CN101868058B - Preparation method of three-dimensional heat source - Google Patents

Preparation method of three-dimensional heat source Download PDF

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Publication number
CN101868058B
CN101868058B CN 200910106809 CN200910106809A CN101868058B CN 101868058 B CN101868058 B CN 101868058B CN 200910106809 CN200910106809 CN 200910106809 CN 200910106809 A CN200910106809 A CN 200910106809A CN 101868058 B CN101868058 B CN 101868058B
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China
Prior art keywords
carbon nano
nano tube
tube
heat source
tube structure
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CN101868058A (en
Inventor
冯辰
刘锴
王佳平
姜开利
刘长洪
范守善
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Application filed by Tsinghua University, Hongfujin Precision Industry Shenzhen Co Ltd filed Critical Tsinghua University
Priority to CN 200910106809 priority Critical patent/CN101868058B/en
Priority to US12/655,507 priority patent/US20100122980A1/en
Priority to US12/658,237 priority patent/US20100154975A1/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 US12/660,356 priority patent/US20110024410A1/en
Priority to US12/660,820 priority patent/US20100163547A1/en
Priority to US12/661,110 priority patent/US20100218367A1/en
Priority to US12/661,133 priority patent/US20100200568A1/en
Priority to US12/661,150 priority patent/US20100170890A1/en
Priority to US12/661,165 priority patent/US20100170891A1/en
Priority to US12/661,115 priority patent/US20100200567A1/en
Priority to US12/661,926 priority patent/US20100187221A1/en
Priority to US12/750,186 priority patent/US20100180429A1/en
Priority to JP2010097289A priority patent/JP5457259B2/en
Publication of CN101868058A publication Critical patent/CN101868058A/en
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2214/00Aspects relating to resistive heating, induction heating and heating using microwaves, covered by groups H05B3/00, H05B6/00
    • H05B2214/04Heating means manufactured by using nanotechnology

Abstract

The invention aims to provide a three-dimensional heat source with long life and high electro-thermal conversion efficiency. The three-dimensional heat source comprises a heating element and at least two electrodes, wherein the heating element comprises a substrate and a plurality of carbon nano tubes distributed in the substrate; the electrodes are arranged at intervals and are respectively connected with the heating element electrically; the heating element forms a hollow three-dimensional structure and the carbon nano tubes in the heating element form at least a self-supporting carbon nano tube structure. The three-dimensional heat source can be used for manufacturing pipelines in plants, heating furnaces in laboratories or electric ovens in kitchens, etc.

Description

The preparation method of cubic heat source
Technical field
The present invention relates to a kind of preparation method of cubic heat source, relate in particular to a kind of preparation method of the cubic heat source based on carbon nano-tube.
Background technology
Thermal source plays an important role in people's production, life, scientific research.Cubic heat source is a kind of of thermal source, and its characteristics are that cubic heat source has a stereochemical structure, heats thereby heated material can be arranged at its inside.Because cubic heat source can heat simultaneously to each position of heated material, therefore, cubic heat source has wide, the homogeneous heating of heating and efficient than advantages of higher.Cubic heat source successfully is used for industrial circle, scientific research field or sphere of life etc., as factory's pipeline, laboratory furnace or kitchen tools roaster etc.
The basic structure of cubic heat source generally includes a heating element.The heating element of existing cubic heat source adopts wire usually, forms by the mode of laying or be wound around as chromenickel wire, copper wire, molybdenum filament or tungsten filament etc.Yet adopt wire to have following shortcoming as heating element: one, wire surface are easily oxidized, cause local electrical resistance to increase, thereby be blown, so useful life is short; Its two, wire is grey-body radiation, therefore, radiation efficiency is low, radiation length is short, and radiation is inhomogeneous; Its three, density of wires is larger, weight is large, uses inconvenience.
The advantages such as be to solve the problem that wire exists as heating element, carbon fiber is because it has good black body radiation performance, and density is little become the focus of heating element investigation of materials.Carbon fiber is during as heating element, and the form with carbon fiber paper exists usually.Described carbon fiber paper comprises paper base material and is distributed in a jumble asphalt base carbon fiber in this paper base material.Wherein, paper base material comprises the mixture of cellulose fiber peacekeeping resin etc., and the diameter of asphalt base carbon fiber is 3~6 millimeters, and length is 5~20 microns.Yet, adopt carbon fiber paper to have following shortcoming as heating element: one, flexible relatively poor so the intensity of this carbon fiber paper is less because the asphalt base carbon fiber in this carbon fiber paper distributes in a jumble, easily break, have equally shorter shortcoming of life-span; Its two, the electric conversion efficiency of carbon fiber paper is lower, is unfavorable for energy-conserving and environment-protective.Since the early 1990s, (see also Helical microtubules of graphitic carbon with carbon nano-tube, Nature, Sumio Iijima, vol354, p56 (1991)) caused that with its unique structure and character people pay close attention to greatly for the nano material of representative.In recent years, along with deepening continuously of carbon nano-tube and nano materials research, its wide application prospect constantly displayed.The people such as Fan Shoushan are on June 16th, 2006 application, on December 19th, 2007 disclosed one piece of publication number be to disclose a kind of nanometer flexible electric heating material in the Chinese publication application of CN101090586A.This thermo electric material comprises a flexible substrate and is dispersed in a plurality of carbon nano-tube in described flexible substrate.These a plurality of carbon nano-tube exist with powdered form, and adhesion is very weak to each other, can't form a self supporting structure with given shape.When the carbon nano-tube of this powdered form was mixed with polymer solution, the carbon nano-tube of this powdered form was very easily reunited, thereby it is inhomogeneous to cause carbon nano-tube to be disperseed in matrix.Agglomeration when disperseing in polymer solution for fear of carbon nano-tube, on the one hand, the mixture that needs to process by supersonic oscillations this carbon nano-tube and polymer solution in the process of disperseing, on the other hand, in this thermo electric material, the quality percentage composition of carbon nano-tube can not be too high, is only 0.1~4%.
And carbon nano-tube is through after above-mentioned dispersion treatment, even carbon nano-tube can be in contact with one another to each other, its adhesion also a little less than, can't form the carbon nano tube structure of a self-supporting.Because content of carbon nanotubes is few, the thermal response speed of thermoelectric material is fast not, and electric conversion efficiency is not high enough, therefore the heating temp of this thermo electric material is not high enough, has limited its range of application.In addition, for carbon nano-tube is disperseed in liquid phase, during the preparation thermo electric material, its flexible substrate can only the selective polymer material, the polymeric material heat resisting temperature is lower, and the method for this kind employing dispersing Nano carbon tubes formation thermo electric material in liquid phase has limited the selection of basis material.
Summary of the invention
In view of this, necessaryly provide a kind of electric conversion efficiency high, and the preparation method of the cubic heat source of heating temp wider range.
A kind of preparation method of cubic heat source, it comprises the following steps: the carbon nano tube structure that a self-supporting is provided, it comprises a plurality of carbon nano-tube, these a plurality of carbon nano-tube attract each other by Van der Waals force, so that carbon nano tube structure has specific shape, still can keep specific shape not by support body supports the time; The three dimensional support structure of one hollow is provided, this carbon nano tube structure is arranged at the surface of the three dimensional support structure of this hollow; Form one first electrode and one second electrode in the two ends of this carbon nano tube structure, this first electrode and the second electrode form with this carbon nano tube structure and are electrically connected to; One basis material precast body is provided, this basis material precast body and carbon nano tube structure is compound, form a composite structure of carbon nano tube, carbon nano tube structure described in this composite structure of carbon nano tube keeps compound shape before substantially.
