size and carbon nano tube structure, can give off the electromagnetic wave of different wavelength range in area size one timing of carbon nano tube structure.Size one timing of supply voltage, it is opposite that the thickness of carbon nano tube structure and line heat source 20 give off electromagnetic wavelength change trend.Promptly when one timing of supply voltage size, the thickness of carbon nano tube structure is thick more, and it is short more that line heat source 20 gives off electromagnetic wavelength; The thickness of carbon nano tube structure is thin more, and it is long more that line heat source 20 gives off electromagnetic wavelength.Particularly, this carbon nano tube structure can produce an infrared heat radiation.Thickness one timing of carbon nano tube structure, the size of supply voltage and line heat source 20 give off electromagnetic wavelength and are inversely proportional to.Promptly when thickness one timing of carbon nano tube structure, supply voltage is big more, and it is short more that line heat source 20 gives off electromagnetic wavelength; Supply voltage is more little, and it is long more that line heat source 20 gives off electromagnetic wavelength.
Be appreciated that this line heat source 20 should be applied to the voltage swing at two electrode 206 two ends according to the thermal endurance restriction of basis material when using, be controlled in the tolerant temperature range of this basis material the heating temp of composite structure of carbon nano tube.For example, when this basis material was organic high molecular polymer, this voltage was smaller or equal to 10 volts, and the heating temp of this thermal source is below 120 ℃.When this basis material was pottery, this voltage range was 10 volts～30 volts, and the heating temp of this thermal source can be 120 ℃～500 ℃.
Basis material in the composite structure of carbon nano tube of this line heat source 20 is flexible polymeric material, and wire supporting construction 202 is when also being made by flexible material, and this line heat source 20 is a flexible wires thermal source 20.This line heat source 20 can be arranged at it body surface that will heat or itself and heated object are provided with at interval in use, utilizes its thermal radiation to heat.In addition, various predetermined figures can also be arranged or be woven into to a plurality of these line heat sources 20 uses.This flexible line heat source 20 can be used to make heating clothes, Warming gloves or heating shoes, electric heater, infrared therapeutic apparatus, electric heater of spontaneous heating etc., is with a wide range of applications.
See also Figure 16, first embodiment of the invention further provides a kind of preparation method of line heat source 20, and it specifically may further comprise the steps:
Step S101 provides a carbon nano tube structure.
According to the difference of carbon nano tube structure, the preparation method of described carbon nano tube structure comprises: direct membrane method, rolled-on method, wadding method etc.To the preparation method of above-mentioned several carbon nano tube structures be narrated respectively below.
(1) comprise at least one carbon nano-tube membrane when this carbon nano tube structure, the preparation method of this carbon nano tube structure may further comprise the steps:
At first, provide a carbon nano pipe array to be formed at a growth substrate, this array is preferably the carbon nano pipe array of super in-line arrangement.
The preparation method of this carbon nano pipe array adopts chemical vapour deposition technique, its concrete steps comprise: a smooth growth substrate (a) is provided, this growth substrate can be selected P type or the substrate of N type silicon growth for use, or select for use the silicon growth substrate that is formed with oxide layer, the embodiment of the invention to be preferably and adopt 4 inches silicon growth substrate; (b) evenly form a catalyst layer on the growth substrate surface, this catalyst layer material can be selected one of alloy of iron (Fe), cobalt (Co), nickel (Ni) or its combination in any for use; (c) the above-mentioned growth substrate that is formed with catalyst layer was annealed in 700 ℃～900 ℃ air about 30 minutes～90 minutes; (d) growth substrate that will handle places reacting furnace, is heated to 500 ℃～740 ℃ under the protective gas environment, feeds carbon-source gas then and reacts about 5 minutes～30 minutes, and growth obtains carbon nano pipe array.This carbon nano-pipe array is classified a plurality of pure nano-carbon tube arrays parallel to each other and that form perpendicular to the growth substrate carbon nanotubes grown as.By above-mentioned control growing condition, do not contain impurity in this carbon nano pipe array that aligns substantially, as agraphitic carbon or residual catalyst metal particles etc.
The carbon nano-pipe array that the embodiment of the invention provides is classified a kind of in single-wall carbon nanotube array, double-walled carbon nano-tube array and the array of multi-walled carbon nanotubes as.The diameter of described carbon nano-tube is 1～50 nanometer, and length is 50 nanometers～5 millimeter.In the present embodiment, the length of carbon nano-tube is preferably 100～900 microns.
Carbon source gas can be selected the more active hydrocarbons of chemical property such as acetylene, ethene, methane for use in the embodiment of the invention, and the preferred carbon source gas of the embodiment of the invention is acetylene; Protective gas is nitrogen or inert gas, and the preferred protective gas of the embodiment of the invention is an argon gas.
Be appreciated that the carbon nano pipe array that the embodiment of the invention provides is not limited to above-mentioned preparation method, also can be graphite electrode Constant Electric Current arc discharge sedimentation, laser evaporation sedimentation etc.
Secondly, adopt a stretching tool from carbon nano pipe array, to pull carbon nano-tube and obtain at least one carbon nano-tube membrane, it specifically may further comprise the steps: (a) from described super in-line arrangement carbon nano pipe array selected one or have a plurality of carbon nano-tube of certain width, present embodiment is preferably and adopts adhesive tape, tweezers or clip contact carbon nano pipe array with certain width with selected one or have a plurality of carbon nano-tube of certain width; (b) with certain speed this selected carbon nano-tube that stretches, thereby form end to end a plurality of carbon nano-tube fragment, and then form a continuous carbon nano tube film.This pulls direction along the direction of growth that is basically perpendicular to carbon nano pipe array.