A kind of preparation method of cubic heat source, comprise the following steps: the carbon nano tube structure of a self-supporting and the three dimensional support structure of a hollow are provided, this carbon nano tube structure comprises a plurality of carbon nano-tube, these a plurality of carbon nano-tube attract each other by Van der Waals force, so that carbon nano tube structure has specific shape, still can keep specific shape not by support body supports the time; This carbon nano tube structure is arranged at the surface of the three dimensional support structure of this hollow; One basis material precast body is provided, and basis material precast body and carbon nano tube structure is compound, forming a composite structure of carbon nano tube, carbon nano tube structure described in this composite structure of carbon nano tube keeps compound shape before substantially; And the space forms two electrodes, and between two electrodes, short circuit phenomenon produces to avoid, and with these two electrodes respectively with this composite structure of carbon nano tube in carbon nano tube structure form and be electrically connected to.
A kind of preparation method of cubic heat source, comprise the following steps: the carbon nano tube structure that a self-supporting is provided, it comprises a plurality of carbon nano-tube, these a plurality of carbon nano-tube attract each other by Van der Waals force, so that carbon nano tube structure has specific shape, still can keep specific shape not by support body supports the time; The one prefabricated body of flexible substrate is provided, and the prefabricated body of this flexible substrate and carbon nano tube structure is compound, forming a flexible carbon nano tube composite construction, carbon nano tube structure described in this flexible carbon nano tube composite construction keeps compound shape before substantially; The three dimensional support structure of one hollow is provided, and this flexible carbon nano tube composite construction is arranged at the surface of the three dimensional support structure of this hollow; And the interval forms two electrodes in the two ends of this flexible carbon nano tube composite construction, and with these two electrodes respectively with this flexible carbon nano tube composite construction in carbon nano tube structure form and be electrically connected to.
compared with prior art, described cubic heat source has the following advantages: because this carbon nano tube structure is a self supporting structure, the carbon nano tube structure of this self-supporting and matrix direct combination, carbon nano-tube is still mutually combined keep the form of a carbon nano tube structure, thereby make in heating element the carbon nano-tube formation conductive network that can evenly distribute, be not subjected to again the restriction of the dispersion concentration of the solution that carbon nano-tube uses in the course of processing, and then make the quality percentage composition of carbon nano-tube in heating element can reach 99%, make this thermal source have higher electric conversion efficiency, and heating temp wider range.
Description of drawings
The structural representation of the cubic heat source that Fig. 1 provides for first embodiment of the invention.
Fig. 2 is that Fig. 1 is along the generalized section of II-II line.
Fig. 3 is that the cubic heat source of first embodiment of the invention comprises that layered carbon nano pipe composite construction is arranged at the schematic diagram on the three dimensional support structure surface of hollow, and wherein basis material permeates in carbon nano tube structure.
Fig. 4 is that the cubic heat source of first embodiment of the invention comprises that layered carbon nano pipe composite construction is arranged at the schematic diagram on the three dimensional support structure surface of hollow, and wherein carbon nano tube structure is compound in basis material.
Fig. 5 is that the cubic heat source of first embodiment of the invention comprises that single wire composite structure of carbon nano tube is arranged at the schematic diagram on the three dimensional support structure surface of hollow.
Fig. 6 is that the cubic heat source of first embodiment of the invention comprises that a plurality of wire composite structure of carbon nano tube are arranged at the schematic diagram on wire supporting construction surface.
Fig. 7 is the stereoscan photograph of a kind of carbon nano-tube membrane of using of the cubic heat source of first embodiment of the invention.
Fig. 8 is the structural representation of the carbon nano-tube membrane that uses of the cubic heat source of first embodiment of the invention.
Fig. 9 is the stereoscan photograph of a kind of carbon nano-tube waddingization film of using of the cubic heat source of first embodiment of the invention.
Figure 10 is the stereoscan photograph that another kind that the cubic heat source of first embodiment of the invention adopts comprises the carbon nano-tube laminate of the carbon nano-tube that is arranged of preferred orient in the same direction.
Figure 11 is that the cubic heat source of first embodiment of the invention uses a kind of stereoscan photograph that comprises the carbon nano-tube laminate of the carbon nano-tube that is arranged of preferred orient along different directions.
Figure 12 is the stereoscan photograph of the carbon nano tube line of a kind of non-torsion of using of the cubic heat source of first embodiment of the invention.
Figure 13 is the stereoscan photograph of the carbon nano tube line of a kind of torsion of using of the cubic heat source of first embodiment of the invention.
Figure 14 is the cross section stereoscan photograph of the heating element that is compounded to form of a kind of carbon nano-tube membrane of using of the cubic heat source of first embodiment of the invention and epoxy resin.
Figure 15 is the preparation method's of the cubic heat source in Fig. 1 flow chart.Figure 16 is the structural representation of the cubic heat source of second embodiment of the invention.
Figure 17 is the cutaway view along XVII-XVII line in Figure 16.
Figure 18 is the cutaway view along XVIII-XVIII line in Figure 16.
Figure 19 is the structural representation of the cubic heat source of third embodiment of the invention.
Figure 20 is the cutaway view along XX-XX line in Figure 19.
Specific embodiment
Describe cubic heat source of the present invention and preparation method thereof in detail below with reference to accompanying drawing.
See also Fig. 1 and Fig. 2, for first embodiment of the invention provides a kind of cubic heat source 100.This cubic heat source 100 comprises three dimensional support structure 102, one heating element 104, one first electrodes 110 and one second electrodes 112 of a hollow.This heating element 104 is arranged at the surface of the three dimensional support structure 102 of this hollow.This first electrode 110 and the second electrode 112 are electrically connected to heating element 104 respectively, thereby are used for making described heating element 104 current flowing that switches on power.
The three dimensional support structure 102 of described hollow is used for supporting heating element 104, make heating element 104 form a stereochemical structure, this stereochemical structure defines a space, and heating element 104 can be heated in this space from multiple directions, thereby promotes the efficiency of heating surface of heating element 104.The three dimensional support structure 102 of hollow can be made by hard material or flexible material.When the three dimensional support structure 102 of this hollow was selected hard material, it can be one or more in pottery, glass, resin, quartz, plastics etc.When the three dimensional support structure 102 of hollow was selected flexible material, it can be one or more in resin, rubber, plastics or flexible fiber etc.When the three dimensional support structure 102 of this hollow was selected flexible material, it also can be bent into arbitrary shape in use as required.In the present embodiment, the three dimensional support structure 102 of this hollow is made by hard material.The three dimensional support structure 102 of described hollow has a hollow-core construction, and it can be full-closed structure, also can be semi-closed structure, its specifically can be according to actual needs as the structure that is heated element change.The structure of the three dimensional support structure 102 of this hollow can be tubulose, spherical, rectangular-shaped etc.The shape of the cross section of the three dimensional support structure 102 of hollow is not also limit, and can be circle, arc, rectangle etc.In the present embodiment, the three dimensional support structure 102 of hollow is a hollow ceramic pipe, and its cross section is a circle.
Described heating element 104 can be arranged at inner surface or the outer surface of the three dimensional support structure 102 of hollow.In the present embodiment, heating element 104 is arranged at the outer surface of the three dimensional support structure 102 of hollow.Described heating element 104 comprises a composite structure of carbon nano tube, and this composite structure of carbon nano tube can be arranged at by the binding agent (not shown) outer surface of the three dimensional support structure 102 of hollow.Described binding agent can be silica gel.This composite structure of carbon nano tube also can pass through mechanical connection manner, as screw, is fixed in the surface of the three dimensional support structure 102 of hollow.The length of this composite structure of carbon nano tube, width and thickness are not limit.Be appreciated that this three dimensional support structure is optional structure, when heating element 104 can self-supporting surrounds when forming a stereochemical structure, can need not three dimensional support structure 102.
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 described carbon nano tube structure comprises one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes.The diameter of described Single Walled Carbon Nanotube is 0.5 nanometer~50 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.In 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 carbon nano-tube, thereby make this carbon nano tube structure have a large amount of holes, described basis material infiltrates in this hole, combines closely with described carbon nano tube structure.The diameter of described hole is less than 10 microns.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 less than or equal to .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 the three dimensional support structure 102 of hollow.
Layered composite structure of carbon nano tube is two-dimensional structure.This layered carbon nano pipe composite construction can wrap up or be wrapped in the outer surface of the three dimensional support structure 102 of hollow, also can adhere to or be fixed in by binding agent or mechanical system the inner surface of the three dimensional support structure 102 of hollow.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:
The first situation sees also Fig. 3, and 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 holes in the carbon nano tube structure 2044 of this stratiform, this basis material 2042 permeates in the hole of the carbon nano tube structure 2044 of this stratiform.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 arrange.When the carbon nano tube structure 2044 of this stratiform comprised the Single Carbon Nanotubes linear structure, this Single Carbon Nanotubes linear structure 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 case sees also Fig. 4, and layered composite structure of carbon nano tube comprises that a matrix 2042 and a carbon nano tube structure 2044 are compound in this matrix 2042.This matrix 2042 is layer structure, and this carbon nano tube structure 2044 is distributed in this matrix 2042, and preferably, this carbon nano tube structure 2044 evenly distributes in matrix 2042.See also Fig. 1, when this carbon nano tube structure 2044 be a plurality of parallel and intervals arrange liner structure of carbon nano tube the time, this liner structure of carbon nano tube extends to the second electrode 112 by the first electrode 110, in the present embodiment, liner structure of carbon nano tube extends to the other end by an end of the three dimensional support structure 102 of hollow.
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 or be coated on the surface of liner structure of carbon nano tube.See also Fig. 5, when this heating element 104 is single wire composite structure of carbon nano tube, this single wire composite structure of carbon nano tube can directly be wound in the outer surface of the three dimensional support structure 102 of described hollow, perhaps is fixed in inner surface or the outer surface of the three dimensional support structure 102 of hollow by binding agent or mechanical system.See also Fig. 1, the first electrode 110 and the second electrode 112 can be electrically connected to the two ends of this single wire composite structure of carbon nano tube respectively.The first electrode 110 and the second electrode 112 are ring-type, also can be the structure of the similar ring-types such as C shape.In the present embodiment, the first electrode 110 and the second electrode 112 almost parallels.See also Fig. 6, when this heating element 104 comprises 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, then are wound around or are wrapped in three dimensional support structure 102 surfaces of described hollow.
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 that forms 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 carbon nano-tube.Carbon nano-tube in this carbon nano-tube film is unordered or ordered arrangement.The orientation of the unordered finger carbon nano-tube here is irregular, and the orientation of the most at least carbon nano-tube of orderly finger here has certain rule.Particularly, when carbon nano-tube film comprised the carbon nano-tube of lack of alignment, carbon nano-tube was wound around mutually or isotropism is arranged; When carbon nano tube structure comprised the carbon nano-tube of ordered arrangement, carbon nano-tube was arranged of preferred orient along a direction or multiple directions.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.In situation of the same area, the thickness of carbon nano tube structure is larger, and thermal response speed is slower; Otherwise the thickness of carbon nano tube structure is less, and thermal response speed is faster.
Described carbon nano-tube membrane is for pulling the carbon nano-tube film that obtains from a carbon nano pipe array.Described carbon nano tube structure can comprise one deck carbon nano-tube membrane or two-layer above carbon nano-tube membrane.The carbon nano-tube membrane comprises a plurality of preferred orientations in the same direction and is parallel to the carbon nano-tube of carbon nano-tube membrane surface alignment.Join end to end by Van der Waals force between described carbon nano-tube.See also Fig. 7 and Fig. 8, each carbon nano-tube membrane comprise a plurality of continuously and the carbon nano-tube fragment 143 that aligns.These a plurality of carbon nano-tube fragments 143 join 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 these a plurality of carbon nano-tube that are parallel to each other 145 closely connect 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 sees also the people such as Fan Shoushan in application on February 9th, 2007, in disclosed No. CN101239712A Chinese publication application on August 13rd, 2008 " carbon nano-tube membrane structure and preparation method thereof ", applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.Be understandable that, when this carbon nano tube structure is comprised of the carbon nano-tube membrane, and the Thickness Ratio of carbon nano tube structure hour, for example less than 10 microns, this carbon nano tube structure has good transparency, and its light transmittance can reach 90%, can be for the manufacture of a transparent thermal source.
When described carbon nano tube structure comprised carbon nano-tube membrane more than two-layer, this multilayer carbon nanotube membrane mutually superposeed and arranges or be set up in parallel.Form an intersecting angle α between the carbon nano-tube that is arranged of preferred orient in adjacent two layers carbon nano-tube membrane, α is more than or equal to 0 degree and less than or equal to 90 degree (0 °≤α≤90 °).Has certain interval between the carbon nano-tube membrane of described multilayer or between the adjacent carbon nano-tube among carbon nano-tube membrane, thereby form a plurality of holes in carbon nano tube structure, the size of hole approximately less than 10 microns so that described matrix infiltrate in these holes.
The carbon nano-tube film of described carbon nano-tube waddingization film for forming by a waddingization method, this carbon nano-tube waddingization film comprises mutual winding and equally distributed carbon nano-tube.The length of carbon nano-tube is preferably 200~900 microns greater than 10 microns.Attract each other, be wound around by Van der Waals force between described carbon nano-tube, form network-like structure.Described carbon nano-tube waddingization film isotropism.Carbon nano-tube in described carbon nano-tube waddingization film is evenly to distribute, and random arrangement forms a large amount of pore structures, and pore-size is approximately less than 10 microns.Length and the width of described carbon nano-tube waddingization film are not limit.See also Fig. 9, due in carbon nano-tube waddingization film, carbon nano-tube is wound around mutually, so this carbon nano-tube waddingization film has good pliability, and is a self supporting structure, can become arbitrary shape and not break by bending fold.Area and the thickness of described carbon nano-tube waddingization film are not all limit, and thickness is 1 micron~1 millimeter, are preferably 100 microns.Described carbon nano-tube waddingization film and preparation method thereof sees also the people such as Fan Shoushan in application on April 13rd, 2007, in disclosed No. CN101284662A Chinese publication application on October 15th, 2008 " preparation method of carbon nano-tube film ", applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
The carbon nano-tube film of described carbon nano-tube laminate for forming by rolling a carbon nano pipe array.This carbon nano-tube laminate comprises equally distributed carbon nano-tube, carbon nano-tube in the same direction or different directions be arranged of preferred orient.Carbon nano-tube can be also isotropic.The mutual part of carbon nano-tube in described carbon nano-tube laminate is overlapping, and attracts each other by Van der Waals force, combines closely, and makes this carbon nano tube structure have good pliability, can become arbitrary shape and not break by bending fold.And owing to attracting each other by Van der Waals force between the carbon nano-tube in 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 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 less than or equal to 15 degree (0≤β≤15 °), this angle β is with to be applied to the pressure that carbon nano-pipe array lists relevant, pressure is larger, this angle is less, and preferably, the carbon nano-tube in this carbon nano-tube laminate is parallel to this growth substrate and arranges.Different according to the mode that rolls, the carbon nano-tube in this carbon nano-tube laminate has different spread patterns.See also Figure 10, when rolling in the same direction, carbon nano-tube is arranged of preferred orient along a fixed-direction.See also Figure 11, when rolling along different directions, carbon nano-tube is arranged of preferred orient along different directions.When vertically rolling carbon nano pipe array from the top of carbon nano pipe array, the carbon nano-tube laminate is isotropic.In this carbon nano-tube laminate, the length of carbon nano-tube is greater than 50 microns.