In above-mentioned drawing process, these a plurality of carbon nano-tube fragments are when tension lower edge draw direction breaks away from growth substrate gradually, because Van der Waals force effect, should selected a plurality of carbon nano-tube fragments be drawn out continuously end to end with other carbon nano-tube fragment respectively, thereby form one continuously, evenly and have a carbon nano-tube film of certain width.This carbon nano-tube film comprises a plurality of end to end carbon nano-tube, and this carbon nano-tube is arranged along draw direction substantially.See also Fig. 8 and Fig. 9, this carbon nano-tube film comprises a plurality of carbon nano-tube that are arranged of preferred orient 145.Further, described carbon nano-tube film comprises a plurality of carbon nano-tube fragments 143 that join end to end and align, and carbon nano-tube fragment 143 two ends interconnect by Van der Waals force.This carbon nano-tube fragment 143 comprises a plurality of carbon nano-tube that are arranged parallel to each other 145.Directly the method for stretching acquisition carbon nano-tube film is simply quick, the suitable industrial applications of carrying out.
The width of this carbon nano-tube film is relevant with the size of carbon nano pipe array, and the length of this carbon nano-tube film is not limit, and can make according to the actual requirements.When the area of this carbon nano pipe array was 4 inches, the width of this carbon nano-tube film was 0.5 nanometer～10 centimetre, and the thickness of this carbon nano-tube film is 0.5 nanometer～100 micron.
At last, utilize above-mentioned carbon nano-tube membrane to prepare carbon nano tube structure.
This carbon nano-tube membrane can directly use as a carbon nano tube structure.Further, can also be with at least two parallel no gaps of carbon nano-tube membrane or/and overlapping laying obtains a carbon nano tube structure.Because this carbon nano-tube membrane has bigger specific area, so this carbon nano-tube membrane has big viscosity, formation one carbon nano tube structure so the multilayer carbon nanotube film can be combined closely mutually.In this carbon nano tube structure, the number of plies of carbon nano-tube membrane is not limit, and has an intersecting angle α between the adjacent two layers carbon nano-tube membrane, 0 °≤α≤90 °, specifically can prepare according to actual demand.
In the present embodiment, further comprise the step of handling carbon nano tube structure with organic solvent, this organic solvent is a volatile organic solvent, can select in ethanol, methyl alcohol, acetone, dichloroethanes and the chloroform one or several mixing for use, and the organic solvent in the present embodiment adopts ethanol.This step of with an organic solvent handling is specially: this carbon nano tube structure is arranged on a substrate surface or the frame structure, by test tube organic solvent is dropped in the whole carbon nano tube structure of carbon nano tube structure surface infiltration, perhaps, also above-mentioned carbon nano tube structure can be immersed in the container that fill organic solvent and soak into.Described carbon nano tube structure after organic solvent soak into to be handled, when the number of plies of carbon nano-tube film more after a little while, under capillary effect, carbon nano-tube adjacent in the carbon nano-tube film can be shrunk to carbon nano tube line spaced apart.And when the number of plies of carbon nano-tube film more for a long time, the multilayer carbon nanotube film after organic solvent is handled is a uniform membrane structure.After organic solvent was handled, the viscosity of carbon nano tube structure reduced, and was more convenient for using.
Described carbon nano-tube membrane and preparation method thereof specifically sees also the CN101239712A number Chinese publication application " carbon nano-tube membrane structure and preparation method thereof " of people such as Fan Shoushan in application on February 9th, 2007.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
(2) comprise at least one carbon nano-tube laminate when this carbon nano tube structure, the preparation method of this carbon nano tube structure may further comprise the steps:
At first, provide a carbon nano pipe array to be formed at a growth substrate, this array is the carbon nano pipe array that aligns.
Described carbon nano pipe array is preferably the carbon nano pipe array that surpasses in-line arrangement.Described carbon nano pipe array is identical with the preparation method of above-mentioned carbon nano pipe array.
Secondly, adopt a device for exerting, push above-mentioned carbon nano pipe array and obtain a carbon nano-tube laminate, its detailed process is:
This device for exerting applies certain pressure and lists in above-mentioned carbon nano-pipe array.In the process of exerting pressure, the effect that carbon nano-pipe array is listed in pressure can separate with growth substrate down, thereby form the carbon nano-tube laminate of forming by a plurality of carbon nano-tube, and described a plurality of carbon nano-tube goes up surperficial parallel with the carbon nano-tube laminate substantially with self supporting structure.
In the embodiment of the invention, device for exerting is a pressure head, pressure head smooth surface, the arrangement mode of carbon nano-tube in the carbon nano-tube laminate of the shape of pressure head and direction of extrusion decision preparation.Particularly, when adopting pressure head edge, plane to push, can obtain isotropic carbon nano-tube laminate perpendicular to the direction of above-mentioned carbon nano pipe array growth substrate; When adopting roller bearing shape pressure head when a certain fixed-direction rolls, can obtain the carbon nano-tube laminate of carbon nano-tube along this fixed-direction orientations; When adopting roller bearing shape pressure head when different directions rolls, can obtain the carbon nano-tube laminate of carbon nano-tube along the different directions orientations.
Be appreciated that, when adopting above-mentioned different modes to push above-mentioned carbon nano pipe array, carbon nano-tube can be toppled under the effect of pressure, and attracts each other, is connected to form the carbon nano-tube laminate of being made up of a plurality of carbon nano-tube with self supporting structure with adjacent carbon nano-tube by Van der Waals force.The surface of described a plurality of carbon nano-tube and this growth substrate β that has angle, wherein, β is more than or equal to zero degree and smaller or equal to 15 degree (0 °≤β≤15 °).According to the mode difference that rolls, the carbon nano-tube in this carbon nano-tube laminate can be arranged of preferred orient along a fixed-direction, sees also Figure 10; Or be arranged of preferred orient along different directions, see also Figure 11.In addition, under the effect of pressure, carbon nano pipe array can separate with the substrate of growth, thereby makes the easy and substrate disengaging of this carbon nano-tube laminate, thereby forms the carbon nano-tube laminate of a self-supporting.