Area and the thickness of this carbon nano-tube laminate are not limit, and can select according to actual needs the time that will heat as heating object.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 larger and applied pressure is less, and the thickness of the carbon nano-tube laminate of preparation is larger, otherwise the height of carbon nano pipe array is less and applied pressure is larger, and the thickness of the carbon nano-tube laminate of preparation is less.Have certain interval between adjacent carbon nano-tube among described carbon nano-tube laminate, thereby form a plurality of holes in the carbon nano-tube laminate, the size of hole is approximately less than 10 microns.Described carbon nano-tube laminate and preparation method thereof sees also the people such as Fan Shoushan in application on June 1st, 2007, in disclosed No. CN101314464A Chinese publication application on December 3rd, 2008 " preparation method of carbon nano-tube film ", applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Select liner structure of carbon nano tube when described carbon nano tube structure, it comprises at least one carbon nanotube long line.When liner structure of carbon nano tube comprised many carbon nanotube long line, carbon nanotube long line be arranged in parallel or mutual spiral winding.
Described carbon nano tube line can be the carbon nano tube line of non-torsion or the carbon nano tube line of torsion.The carbon nano tube line of this non-torsion obtains for the carbon nano-tube membrane is processed by organic solvent.See also Figure 12, the carbon nano tube line of this non-torsion comprises a plurality of along the arrangement of carbon nano tube line length direction and end to end carbon nano-tube.Preferably, the carbon nano tube line of this non-torsion comprises a plurality of carbon nano-tube fragments, joins end to end by Van der Waals force between these a plurality of carbon nano-tube fragments, and each carbon nano-tube fragment comprises a plurality of carbon nano-tube that are parallel to each other and combine closely by Van der Waals force.This carbon nano-tube fragment has length, thickness, uniformity and shape arbitrarily.The carbon nano-tube line length of this non-torsion is not limit, and diameter is 0.5 nanometer~100 micron.
The carbon nano tube line of described torsion is for adopting a mechanical force that acquisition is reversed at described carbon nano-tube membrane two ends in opposite direction.See also Figure 13, the carbon nano tube line of this torsion comprises a plurality of carbon nano-tube of arranging around the carbon nano tube line axial screw.Preferably, the carbon nano tube line of this torsion comprises a plurality of carbon nano-tube fragments, joins end to end by Van der Waals force between these a plurality of carbon nano-tube fragments, and each carbon nano-tube fragment comprises a plurality of carbon nano-tube that are parallel to each other and combine closely by Van der Waals force.This carbon nano-tube fragment has length, thickness, uniformity and shape arbitrarily.The carbon nano-tube line length of this torsion is not limit, and diameter is 0.5 nanometer~100 micron.Described carbon nano tube line and preparation method thereof sees also the people such as Fan Shoushan in application on September 16th, 2002, No. CN100411979C China's bulletin patent " a kind of Nanotubes and manufacture method thereof " in bulletin on August 20th, 2008, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd., and in disclosed No. CN1982209A Chinese publication application on June 20 " carbon nano-tube filament and preparation method thereof " in 2007, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Further, can adopt a volatile organic solvent to process the carbon nano tube line of this torsion.Under the capillary effect that produces when volatile organic solvent volatilizees, carbon nano-tube adjacent in the carbon nano tube line of the torsion after processing is combined closely by Van der Waals force, diameter and the specific area of the carbon nano tube line of torsion are further reduced, thereby its density and intensity are further increased.
Because this carbon nano tube line obtains for adopting organic solvent or mechanical force to process above-mentioned carbon nano-tube membrane, this carbon nano-tube membrane is self supporting structure, therefore this carbon nano tube line is also self supporting structure.In addition, owing to having the gap between the adjacent carbons nanotube in this carbon nano tube line, therefore this carbon nano tube line has a large amount of holes, the size of hole is approximately less than 10 microns.
The carbon nano tube structure of the embodiment of the present invention comprises a plurality of carbon nano-tube membranes along the stacked setting of equidirectional, and in carbon nano tube structure, carbon nano-tube all is arranged of preferred orient in the same direction thereby make.
The material of described matrix can be selected from macromolecular material or nonmetallic materials etc.This matrix or the presoma that forms this matrix are liquid state or gaseous state at a certain temperature, thereby the presoma of this matrix or this matrix can be penetrated in the gap or hole of this carbon nano tube structure in the preparation process of the heating element 104 of cubic heat source 100, and form the composite construction that a solid matrix combines with carbon nano tube structure.The material of this matrix 164 should have certain heat resistance, makes it unlikelyly in the working temperature of this cubic heat source 100 be subjected to heat damage, distortion, fusing, gasification or decomposition.This macromolecular material can comprise one or more of thermoplastic polymer or thermosetting polymer, as one or more in cellulose, polyethylene terephthalate, acryl resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, phenolic resins, epoxy resin, silica gel and polyester etc.These nonmetallic materials can comprise one or more in glass, pottery and semi-conducting material.
Owing to having the gap between the carbon nano-tube in carbon nano tube structure, thereby form a plurality of holes in carbon nano tube structure, and because the presoma of matrix or matrix is liquid state or gaseous state at a certain temperature, this matrix can infiltrate in this carbon nano tube structure hole with the carbon nano tube structure compound tense.Figure 14 is the cross-sectional view of the composite structure of carbon nano tube of carbon nano tube structure and the compound rear formation of epoxy resin in the present embodiment.This carbon nano tube structure is a carbon nano-tube membrane.Can find, compound with epoxy resin after, carbon nano tube structure still can keep the form before compound substantially, carbon nano-tube is arranged in epoxy resin-base substantially in the same direction.
This matrix can only be filled in the hole of described carbon nano tube structure, also can coat whole carbon nano tube structure fully.When this heating element 104 comprises a plurality of carbon nano tube structure, but this a plurality of carbon nano tube structures space or being arranged in this matrix of being in contact with one another.When this carbon nano tube structure is planar structure, but this planar structure space or being arranged side by side or stacked being arranged in matrix of being in contact with one another; When this carbon nano tube structure is linear structure, but this linear structure space or being arranged side by side in matrix of being in contact with one another.When carbon nano tube structure is arranged at intervals in matrix, can save the consumption of the required carbon nano tube structure of this heating element 104 of preparation.In addition, visual actual needs is arranged on carbon nano tube structure the ad-hoc location of matrix, thereby makes this heating element 104 have different heating-up temperatures at diverse location.
Described matrix permeability can play the effect of fixing the carbon nano-tube in this carbon nano tube structure in the hole of carbon nano tube structure, make the not reason external force friction or scratch and come off of carbon nano-tube in carbon nano tube structure in use.When described matrix coated whole carbon nano tube structure, this matrix can further be protected this carbon nano tube structure, guarantees simultaneously this heating element 104 and exterior insulation.In addition, this matrix can further play heat conduction and make the purpose of uniform heat distribution.Further, when this carbon nano tube structure steep temperature rise, this matrix can play the effect of buffering heat, makes the variations in temperature of this heating element 104 comparatively soft.When this basis material is flexible material, can strengthen flexibility and the toughness of composite structure of carbon nano tube.
By the carbon nano tube structure direct combination of matrix and self-supporting is formed heating element 104, carbon nano-tube is evenly distributed in heating element 104, and the content of carbon nano-tube reach 99%, improved the heating temp of cubic heat source 100.Because this carbon nano tube structure is a self supporting structure, and carbon nano-tube evenly distributes in carbon nano tube structure, carbon nano tube structure and matrix direct combination with this self-supporting, carbon nano-tube is still mutually combined keep the form of a carbon nano tube structure, thereby make in heating element 104 the carbon nano-tube formation conductive network that can evenly distribute, be not subjected to again carbon nano-tube to disperse the restriction of concentration in solution, make the quality percentage composition of carbon nano-tube in composite structure of carbon nano tube can reach 99%.
Described the first electrode 110 and the second electrode 112 are made by electric conducting material, and the shape of this first electrode 110 and the second electrode 112 is not limit, and can be conducting film, sheet metal or metal lead wire.Preferably, the first electrode 110 and the second electrode 112 are one deck conducting film.When being used for miniature cubic heat source 100, the thickness of this conducting film is 0.5 nanometer~100 micron.The material of this conducting film can be metal, alloy, indium tin oxide (ITO), antimony tin oxide (ATO), conductive silver glue, conducting polymer or conductive carbon nanotube etc.This metal or alloy material can be the alloy of aluminium, copper, tungsten, molybdenum, gold, titanium, neodymium, palladium, caesium or its combination in any.In the present embodiment, the material of described the first electrode 110 and the second electrode 112 is the Metal Palladium film, and thickness is 5 nanometers.Described Metal Palladium and carbon nano-tube have wetting effect preferably, are conducive to form good electrically contacting between described the first electrode 110 and the second electrode 112 and described heating element 104, reduce ohmic contact resistance.
Described the first electrode 110 and the second electrode 112 are electrically connected to carbon nano tube structure in heating element 104.Wherein, the first electrode 110 and the second electrode 112 intervals arrange so that heating element 104 when being applied to cubic heat source 100 the certain resistance of access avoid short circuit phenomenon to produce.
When matrix only is filled in the hole of this carbon nano tube structure, because part carbon nano-tube in this carbon nano tube structure partly is exposed to heating element 104 surfaces, this first electrode 110 and the second electrode 112 can be arranged on the surface of heating element 104, thereby this first electrode 110 and the second electrode 112 are electrically connected to carbon nano tube structure.This first electrode 110 and the second electrode 112 can be arranged on the same surface of heating element 104 and also can be arranged on the different surfaces of heating element 104.In addition, when matrix in this heating element 104 coats whole carbon nano tube structure, for this first electrode 110 and the second electrode 112 are electrically connected to this carbon nano tube structure, this first electrode 110 and the second electrode 112 can be arranged in the matrix of heating element 104, and directly contact with carbon nano tube structure.At this moment, for making this first electrode 110 and the second electrode 112 and external power source conducting, this first electrode 110 and the second electrode 112 can partly be exposed to outside heating element 104; Perhaps, this cubic heat source 100 can further comprise two lead-in wires, is electrically connected to this first electrode 110 and the second electrode 112 respectively, and draws from this matrix inside.
When in this carbon nano tube structure during the carbon nano-tube ordered arrangement, the orientation of this carbon nano-tube can be along extending from the first electrode 110 to second electrode 112 directions.Described the first electrode 110 and the second electrode 112 can be arranged at this heating element 104 or carbon nano tube structure surface by a conductive adhesive (not shown), conductive adhesive can also be fixed in described the first electrode 110 and the second electrode 112 on the surface of carbon nano tube structure when realizing that the first electrode 110 and the second electrode 112 electrically contact with carbon nano tube structure better.This conductive adhesive can be elargol.
The structure and material that is appreciated that the first electrode 110 and the second electrode 112 is not all limit, and it arranges purpose is in order to make carbon nano tube structure current flowing in described heating element 104.Therefore, 112 needs of described the first electrode 110 and the second electrode conduction, and and described heating element 104 in form between carbon nano tube structure and electrically contact all in protection scope of the present invention.The particular location of described the first electrode 110 and the second electrode 112 is not limit, and only need guarantee that the first electrode 110 is electrically connected to heating element 104 respectively with the second electrode 112.Because heating element 104 is a composite structure of carbon nano tube, this carbon nano tube compound material comprises a matrix and the carbon nano tube structure that is distributed in this matrix, really play the carbon nano tube structure that is of heat effect, therefore, the first electrode 110 and the second electrode 112 should be electrically connected to carbon nano tube structure.Described cubic heat source 100 can comprise that also a plurality of electrodes are electrically connected to described heating element 104, and its quantity is not limit, and realizes selectively heating regional of heating element 104 by controlling different electrodes.In these a plurality of electrodes, any two electrodes can be electrically connected to external circuit respectively, make heating element 104 work that are electrically connected between these two electrodes.Preferably, any two the adjacent electrodes in these a plurality of electrodes are electrically connected to external power source respectively by the external wire (not shown), i.e. the electrode of alternate intervals setting connects negative or positive electrode simultaneously.
Described cubic heat source 100 further comprises a heat-reflecting layer 108, and heat-reflecting layer 108 is used for the heat that reflection heating element 104 sends, and makes it effectively to the three dimensional support structure 102 inner spaces heating of hollow.Therefore, heat-reflecting layer 108 is positioned at heating element 104 peripheries, when heating element 104 was arranged at the inner surface of three dimensional support structure 102 of hollow, heat-reflecting layer 108 was arranged between the three dimensional support structure 102 of hollow and heating element 104 or is arranged at the outer surface of the three dimensional support structure 102 of hollow; When heating element 104 was arranged at the outer surface of three dimensional support structure 102 of hollow, heat-reflecting layer 108 was arranged at the outer surface of heating element, and namely heating element 104 is arranged between the three dimensional support structure 102 and heat-reflecting layer 108 of hollow.In the present embodiment, be arranged at the outer surface of the three dimensional support structure 102 of hollow due to heating element 104, so heat-reflecting layer 108 is arranged at the outer surface of heating element 104.The material of heat-reflecting layer 108 is a white insulating material, as: metal oxide, slaine or pottery etc.Heat-reflecting layer 108 is arranged at the outer surface of the three dimensional support structure 102 of hollow by the method for sputter or coating.In the present embodiment, the material of heat-reflecting layer 108 is preferably alundum (Al2O3), and its thickness is 100 microns~0.5 millimeter.Be appreciated that this heat-reflecting layer 108 is an optional structure, when cubic heat source 100 did not comprise heat-reflecting layer, this cubic heat source 100 also can be used for external heat.
Described cubic heat source 100 further comprises an insulating protective layer (not shown).Described insulating protective layer is used for preventing that this cubic heat source 100 from electrically contacting with external world's formation in use, can also prevent the carbon nano tube structure absorption introduced contaminants in heating element 104 simultaneously.Insulating protective layer be arranged at heating element with can with surface that the external world contacts on.Be appreciated that described insulating protective layer 106 is an optional structure.When heating element 104 does not contact with the external world or during when the complete coated carbon nano tube structure of matrix, can need not insulating protective layer.The material of described insulating protective layer is an insulating material, as: rubber, resin etc.Described insulation protection layer thickness is not limit, and can select according to actual conditions.Preferably, the thickness of this insulating protective layer is 0.5~2 millimeter.This insulating protective layer can be formed at by the method for coating or sputter the surface of heating element 104.In the present embodiment, be arranged at due to heating element 104 between the three dimensional support structure 102 and heat-reflecting layer 108 of hollow, so need not insulating protective layer.
The present embodiment provides a kind of method of using above-mentioned cubic heat source 100 heating objects, and it comprises the following steps: an object to be heated is provided; Object to be heated is arranged in the inner space of this cubic heat source 100; Cubic heat source 100 is connected the supply voltage of 1 volt~20 volts of wire accesses with the second electrode 112 by the first electrode 110, making cubic heat source 100 heating powers is 1 watt~40 watts, and this cubic heat source can give off the long electromagnetic wave of wavelength.The temperature of measuring heating element 104 surfaces of finding this cubic heat source 100 by temperature measuring set is 50 ℃~500 ℃, the heating heated material.As seen, this composite structure of carbon nano tube has higher electric conversion efficiency.Because the heat on heating element 104 surfaces passes to heated material with thermal-radiating form, heating effect is can be because of the distance of various piece in heated material and cubic heat source 100 not different and produce larger differently, can realize the homogeneous heating to heated material.For the object with black matrix structure, when being 200 ℃~450 ℃, its corresponding temperature just can send thermal radiation invisible to the human eye (infrared ray), and the thermal radiation of this moment is the most stable, most effective, and the thermal radiation heat that produces is maximum.
This cubic heat source 100 can directly contact it with body surface to be heated or itself and heated object interval are arranged in use, utilizes its thermal radiation to heat.This cubic heat source 100 can be widely used in as factory's pipeline, laboratory furnace or kitchen tools roaster etc.
See also Figure 15, the embodiment of the present invention further provides a kind of preparation method of above-mentioned cubic heat source 100, and it comprises the following steps:
Step 1 provides a carbon nano tube structure, and this carbon nano tube structure comprises a plurality of holes.