Those skilled in the art of the present technique should understand, above-mentioned carbon nano pipe array to topple over degree relevant with the size of pressure, pressure is big more, inclination angle (being the angle of the carbon nano-tube and the carbon nano pipe array direction of growth) is big more.The thickness of the carbon nano-tube laminate of preparation depends on the height and the pressure size of carbon nano pipe array.The height of carbon nano pipe array is big more and applied pressure is more little, and then the thickness of Zhi Bei carbon nano-tube laminate is big more; Otherwise the height of carbon nano pipe array is more little and applied pressure is big more, and then the thickness of Zhi Bei carbon nano-tube laminate is more little.The width of this carbon nano-tube laminate is relevant with the size of the substrate that carbon nano pipe array is grown, and the length of this carbon nano-tube laminate is not limit, and can make according to the actual requirements.The thickness of the carbon nano-tube laminate that obtains in the embodiment of the invention is 1 micron～2 millimeters.
Comprise a plurality ofly in the above-mentioned carbon nano-tube laminate, attract each other by Van der Waals force between the described carbon nano-tube, so this carbon nano-tube laminate has good toughness along same direction or the carbon nano-tube that is arranged of preferred orient.In this carbon nano-tube laminate, even carbon nanotube distributes, and is regularly arranged.
Be appreciated that this carbon nano-tube laminate has certain thickness, and can control its thickness by the height and the pressure size of carbon nano pipe array.So this carbon nano-tube laminate can directly be used as a carbon nano tube structure.In addition, can or be arranged side by side formation one carbon nano tube structure with the stacked setting of two-layer at least carbon nano-tube laminate.
The length of carbon nano-tube is greater than 50 microns in this carbon nano-tube laminate.Described carbon nano-tube laminate and preparation method thereof specifically saw also people such as Fan Shoushan in application on June 1st, 2007, in disclosed CN101314464A Chinese patent application on December 3 " preparation method of carbon nano-tube film " in 2008.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
(3) when this carbon nano tube structure comprised at least one carbon nano-tube waddingization film, the preparation method of this carbon nano tube structure may further comprise the steps:
At first, provide a carbon nanometer tube material.
Described carbon nanometer tube material can be the carbon nano-tube by prepared in various methods such as chemical vapour deposition technique, graphite electrode Constant Electric Current arc discharge sedimentation or laser evaporation sedimentations.
In the present embodiment, adopt blade or other instruments that the above-mentioned carbon nano pipe array that aligns is scraped from substrate, obtain a carbon nanometer tube material.Preferably, in the described carbon nanometer tube material, the length of carbon nano-tube is greater than 100 microns.
Next adds to above-mentioned carbon nanometer tube material in one solvent and wadding a quilt with cotton processing obtains a carbon nanotube flocculent structure, above-mentioned carbon nanotube flocculent structure is separated from solvent, and this carbon nanotube flocculent structure typing is handled to obtain a carbon nano-tube film.
In the embodiment of the invention, the optional water of solvent, volatile organic solvent etc.The waddingization processing can be by adopting methods such as ultrasonic wave dispersion treatment or high strength stirring.Preferably, the embodiment of the invention adopts ultrasonic wave to disperse 10 minutes～30 minutes.Because carbon nano-tube has great specific area, has bigger Van der Waals force between the carbon nano-tube of twining mutually.Above-mentioned wadding processing can't be dispersed in the carbon nano-tube in this carbon nanometer tube material in the solvent fully, attracts each other, twines by Van der Waals force between the carbon nano-tube, forms network-like structure.
In the embodiment of the invention, the method for described separating carbon nano-tube flocculent structure specifically may further comprise the steps: pour the above-mentioned solvent that contains carbon nanotube flocculent structure into one and be placed with in the funnel of filter paper; Thereby standing and drying a period of time obtains a carbon nanotube flocculent structure of separating, and Figure 17 is the photo of this carbon nanotube flocculent structure.
In the embodiment of the invention, the typing processing procedure of described carbon nanotube flocculent structure specifically may further comprise the steps: above-mentioned carbon nanotube flocculent structure is placed a container; This carbon nanotube flocculent structure is spread out according to reservation shape; Apply certain pressure in the carbon nanotube flocculent structure of spreading out; And, with the oven dry of solvent residual in this carbon nanotube flocculent structure or the equal solvent acquisition one carbon nano-tube waddingization film afterwards that volatilize naturally.
Be appreciated that the embodiment of the invention can control the thickness and the surface density of this carbon nano-tube waddingization film by controlling area that this carbon nanotube flocculent structure spreads out.The area that carbon nanotube flocculent structure is spread out is big more, and then the thickness of this carbon nano-tube waddingization film and surface density are just more little.The thickness of the carbon nano-tube waddingization film that obtains in the embodiment of the invention is 1 micron～2 millimeters.
In addition, the step that carbon nanotube flocculent structure is handled in above-mentioned separation and typing also can be directly mode by suction filtration realize, specifically may further comprise the steps: a miillpore filter and a funnel of bleeding is provided; The above-mentioned solvent that contains carbon nanotube flocculent structure is poured in this funnel of bleeding through this miillpore filter; Suction filtration and dry back obtain a carbon nano-tube waddingization film.This miillpore filter is that a smooth surface, aperture are 0.22 micron filter membrane.Because suction filtration mode itself will provide a bigger gas pressure in this carbon nanotube flocculent structure, this carbon nanotube flocculent structure can directly form a uniform carbon nano-tube waddingization film through suction filtration.And because microporous membrane surface is smooth, this carbon nano-tube waddingization film is peeled off easily, obtains the carbon nano-tube waddingization film of a self-supporting.
See also Figure 12, comprise the carbon nano-tube of mutual winding in the above-mentioned carbon nano-tube waddingization film, attract each other, twine by Van der Waals force between the described carbon nano-tube, form network-like structure, so this carbon nano-tube waddingization film has good toughness.In this carbon nano-tube waddingization film, even carbon nanotube distributes, and random arrangement makes this carbon nano-tube waddingization film isotropism.
Be appreciated that this carbon nano-tube waddingization film has certain thickness, and can control its thickness by controlling area and the pressure size that this carbon nanotube flocculent structure spreads out.So this carbon nano-tube waddingization film can directly use as a carbon nano tube structure.In addition, can or be arranged side by side formation one carbon nano tube structure with two-layer at least carbon nano-tube waddingization film-stack setting.