Because carbon nano tube structure can comprise the carbon nano-tube membrane, the carbon nano-tube laminate, one or more in carbon nano-tube waddingization film or liner structure of carbon nano tube, thus the preparation method of carbon nano tube structure respectively corresponding above-mentioned four kinds of structures be divided into four kinds of methods.
(1) preparation method of carbon nano-tube membrane comprises the following steps:
At first, provide a carbon nano pipe array to be formed at a growth substrate, this array is the carbon nano pipe array of super in-line arrangement.
The preparation method of this carbon nano pipe array adopts chemical vapour deposition technique, its concrete steps comprise: a smooth growth substrate (a) is provided, this growth substrate can be selected P type or the substrate of N-type silicon growth, or select the silicon growth substrate that is formed with oxide layer, the embodiment of the present invention to be preferably and adopt the silicon growth substrate of 4 inches; (b) form a catalyst layer at the growth substrate surface uniform, this catalyst layer material can be selected one of alloy of iron (Fe), cobalt (Co), nickel (Ni) or its combination in any; (c) the above-mentioned growth substrate that is formed with catalyst layer was annealed in the air of 700 ℃~900 ℃ approximately 30 minutes~90 minutes; (d) growth substrate that will process is placed in reacting furnace, is heated to 500 ℃~740 ℃ under the protective gas environment, then passes into carbon-source gas reaction approximately 5 minutes~30 minutes, and growth obtains carbon nano pipe array.This carbon nano-pipe array is classified a plurality of parallel to each other and pure nano-carbon tube arrays of forming perpendicular to the carbon nano-tube of growth substrate growth as.By above-mentioned control growth conditions, substantially do not contain impurity in this carbon nano pipe array that aligns, as agraphitic carbon or residual catalyst metal particles etc.
The carbon nano-pipe array that the embodiment of the present invention provides is classified a kind of in single-wall carbon nanotube array, double-walled carbon nano-tube array and array of multi-walled carbon nanotubes as.The diameter of described 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.
In the embodiment of the present invention, carbon source gas can be selected the more active hydrocarbons of chemical property such as acetylene, ethene, methane, and the preferred carbon source gas of the embodiment of the present invention is acetylene; Protective gas is nitrogen or inert gas, and the preferred protective gas of the embodiment of the present invention is argon gas.
Be appreciated that the carbon nano pipe array that the embodiment of the present invention provides is not limited to above-mentioned preparation method, also can be graphite electrode Constant Electric Current arc discharge sedimentation, laser evaporation sedimentation etc.
Secondly, adopt a stretching tool to pull carbon nano-tube from carbon nano pipe array and obtain at least one carbon nano-tube membrane, it specifically comprises the following steps: (a) from described super in-line arrangement carbon nano pipe array selected one or have a plurality of carbon nano-tube of certain width, the 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 membrane.This pulls direction along the direction of growth that is basically perpendicular to carbon nano pipe array.
In above-mentioned drawing process, when these a plurality of carbon nano-tube fragments break away from growth substrate gradually along draw direction under the pulling force effect, due to van der Waals interaction, 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 membrane of certain width.
The width of this carbon nano-tube membrane is relevant with the size of carbon nano pipe array, and the length of this carbon nano-tube membrane 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 membrane was 0.5 nanometer~10 centimetre, and the thickness of this carbon nano-tube membrane is 0.5 nanometer~100 micron.
(2) preparation method of carbon nano-tube waddingization film comprises the following steps:
At first, provide a carbon nanometer tube material.
Described carbon nanometer tube material can be the carbon nano-tube by the preparation of the whole bag of tricks such as chemical vapour deposition technique, graphite electrode Constant Electric Current arc discharge sedimentation or laser evaporation sedimentation.
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 described carbon nanometer tube material, the length of carbon nano-tube is greater than 100 microns.
Secondly, add to above-mentioned carbon nanometer tube material in one solvent and wadding a quilt with cotton processing acquisition one carbon nanotube flocculent structure, above-mentioned carbon nanotube flocculent structure is separated from solvent, and to this carbon nanotube flocculent structure heat treatment to obtain a carbon nano-tube waddingization film.
In the embodiment of the present invention, the optional water of solvent, volatile organic solvent etc.The waddingization processing can be by adopting the methods such as ultrasonic wave dispersion treatment or high strength stirring.Preferably, the embodiment of the present invention adopts ultrasonic wave to disperse 10 minutes~30 minutes.Because carbon nano-tube has great specific area, has larger Van der Waals force between the carbon nano-tube that mutually is wound around.Above-mentioned wadding processing can't be dispersed in the carbon nano-tube in this carbon nanometer tube material in solvent fully, attracts each other, is wound around by Van der Waals force between carbon nano-tube, forms network-like structure.
In the embodiment of the present invention, the method for described separating carbon nano-tube flocculent structure specifically comprises the following steps: pour the above-mentioned solvent that contains carbon nanotube flocculent structure into one and be placed with in the funnel of filter paper; Thereby standing and drying a period of time obtains a carbon nanotube flocculent structure of separating.
In the embodiment of the present invention, the heat treatment process of described carbon nanotube flocculent structure specifically comprises the following steps: above-mentioned carbon nanotube flocculent structure is placed in 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 naturally volatilize.
Be appreciated that the embodiment of the present invention can control by controlling area that this carbon nanotube flocculent structure spreads out thickness and the surface density of this carbon nano-tube waddingization film.The area that carbon nanotube flocculent structure is spread out is larger, and the thickness of this carbon nano-tube waddingization film and surface density are just less.
In addition, the step of above-mentioned separation and heat treatment carbon nanotube flocculent structure also can be directly mode by suction filtration realize, specifically comprise the following steps: a hole filter membrane 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 hole filter membrane; Suction filtration and the dry rear carbon nano-tube waddingization film that obtains.This hole filter membrane is a smooth surface, be of a size of the filter membrane of 0.22 micron.Because suction filtration mode itself will provide a larger gas pressure in this carbon nanotube flocculent structure, this carbon nanotube flocculent structure is through the direct formation one uniform carbon nano-tube waddingization film of suction filtration.And due to hole filter membrane smooth surface, this carbon nano-tube waddingization film is easily peeled off, and obtains the carbon nano-tube waddingization film of a self-supporting.
Be appreciated that this carbon nano-tube waddingization film has certain thickness, and the thickness that can control carbon nano-tube waddingization film by controlling area that this carbon nanotube flocculent structure spreads out and pressure size.This carbon nano-tube waddingization film can be used as a carbon nano tube structure and uses, and also can or be arranged side by side two-layer at least carbon nano-tube waddingization film-stack setting and form a carbon nano tube structure.
(3) preparation method of carbon nano-tube laminate comprises the following 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, carbon nano-pipe array is listed under the effect of pressure and can separates with growth substrate, thereby form the carbon nano-tube laminate with self supporting structure that is formed 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.
In the embodiment of the present invention, device for exerting is a pressure head, the arrangement mode of carbon nano-tube in the carbon nano-tube laminate that pressure head smooth surface, the shape of pressure head and the direction of extrusion determine to prepare.Preferably, when adopting pressure head edge, plane to push perpendicular to the direction of above-mentioned carbon nano pipe array growth substrate, can obtain carbon nano-tube is the carbon nano-tube laminate that isotropism is arranged; When adopting roller bearing shape pressure head to roll along a certain fixed-direction, can obtain carbon nano-tube along the carbon nano-tube laminate of this fixed-direction orientations; When adopting roller bearing shape pressure head to roll along different directions, can obtain carbon nano-tube along the carbon nano-tube laminate of 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 by Van der Waals force the carbon nano-tube laminate with self supporting structure that is comprised of a plurality of carbon nano-tube with adjacent carbon nano-tube.
Those skilled in the art of the present technique should understand, above-mentioned carbon nano pipe array to topple over degree (i.e. the orientation angulation of the orientation of carbon nano pipe array carbon nano pipe array when not being extruded after the extruding) relevant with the size of pressure, pressure is larger, and the inclination angle is larger.The thickness of the carbon nano-tube laminate of preparation depends on height and the pressure size of carbon nano pipe array.The height of carbon nano pipe array is larger and applied pressure is less, and the thickness of the carbon nano-tube laminate of preparation is larger; Otherwise the height of carbon nano pipe array is less and applied pressure is larger, and the thickness of the carbon nano-tube laminate of preparation is less.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.
Be appreciated that this carbon nano-tube laminate has certain thickness, and can control its thickness by height and the pressure size of carbon nano pipe array.So this carbon nano-tube laminate can directly be used as a carbon nano tube structure.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.
(4) preparation method of liner structure of carbon nano tube comprises the following steps:
At first, provide at least one carbon nano-tube membrane.
The formation method of this carbon nano-tube membrane is identical with the formation method of carbon nano-tube membrane in ().
Secondly, process this carbon nano-tube membrane, form at least one carbon nano tube line.
The step of this processing carbon nano-tube membrane can be processed this carbon nano-tube membrane for adopting organic solvent, thereby obtains the carbon nano tube line of a non-torsion, or for the employing mechanical external force reverses this carbon nano-tube membrane, thereby obtain a carbon nano tube line that reverses.
It is similar that this employing organic solvent is processed the method for the viscosity that adopts organic solvent reduction carbon nano-tube membrane in method and () of carbon nano tube line that carbon nano-tube membrane forms non-torsion, its difference is, when needs form the carbon nano tube line of non-torsion, the two ends of carbon nano-tube membrane are unfixing, namely the carbon nano-tube membrane are not arranged on substrate surface or frame structure.
Adopt step that mechanical external force reverses this carbon nano-tube membrane to form for adopting a mechanical force that described carbon nano-tube film two ends are reversed in opposite direction the carbon nano tube line that reverses.Further, can adopt a volatile organic solvent to process the carbon nano tube line of this torsion.Under the capillary effect that produces when volatile organic solvent volatilizees, carbon nano-tube adjacent in the carbon nano tube line of the torsion after processing is combined closely by Van der Waals force, the specific area of the carbon nano tube line of torsion is reduced, viscosity reduces, and all increases with carbon nano tube line phase specific density and the intensity of the torsion of processing without organic solvent.
Again, utilize above-mentioned carbon nano tube line to prepare at least one liner structure of carbon nano tube, and obtain a carbon nano tube structure.
The carbon nano tube line of above-mentioned torsion or the carbon nano tube line of non-torsion are a self supporting structure, can directly use as a carbon nano tube structure.In addition, a plurality of carbon nano tube lines can be arranged in parallel into a pencil liner structure of carbon nano tube, a plurality of carbon nano tube lines that perhaps this are arranged in parallel reverse step through one and obtain hank wire liner structure of carbon nano tube.Further, these a plurality of carbon nano tube lines or liner structure of carbon nano tube can be parallel to each other, intersect or weave, obtain a planar carbon nano tube structure.
Adopt one or more the preparation carbon nano tube structures in above-mentioned carbon nano-tube membrane, carbon nano-tube waddingization film, carbon nano-tube laminate and liner structure of carbon nano tube.
Step 2 provides the three dimensional support structure 102 of a hollow, this carbon nano tube structure is arranged at the surface of the three dimensional support structure 102 of this hollow.
The three dimensional support structure 102 of described hollow is used for supporting 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 three dimensional support structure 102 of the preferred hollow of the present embodiment is an earthenware.
The method that above-mentioned carbon nano tube structure is arranged at three dimensional support structure 102 surfaces of described hollow is: three dimensional support structure 102 outer surfaces that a carbon nano tube structure directly can be wound around or be wrapped in described hollow.Perhaps, also can one carbon nano tube structure be fixed in three dimensional support structure 102 inner surfaces or the outer surface of described hollow by binding agent or mechanical means.
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 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 the three dimensional support structure 102 of described hollow.
Step 3, the interval forms one first electrode 110 and one second electrode 112, and the first electrode 110 and one second electrode 112 are electrically connected to this carbon nano tube structure formation respectively.
The set-up mode of described two first electrodes 110 and the second electrode 112 is relevant with carbon nano tube structure, needs the direction of part carbon nano-tube along the first electrode 110 to the second electrode 112 in the assurance carbon nano tube structure to extend.
Described the first electrode 110 and the second electrode 112 can be arranged on the same surface of carbon nano tube structure or on different surfaces, and the first electrode 110 and the second electrode 112 are around the surface that is arranged at carbon nano tube structure.Wherein, the setting of being separated by between the first electrode 110 and the second electrode 112, the certain resistance of time access avoids short circuit phenomenon to produce so that carbon nano tube structure is applied to cubic heat source 100.Carbon nano tube structure itself has good adhesiveness and conductivity, thus the first electrode 110 and the second electrode 112 can and carbon nano tube structure between form and well electrically contact.
Described the first electrode 110 and the second electrode 112 are 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 the first electrode 110 and the second electrode 112, then these two palladium films are electrically connected to a conductive lead wire respectively.
Described the first electrode 110 and the second electrode 112 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 respectively two ends along three dimensional support structure 102 length directions of hollow as the first electrode 110 and the second electrode 112.
Be appreciated that in the present embodiment, can also first form two the first electrode 110 and the second electrodes 112 parallel and interval arranges on the surface of carbon nano tube structure, and this first electrode 110 and the second electrode 112 are electrically connected to carbon nano tube structure.Then, the carbon nano tube structure that this is formed with the first electrode 110 and the second electrode 112 is arranged at the surface of the three dimensional support structure 102 of above-mentioned hollow.After forming the first electrode 110 and the second electrode 112, can further form two conductive lead wires, lead to external circuit from the first electrode 110 and the second electrode 112 respectively.
Step 4 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 comprises macromolecular material or nonmetallic materials etc.Particularly, this macromolecular material can comprise one or more in thermoplastic polymer or thermosetting polymer, therefore this basis material precast body can be for generating the polymer monomer solution of this thermoplastic polymer or thermosetting polymer, or the mixed liquor that forms after dissolving in volatile organic solvent of this thermoplastic polymer or thermosetting polymer.These nonmetallic materials can comprise one or more in glass, pottery and semi-conducting material, therefore 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 the prefabricated body of this liquid matrix be infiltrated this carbon nano tube structure and solidifies this basis material precast body, thereby this basis material is infiltrated in the hole 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 carbon nano tube structure, thereby this basis material is full of in the hole 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.
The 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, and the method specifically comprises the following steps:
(1) provide a liquid thermosetting macromolecular material.
The viscosity of described liquid thermosetting macromolecular material is lower than 5 handkerchief seconds, and can at room temperature keep this viscosity more than 30 minutes.The embodiment of the present invention preferably prepares the liquid thermosetting macromolecular material with epoxy resin, and it specifically comprises the following steps:
At first, the mixture of glycidol ether type epoxy and glycidyl ester type epoxy is placed in a container, be heated to 30 ℃~60 ℃, and the mixture of the type epoxy of glycidol ether described in container and glycidyl ester type epoxy was stirred 10 minutes, until 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 the 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.
(2) adopt described liquid thermosetting macromolecular material to infiltrate described carbon nano tube structure.
The method that adopts described liquid thermosetting macromolecular material to infiltrate described carbon nano tube structure comprises the following steps:
At first, the three dimensional support structure 102 that is provided with the hollow of carbon nano tube structure is placed in a mould;
Secondly, described liquid thermosetting macromolecular material is injected in described mould, infiltrates described carbon nano tube structure.In order to allow the liquid thermosetting macromolecular material fully infiltrate described carbon nano tube structure, the time that infiltrates described carbon nano tube structure can not be less than 10 minutes.
In the present embodiment, 100 layers of carbon nano-tube membrane stacked surface that is wrapped in ceramic bar are placed in mould.Then the liquid thermosetting macromolecular material with epoxy resin is injected in described mould, infiltrates described carbon nano tube structure 20 minutes.