The area and the thickness of described carbon nano-tube waddingization film are not all limit, and thickness is 1 micron～1 millimeter, are preferably 100 microns.Described carbon nano-tube waddingization film and preparation method thereof specifically saw also people such as Fan Shoushan in application on April 13rd, 2007, in disclosed CN101284662A Chinese patent application on October 15 " preparation method of carbon nano-tube film " in 2008.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
(4) when this carbon nano tube structure comprises at least one liner structure of carbon nano tube, the preparation method of this carbon nano tube structure may further comprise the steps:
At first, provide at least one carbon nano-tube membrane.
The formation method of this carbon nano-tube membrane is identical with the formation method of carbon nano-tube membrane in the step ().
Secondly, handle this carbon nano-tube membrane, form at least one carbon nano tube line.
The step of this processing carbon nano-tube membrane can be handled this carbon nano-tube membrane for adopting organic solvent, thereby obtains a non-carbon nano tube line that reverses, or for the employing mechanical external force reverses this carbon nano-tube membrane, thereby obtain a carbon nano tube line that reverses.
The step that adopts organic solvent to handle this carbon nano-tube membrane is specially: the whole surface of organic solvent being soaked into described carbon nano-tube membrane, under the capillary effect that when volatile organic solvent volatilizees, produces, the a plurality of carbon nano-tube that are parallel to each other in the carbon nano-tube membrane are combined closely by Van der Waals force, thereby make the carbon nano-tube membrane be punctured into a non-carbon nano tube line that reverses.This organic solvent is a volatile organic solvent, as ethanol, methyl alcohol, acetone, dichloroethanes or chloroform, adopts ethanol in the present embodiment.Compare with the carbon nano-tube membrane of handling without organic solvent by the non-carbon nano tube line that reverses that organic solvent is handled, specific area reduces, and viscosity reduces.Be appreciated that, it is similar that this employing organic solvent is handled the method for the viscosity that adopts organic solvent reduction carbon nano-tube membrane in method that carbon nano-tube membrane forms the non-carbon nano tube line that reverses and the step (), its difference is, when needs form the non-carbon nano tube line that reverses, the two ends of carbon nano-tube membrane are unfixing, promptly the carbon nano-tube membrane are not arranged on substrate surface or the frame structure.
The step that adopts mechanical external force to reverse this carbon nano-tube membrane is reversed described carbon nano-tube film two ends in opposite direction for adopting a mechanical force.In the embodiment of the invention, specifically can provide an afterbody can cling the spinning axle of carbon nano-tube membrane.The afterbody of this spinning axle with after the carbon nano-tube membrane combine, should be spinned and spool rotated this carbon nano-tube membrane, formation one carbon nano tube line that reverses in rotary manner.The rotation mode that is appreciated that above-mentioned spinning axle is not limit, and can just change, and can reverse yet, and perhaps rotates and reverse to combine.
Further, can adopt a volatile organic solvent to handle the carbon nano tube line that this reverses.Under the capillary effect that when volatile organic solvent volatilizees, produces, adjacent carbon nano-tube is combined closely by Van der Waals force in the carbon nano tube line that reverses after the processing, the specific area of the carbon nano tube line that reverses is reduced, viscosity reduces, and specific density and intensity all increase mutually with the carbon nano tube line of handling without organic solvent that reverses.
Described carbon nano tube line and preparation method thereof specifically sees also people such as Fan Shoushan in application on September 16th, 2002, in CN100411979C number China's bulletin patent " a kind of carbon nano-tube rope and manufacture method thereof " of bulletin on August 20th, 2008, and in the CN1982209A number Chinese publication application " carbon nano-tube filament and preparation method thereof " of application on December 16th, 2005.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Once more, utilize above-mentioned carbon nano tube line to prepare at least one liner structure of carbon nano tube, and obtain a carbon nano tube structure.
Above-mentioned carbon nano tube line that reverses or the non-carbon nano tube line that reverses are a self supporting structure, can directly use as a liner structure of carbon nano tube.In addition, a plurality of carbon nano tube lines can be arranged in parallel into the liner structure of carbon nano tube of a pencil structure, perhaps a plurality of carbon nano tube lines that this is arranged in parallel reverse the liner structure of carbon nano tube that step obtains the hank line structure through one.Further, these a plurality of carbon nano tube lines or liner structure of carbon nano tube can be arranged in parallel, arranged in a crossed manner or be woven into the carbon nano tube structure of a stratiform.
Step S102 provides a wire supporting construction 202, and this carbon nano tube structure is arranged at the surface of this wire supporting construction 202.
Described wire supporting construction 202 is used to support carbon nano tube structure, and its material can be hard material, as: pottery, glass, resin, quartz etc., can also select flexible material, as: plastics or flexible fiber etc.The preferred wire supporting construction 202 of present embodiment is a ceramic bar.
The method that above-mentioned carbon nano tube structure is arranged at described wire supporting construction 202 surfaces is: because carbon nano tube structure has viscosity, so a carbon nano tube structure directly can be twined or is wrapped in described wire supporting construction 202 surfaces, and be fixed in wire supporting construction 202 surfaces by its viscosity.Perhaps, also can one carbon nano tube structure be fixed in described wire supporting construction 202 surfaces by binding agent.Described binding agent is a silica gel.
The set-up mode that is appreciated that described carbon nano tube structure is relevant with the concrete structure of this carbon nano tube structure.When carbon nano tube structure comprises carbon nano-tube membrane or carbon nano-tube laminate, and carbon nano-tube is when same direction or different directions are arranged of preferred orient in the carbon nano-tube laminate, needs to guarantee that the part carbon nano-tube in this carbon nano tube structure arranged to the other end by an end of wire supporting construction 202.When carbon nano tube structure comprises the waddingization film or comprises the carbon nano-tube laminate, and in the carbon nano-tube laminate during carbon nano-tube isotropism, the set-up mode of described carbon nano tube structure is not limit.When carbon nano tube structure comprises liner structure of carbon nano tube, single liner structure of carbon nano tube can be wound in wire supporting construction 202 surperficial or a plurality of liner structure of carbon nano tube are parallel, intersect or after braiding is arranged to a stratiform carbon nano tube structure, be wrapped in the surface of wire supporting construction 202 again.Be appreciated that when a plurality of liner structure of carbon nano tube being set in parallel in wire supporting construction 202 surperficial, liner structure of carbon nano tube needs the length direction setting of shape supporting construction 202 along the line.
In the present embodiment, carbon nano tube structure adopts 100 layers of carbon nano-tube membrane overlapping and arranged in a crossed manner, and the angle of intersecting between the adjacent two layers carbon nano-tube membrane is 90 degree.The thickness of these 100 layers of carbon nano-tube membranes is 300 microns.Utilize the viscosity of carbon nano tube structure itself, this carbon nano tube structure is wrapped in the surface of described wire supporting construction 202.
Further, before carbon nano tube structure is arranged at the surface of wire supporting construction 202, can also form a heat-reflecting layer 210 in the surface of wire supporting construction 202.The method that forms a heat-reflecting layer 210 in the surface of wire supporting construction 202 comprise apply and plated film in one or more.The material of described heat-reflecting layer 210 is a white insulating material, as: metal oxide, slaine or pottery etc.In the present embodiment, heat-reflecting layer 210 materials are preferably alundum (Al, and its thickness is 100 microns.
Step S 103, form two electrodes 206 at interval, and these two electrodes 206 are electrically connected with this carbon nano tube structure formation respectively.
The set-up mode of described two electrodes 206 is relevant with carbon nano tube structure, needs the part carbon nano-tube in the assurance carbon nano tube structure to extend to the direction of another electrode 206 along one of them electrode 206.
Described two electrodes 206 can be arranged on the same surface of carbon nano tube structure or on the different surfaces, and two electrodes 206 are around the surface that is arranged at carbon nano tube structure.Wherein, two electrodes 206 are provided with at interval, avoid short circuit phenomenon to produce so that carbon nano tube structure inserts certain resistance when being applied to line heat source 20.Carbon nano tube structure itself has good adhesiveness and conductivity, thus electrode 206 can and carbon nano tube structure between form and well electrically contact.
Described electrode 206 is conductive film, sheet metal or metal lead wire.The material of this conductive film can be metal, alloy, indium tin oxide (ITO), antimony tin oxide (ATO), conductive silver glue, conducting polymer etc.This conductive film can pass through physical vaporous deposition, and chemical vapour deposition technique or other method are formed at the carbon nano tube structure surface.This sheet metal can be copper sheet or aluminium flake etc.This sheet metal or metal lead wire can be fixed in the carbon nano tube structure surface by conductive adhesive.In the present embodiment, by sputtering method respectively at two palladium films of this carbon nano tube structure surface deposition as electrode 206, then these two palladium films are electrically connected with a conductive lead wire respectively.
Described electrode 206 can also be a metallic carbon nanotubes structure.This carbon nano tube structure comprises and aligning and equally distributed metallic carbon nanotubes.Particularly, this carbon nano tube structure comprises at least one carbon nano-tube membrane or at least one carbon nano tube line.Preferably, two carbon nano-tube membranes are arranged at the two ends of shape supporting construction 202 length directions along the line respectively as electrode 206.
Be appreciated that in the present embodiment, can also form two parallel and electrodes 206 that be provided with at interval earlier on the surface of carbon nano tube structure, and this electrode 206 be electrically connected with carbon nano tube structure.Then, the carbon nano tube structure that this is formed with electrode 206 is arranged at the surface of above-mentioned wire supporting construction 202.After forming two electrodes 206, can further form two conductive lead wires, lead to external power source from two electrodes 206 respectively.
Step S104 provides a basis material precast body, and basis material precast body and carbon nano tube structure is compound, forms a composite structure of carbon nano tube.
Described basis material precast body can or prepare forerunner's reactant of this basis material for the formed solution of basis material.This basis material precast body should be liquid state or gaseous state at a certain temperature.Described basis material precast body and carbon nano tube structure composite methods are comprised coating, deposition, printing, one or more in dipping and the spraying.
Described basis material comprises macromolecular material or nonmetallic materials etc.Particularly, this macromolecular material can comprise one or more in thermoplastic polymer or the thermosetting polymer, so this basis material precast body can be for generating the polymer monomer solution of this thermoplastic polymer or thermosetting polymer, or this thermoplastic polymer or thermosetting polymer dissolves the mixed liquor of back formation in volatile organic solvent.These nonmetallic materials can comprise one or more in glass, pottery and the semi-conducting material, so the slurry that this basis material precast body can be made for the nonmetallic materials particle, prepare the reacting gas of these nonmetallic materials or be these nonmetallic 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 basis material precast body of gaseous state, and make this basis material precast body be deposited on the carbon nano tube surface of carbon nano tube structure.In addition, a large amount of nonmetallic materials particles can be disperseed in solvent, form a slurry as this basis material precast body.
When this basis material precast body is liquid state, can be by soaking into this carbon nano tube structure and solidify this basis material precast body by liquid state basis material precast body, thereby this basis material is infiltrated in the micropore of this carbon nano tube structure, form a composite structure of carbon nano tube; When this basis material precast body is gaseous state, this basis material precast body can be deposited on the carbon nano tube surface in the carbon nano tube structure, thereby this basis material is full of in the micropore of this carbon nano tube structure, form a composite structure of carbon nano tube.When this basis material precast body is slurry, can pass through method and this carbon nano tube structure formation composite constructions such as coating, spraying.
Present embodiment adopts the injecting glue method that macromolecular material and carbon nano tube structure is compound, forms a composite structure of carbon nano tube, sees also Figure 18, and this method specifically may further comprise the steps:
Step S1041: a liquid thermosetting macromolecular material is provided.
The viscosity of described liquid thermosetting macromolecular material was lower than for 5 handkerchief seconds, and can at room temperature keep this viscosity more than 30 minutes.The viscosity of described liquid thermosetting macromolecular material 14 was lower than for 5 handkerchief seconds, and can at room temperature keep this viscosity more than 30 minutes.Described thermoset macromolecule material comprises macromolecular material and additives such as curing agent, modifier, filler or diluent.Wherein, the content of macromolecular material accounts for 70%～95% of described thermoset macromolecule material quality, and the content of described additive accounts for 5%～30% of described thermoset macromolecule material quality.Described macromolecular material is one or several mixing in phenolic resins, epoxy resin, bimaleimide resin, polyphenyl and oxazines resin, cyanate ester resin, polyimide resin, polyurethane, polymethyl methacrylate and the unsaturated polyamides resin etc.Described curing agent is used to promote the curing of described thermoset macromolecule material, and it comprises one or several mixing in fatty amine, aliphatic cyclic amine, aromatic amine, polyamide, acid anhydrides, resinae and the tertiary amine.Described modifier is used to improve flexibility, shearing resistance, bending resistance, the anti-impact of described thermoset macromolecule material or improves insulating properties etc.Modifier commonly used comprises one or several mixing in polysulfide rubber, polyamide, polyvinyl alcohol uncle butyraldehyde or the acrylonitrile-butadiene rubber class.Radiating condition when described filler is used to improve described thermoset macromolecule material and solidifies has used filler also can reduce the consumption of described thermoset macromolecule material, reduces cost.Customary filler comprises one or several mixing in asbestos fibre, glass fibre, silica flour, porcelain powder, aluminium oxide and the silica white.Described diluent is used to reduce resin viscosity, improves the permeability of resin.Described diluent comprises one or several mixing in diglycidyl ether, polyglycidyl ether, epoxy propane butyl ether, expoxy propane phenyl ether, diepoxy propane ethylether, three expoxy propane propyl ethers and the chavicol.
The embodiment of the invention preferably prepares the liquid thermosetting macromolecular material with epoxy resin, and it specifically may further comprise the steps:
At first, the mixture of glycidol ether type epoxy and glycidyl ester type epoxy is placed a container, be heated to 30 ℃～60 ℃, and the mixture of type epoxy of glycidol ether described in the container and glycidyl ester type epoxy stirred 10 minutes, till the mixture of described glycidol ether type epoxy and glycidyl ester type epoxy mixes.
Secondly, fatty amine and diglycidyl ether are joined in the mixture of described glycidol ether type epoxy that stirs and glycidyl ester type epoxy and carry out chemical reaction.
At last, the mixture of described glycidol ether type epoxy and glycidyl ester type epoxy is heated to 30 ℃～60 ℃, thereby obtains a liquid thermosetting macromolecular material that contains epoxy resin.
Step S1042: adopt described liquid thermosetting macromolecular material to soak into described carbon nano tube structure.
Adopt the method that described liquid thermosetting macromolecular material soaks into described carbon nano tube structure may further comprise the steps:
At first, the wire supporting construction 202 that is provided with carbon nano tube structure is placed a mould;
Secondly, described liquid thermosetting macromolecular material is injected in the described mould, soaks into described carbon nano tube structure.In order to allow the liquid thermosetting macromolecular material fully soak into described carbon nano tube structure, the time of soaking into described carbon nano tube structure can not be less than 10 minutes.
In the present embodiment 100 layers of stacked surface that is wrapped in ceramic bar of carbon nano-tube membrane are placed in the mould.Liquid thermosetting macromolecular material with epoxy resin is injected in the described mould then, soaks into described carbon nano tube structure 20 minutes.
Be appreciated that, the method that described liquid thermosetting macromolecular material is soaked into described carbon nano tube structure is not limit the method for injection, described liquid thermosetting macromolecular material can also be inhaled in the described carbon nano tube structure by capillarity, soak into described carbon nano tube structure, perhaps described carbon nano tube structure is immersed in the described liquid thermosetting macromolecular material.
Step S1043: solidify liquid thermoset macromolecule material, obtain a carbon nano-tube macromolecular material composite construction.
In the present embodiment, the curing that contains the thermoset macromolecule material of epoxy resin specifically may further comprise the steps:
At first, with this mold heated to 50 ℃～70 ℃, the thermoset macromolecule material that contains epoxy resin under this temperature was kept this temperature 1 hour～3 hours for liquid, made this thermoset macromolecule material continue heat absorption to increase its curing degree by a heater.
Secondly, continue this mould to 80 of heating ℃～100 ℃, under this temperature, kept 1 hour～3 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.
Once more, continue this mould to 110 of heating ℃～150 ℃, under this temperature, kept 2 hours～20 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.
At last, stop the heating, treat that this mould is cooled to room temperature after, the demoulding can get a carbon nano-tube macromolecular material composite construction.
Be appreciated that said method can also once be heated to this mould 110 ℃～150 ℃ and be cured.The application number that the concrete steps of above-mentioned preparation composite structure of carbon nano tube can be applied on December 14th, 2007 referring to people such as Fan Shoushan is 200710125109.8 China's Mainland patent application " preparation method of carbon nano tube compound material ".For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
The step that is appreciated that formation electrode 206 among the above-mentioned steps S103 can be carried out after step S104 forms this composite structure of carbon nano tube.When this basis material only is filled in the micropore of this carbon nano tube structure, thereby when making carbon nano-tube partly be exposed to the composite structure of carbon nano tube surface, can adopt the method identical that two electrodes 206 directly are formed at this composite structure of carbon nano tube surface, and be electrically connected with carbon nano tube structure formation with step S103.When this basis material all coats this carbon nano tube structure, can adopt a step of cutting to cut this composite structure of carbon nano tube, thereby make this carbon nano tube structure be exposed to the composite structure of carbon nano tube surface, and then the employing method identical with step S103 is electrically connected these two electrodes 206 with the carbon nano tube structure that comes out.
Further, present embodiment can also form an insulating protective layer 208 in the outer surface of this heating element 204, and heating element 204 is covered.The material of described insulating protective layer 208 is an insulating material, as: rubber, resin etc.Described insulating protective layer 208 thickness are not limit, and can select according to actual conditions.In the present embodiment, the material of this insulating protective layer 208 adopts rubber, and its thickness is 0.5 millimeter.This insulating protective layer 208 can be fixed in heating element 204 surfaces by the method for binding agent or mechanical fixation.In addition, when the material of this insulating protective layer 208 is a thermoplastic polymer, can be with this thermoplastic polymer at high temperature in melting state coating or be wrapped in heating element 204 surfaces, solidify to form this insulating protective layer 208 when treating low temperature.In addition; when this insulating protective layer 208 is a flexible polymer, during as a PETG (PET) film, can pass through a heat-press step; with this insulating protective layer 205 and these heating element 204 stack and hot pressing, make insulating protective layer 208 and heating element 204 strong bonded.
See also Figure 19, selectively, when the heating element in the first embodiment of the invention 204 was a flexible carbon nano tube composite construction, this line heat source 20 can prepare by the following method, specifically may further comprise the steps:
Step S401 provides a carbon nano tube structure.
Step S402 provides a flexible substrate prefabricated body, and prefabricated body of flexible substrate and carbon nano tube structure is compound, forms a flexible carbon nano tube composite construction.
Step S403 provides a wire supporting construction 202, and this flexible carbon nano tube composite construction is arranged at the surface of wire supporting construction 202.
Step S404 forms at interval two electrodes 206, and with these two electrodes 206 respectively with this flexible carbon nano tube composite construction in carbon nano tube structure form and be electrically connected.When carbon nano tube structure is coated by basis material fully, can further make this carbon nano tube structure partly be exposed to the flexible carbon nano tube composite structure surface, thereby guarantee that electrode 206 is electrically connected with carbon nano tube structure by modes such as cuttings.
Be appreciated that also can be pre-formed two electrodes 206 is electrically connected with carbon nano tube structure, again carbon nano tube structure and the prefabricated bluk recombination of flexible substrate formed composite structure of carbon nano tube.
See also Figure 20, second embodiment of the invention provides a kind of line heat source 30, and this line heat source 30 comprises that a heating element 304 and two electrodes 302 are provided with at interval and are electrically connected with this heating element 304.This heating element 304 comprises a wire composite structure of carbon nano tube.Described wire composite structure of carbon nano tube is identical with described wire composite structure of carbon nano tube in the first embodiment of the invention.Described wire composite structure of carbon nano tube comprises at least one liner structure of carbon nano tube and basis material, and described basis material permeates in described at least one liner structure of carbon nano tube.Described liner structure of carbon nano tube comprises a plurality of micropores, and described basis material permeates in the micropore of this liner structure of carbon nano tube.Described wire composite structure of carbon nano tube can also comprise that a matrix and at least one liner structure of carbon nano tube are compound in this matrix.Be appreciated that this liner structure of carbon nano tube directly is positioned in the mould that the liquid thermosetting macromolecular material is injected into soaks into this liner structure of carbon nano tube in the mould then, being heating and curing at last to prepare this wire composite structure of carbon nano tube.Described liner structure of carbon nano tube and basis material are identical with liner structure of carbon nano tube and basis material in the first embodiment of the invention.Because liner structure of carbon nano tube has the self-supporting characteristic, this wire composite structure of carbon nano tube also has the self-supporting characteristic.Described electrode 302 can be looped around the surface of this wire carbon nano tube compound material and be electrically connected with described liner structure of carbon nano tube.The material of described electrode 302 is identical with electrode 206 in the first embodiment of the invention.
Described line heat source and preparation method thereof has the following advantages: first, because this carbon nano tube structure is a self supporting structure, and carbon nano-tube evenly distributes in carbon nano tube structure, the carbon nano tube structure and the basis material of this self-supporting is directly compound, carbon nano-tube is still mutually combined keep the form of a carbon nano tube structure, thereby make in the heating element carbon nano-tube formation conductive network that can evenly distribute, be not subjected to carbon nano-tube in solution, to disperse the restriction of concentration again, make the quality percentage composition of carbon nano-tube in heating element can reach 99%, make this thermal source have higher heating properties.In addition, the kind of this basis material is not limited to polymer, makes the range of application of this thermal source more extensive.Second, because carbon nano-tube has intensity and toughness preferably, the intensity of carbon nano tube structure is bigger, better flexible, be difficult for breaking, make it have long useful life, especially, when this carbon nano tube structure and flexible substrate material are compounded to form heating element, can prepare a flexible thermal source, make this thermal source have wider range of application.The 3rd, even carbon nanotube in the carbon nano tube structure distributes, so heating element has homogeneous thickness and resistance, and heating evenly.Because the electric conversion efficiency height of carbon nano-tube, so this line heat source has the characteristics rapid, that thermo-lag is little, rate of heat exchange is fast, radiation efficiency is high that heat up.The 4th, the diameter of carbon nano-tube is less, makes carbon nano tube structure can have less thickness, can prepare the micro wire thermal source, is applied to the heating of microdevice.The 5th, when carbon nano tube structure comprised the carbon nano-tube membrane, carbon nano-tube was arranged of preferred orient along same direction in this carbon nano-tube membrane, has electric conductivity preferably, made this thermal source have heating properties preferably.The 6th, this forms the carbon nano tube structure of self-supporting, and it is simple that this carbon nano tube structure and basis material directly are compounded to form the method for heating element, and the content of carbon nano-tube in heating element can be controlled easily.With basis material compound after, this carbon nano tube structure still can keep original form, has the heating property suitable with the pure nano-carbon tube structure.
In addition, those skilled in the art also can do other variations in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention all should be included within the present invention's scope required for protection.Particularly; scope for claim to a method in claims; the order of each step should not be limited to the order narrated in the claim item, the implementing in proper order of each step according to other, and use the present invention design also should be within protection scope of the present invention.

Claims (18)

1. line heat source is characterized in that it comprises:
One wire supporting construction;
One heating element is arranged at the surface of described wire supporting construction; And
Two electrodes, this two electrode gap settings and be electrically connected with this heating element;
Described heating element comprises at least one composite structure of carbon nano tube, this composite structure of carbon nano tube comprises that a matrix and a carbon nano-tube membrane structure are compound in this matrix, and this carbon nano-tube membrane structure comprises a plurality of carbon nano-tube that are arranged of preferred orient along a fixed-direction or different directions.
2. line heat source as claimed in claim 1 is characterized in that, the carbon nano-tube in the described carbon nano-tube membrane structure and the surface of the carbon nano-tube membrane structure β that has angle, and wherein, β is more than or equal to 0 degree and smaller or equal to 15 degree.
3. line heat source as claimed in claim 1 is characterized in that, the carbon nano-tube in the described carbon nano-tube membrane structure partly overlaps, and attracts each other by Van der Waals force, combines closely.
4. line heat source as claimed in claim 1 is characterized in that, described carbon nano-tube film thickness of structure is 1 micron to 1 millimeter.
5. line heat source as claimed in claim 4 is characterized in that, the unit are thermal capacitance of described carbon nano-tube membrane structure is less than 2 * 10 -4Every square centimeter of Kelvin of joule.
6. line heat source as claimed in claim 4 is characterized in that, the unit are thermal capacitance of described carbon nano-tube membrane structure is smaller or equal to 1.7 * 10 -6Every square centimeter of Kelvin of joule.
7. line heat source as claimed in claim 1 is characterized in that, described at least one composite structure of carbon nano tube twines or be coated on the surface of described wire supporting construction.
8. line heat source as claimed in claim 1 is characterized in that, described matrix coats this carbon nano-tube membrane structure fully.
9. line heat source as claimed in claim 1 is characterized in that, described matrix is partially submerged in this carbon nano-tube membrane structure at least.
10. line heat source as claimed in claim 1 is characterized in that described basis material comprises one or more in macromolecular material and the Inorganic Non-metallic Materials.
11. line heat source as claimed in claim 1 is characterized in that, described at least two electrodes are electrically connected with described carbon nano-tube membrane structure respectively.
12. line heat source as claimed in claim 1, it is characterized in that, described line heat source further comprises a heat-reflecting layer, and described heat-reflecting layer is arranged between described heating element and the wire supporting construction, and the material of this heat-reflecting layer is one or more in metal oxide, slaine and the pottery.
13. line heat source as claimed in claim 1 is characterized in that, described line heat comprises that further an insulating protective layer protective layer is arranged at the heating element surface.
14. a line heat source is characterized in that it comprises:
One wire supporting construction;
One heating element is arranged at the surface of wire supporting construction; And
Two electrodes, this two electrode gap settings and be electrically connected with this heating element,
Described heating element comprises at least one composite structure of carbon nano tube, described composite structure of carbon nano tube comprises a carbon nano-tube membrane structure and a basis material, this carbon nano-tube membrane structure comprises a plurality of carbon nano-tube that are arranged of preferred orient along a fixed-direction or different directions, and described basis material is compound in this carbon nano-tube membrane structure.
15. line heat source as claimed in claim 14 is characterized in that, described carbon nano-tube membrane structure has a plurality of micropores, and described basis material permeates in the micropore of this carbon nano-tube membrane structure.
16. line heat source as claimed in claim 15 is characterized in that, described micropore size is less than 10 microns.
17. a line heat source is characterized in that it comprises:
One wire supports inner core;
One heating element supports inner core around coating described wire, described heating element comprises at least one composite structure of carbon nano tube, this composite structure of carbon nano tube comprises that a matrix and a carbon nano-tube membrane structure are compound in this matrix, and this carbon nano-tube membrane structure comprises a plurality of carbon nano-tube that are arranged of preferred orient along along a fixed-direction or different directions;
Two electrodes, this two electrode gap settings and be electrically connected with this heating element; And
One insulating protective layer protective layer coats this heating element.
18. line heat source as claimed in claim 17 is characterized in that, the carbon nano-tube in the described carbon nano-tube membrane structure and the surface of the carbon nano-tube membrane structure β that has angle, and wherein, β is more than or equal to 0 degree and smaller or equal to 15 degree.
CN200910106807A 2008-06-07 2009-04-20 Line heat source Pending CN101868071A (en)

Priority Applications (19)

Application Number Priority Date Filing Date Title
CN200910106807A CN101868071A (en) 2009-04-20 2009-04-20 Line heat source
US12/655,507 US20100122980A1 (en) 2008-06-13 2009-12-31 Carbon nanotube heater
US12/658,184 US20100147828A1 (en) 2008-06-13 2010-02-04 Carbon nanotube heater
US12/658,193 US20100147829A1 (en) 2008-06-13 2010-02-04 Carbon nanotube heater
US12/658,182 US20100147827A1 (en) 2008-06-13 2010-02-04 Carbon nanotube heater
US12/658,198 US20100147830A1 (en) 2008-06-07 2010-02-04 Carbon nanotube heater
US12/658,237 US20100154975A1 (en) 2008-06-13 2010-02-04 Carbon Nanotube heater
US12/660,356 US20110024410A1 (en) 2008-06-13 2010-02-25 Carbon nanotube heater
US12/660,820 US20100163547A1 (en) 2008-06-13 2010-03-04 Carbon nanotube heater
US12/661,165 US20100170891A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,133 US20100200568A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,150 US20100170890A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,110 US20100218367A1 (en) 2008-06-13 2010-03-11 Method for making carbon nanotube heater
US12/661,115 US20100200567A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,926 US20100187221A1 (en) 2008-06-13 2010-03-25 Carbon nanotube hearter
US12/750,186 US20100180429A1 (en) 2008-06-13 2010-03-30 Carbon nanotube heater
JP2010097277A JP5448999B2 (en) 2009-04-20 2010-04-20 Wire heat source
JP2013018268A JP5608767B2 (en) 2009-04-20 2013-02-01 Wire heat source
JP2013018267A JP5560354B2 (en) 2009-04-20 2013-02-01 Wire heat source

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CN113115489A (en) * 2021-03-18 2021-07-13 深圳烯湾科技有限公司 Conductive heating element and preparation method thereof

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