Be appreciated that, the method of the described carbon nano tube structure of described liquid thermosetting macromolecular material infiltration is not limit the method for injection, described liquid thermosetting macromolecular material can also be inhaled in described carbon nano tube structure by capillarity, infiltrate described carbon nano tube structure, perhaps described carbon nano tube structure is immersed in described liquid thermosetting macromolecular material.
(3) 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 comprises the following steps:
At first, with this mold heated to 50 ℃~70 ℃, contain the thermoset macromolecule material of epoxy resin for liquid by a heater at this temperature, kept this temperature 1 hour~3 hours, make this thermoset macromolecule material continue heat absorption to increase its curing degree.
Secondly, continue this mould to 80 of heating ℃~100 ℃, kept at this temperature 1 hour~3 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.
Again, continue this mould to 110 of heating ℃~150 ℃, kept at this temperature 2 hours~20 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.
At last, stopped heating, after this mould was cooled to room temperature, the demoulding can get a carbon nano-tube macromolecular material composite construction.
The application number that the concrete steps of above-mentioned preparation composite structure of carbon nano tube can be applied on December 14th, 2007 referring to people such as Fan Shoushan is 200710125109.8 China's Mainland patent application " preparation method of carbon nano tube compound material ".For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Be appreciated that the above-mentioned curing that contains the thermoset macromolecule material of epoxy resin also can adopt the method that once heats up, directly temperature risen to 150 ℃, the thermoset macromolecule material heat absorption is solidified.
Be appreciated that in above-mentioned steps three that the step that forms the first electrode 110 and the second electrode 112 can carry out after step 4 forms this composite structure of carbon nano tube.When this basis material only is filled in the hole of this carbon nano tube structure, thereby make carbon nano-tube partly be exposed to composite structure of carbon nano tube when surface, can adopt the method identical with step 3 that the first electrode 110 and the second electrode 112 directly are formed at this composite structure of carbon nano tube surface and be electrically connected to carbon nano tube structure formation.When this basis material all coats this carbon nano tube structure, can adopt the step of a 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 3 is electrically connected to this first electrode 110 and the second electrode 112 with the carbon nano tube structure that comes out.
Further, when cubic heat source 100 comprises that a heat-reflecting layer 108 is arranged at zone of heating 104 peripheral, after forming composite structure of carbon nano tube, can further include one and form a heat-reflecting layer 108 in the step of the outer surface of composite structure of carbon nano tube.Forming heat-reflecting layer 108 can realize by the method for coating or plated film.When the material of this heat-reflecting layer 108 is slaine or metal oxide, the particle of this slaine or metal oxide can be scattered in solvent, form a slurry, and this slurry coating or silk screen printing is surperficial in the three dimensional support structure of hollow, form this heat-reflecting layer.This solvent not should with slaine or metal oxide generation chemical reaction.In addition, this heat-reflecting layer 108 also can form by methods such as plating, chemical plating, sputter, vacuum evaporation, chemical vapour deposition (CVD) or physical vapour deposition (PVD)s.The embodiment of the present invention adopts physical vaporous deposition at ceramic base plate surface deposition one deck alundum (Al2O3) layer, as heat-reflecting layer.
The material of described heat-reflecting layer 108 is a white insulating material, as: metal oxide, slaine or pottery etc.In the present embodiment, heat-reflecting layer 210 materials are preferably alundum (Al2O3), and its thickness is 100 microns.The position that is appreciated that heat-reflecting layer 108 is not limit, and can decide according to the actual heating direction of cubic heat source.
Selectively, when the heating element 104 in first embodiment of the invention was a flexible carbon nano tube composite construction, this line heat source 100 can prepare by the following method, specifically comprises the following steps:
At first, provide a carbon nano tube structure.
Secondly, provide a prefabricated body of flexible substrate, and the prefabricated body of flexible substrate and carbon nano tube structure is compound, form a flexible carbon nano tube composite construction.
Again, provide the three dimensional support structure 102 of a hollow, and this flexible carbon nano tube composite construction is arranged at the surface of the three dimensional support structure 102 of hollow.
At last, the interval forms the first electrode 111 and the second electrode 112, and with this first electrode 111 and the second electrode 112 respectively with this flexible carbon nano tube composite construction in carbon nano tube structure form and be electrically connected to.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 by modes such as cuttings, thereby guarantee that the first electrode 111 and the second electrode 112 are electrically connected to carbon nano tube structure.
Be appreciated that also can be pre-formed the first electrode 111 and the second electrode 112 is electrically connected to carbon nano tube structure, then carbon nano tube structure and the prefabricated bluk recombination of flexible substrate are formed composite structure of carbon nano tube.
See also Figure 16,17 and 18, second embodiment of the invention provides a kind of cubic heat source 200.This cubic heat source 200 comprises a heating element 204, a heat-reflecting layer 208, the first electrode 210 and the second electrode 212.This heating element 204 consists of the three-dimensional structure of a hollow.This first electrode 210 and the second electrode 212 are electrically connected to heating element 204 respectively, thereby are used for making described heating element 204 current flowing that switches on power.Described heating element 204 is folded to form the hollow three-dimensional structure of a cubic shaped.Described the first electrode 210 and the second electrode 212 intervals arrange, and are arranged at respectively on the relative side of hollow three-dimensional structure of heating element 204 formed cubic shaped, and can play the effect of supporting heating element 204.Described the first electrode 210 and the second electrode 212 are wire, and roughly are parallel to each other.Described heat-reflecting layer 208 is arranged at the outer surface of heating element 204.This cubic heat source 200 can further comprise a plurality of electrodes, and these a plurality of electrode gap be arranged in parallel, and heating element 204 is arranged at the periphery of these a plurality of electrodes, take these a plurality of electrodes as supporter, forms the stereochemical structure of a hollow.Be appreciated that these a plurality of electrodes can regard the three dimensional support structure of a hollow as.Cubic heat source 200 and the first embodiment in the present embodiment are basic identical, and its difference is that the cubic heat source 200 of this enforcement in vertical adopts electrodes to be used for supporting heating element 204 as the three dimensional support structure of hollow.
See also Figure 19 and 20, third embodiment of the invention provides a kind of cubic heat source 300.This cubic heat source 300 comprises three dimensional support structure 302, one heating element 304, one first electrodes 310 and one second electrodes 312 of a hollow.This heating element 304 is arranged at the outer surface of the three dimensional support structure 302 of this hollow.This first electrode 310 and the second electrode 312 also are electrically connected to heating element 104 respectively, establish on the outer surface that the interval is placed in heating element 204, thereby for making described heating element 104 current flowing that switches on power.This three dimensional support structure 302 is a hemispherical hollow three-dimensional structure, and heating element 304 is coated on the outer surface of this three dimensional support structure 302, and formation one is hemispherical, or semielliptical shape structure.The first electrode 310 is point-like, is positioned at the bottom of heating element 302, and the second electrode 312 is ring-type, is surrounded on the top of the heating element 302 of hemispherical structure.This cubic heat source 300 further comprises a heat-reflecting layer 308, and this heat-reflecting layer is arranged at the periphery of heating element 304.In the present embodiment, these heat-reflecting layer 308 covering first electrodes 310 and the second electrode 312 are arranged at the outer surface of heating element 304.Cubic heat source 300 and the first embodiment in the present embodiment are basic identical, and its difference is that the cubic heat source 300 of this enforcement in vertical is the hollow three-dimensional structure of a hemispherical or semielliptical shape.Certainly cubic heat source 300 is also can be the shape of other similar nearly end openings.
described cubic heat source 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, carbon nano tube structure and matrix direct combination with this self-supporting, carbon nano-tube is still mutually combined keep the form of a carbon nano tube structure, thereby make in heating element the carbon nano-tube formation conductive network that can evenly distribute, be not subjected to again carbon nano-tube to disperse the restriction of concentration in solution, make the quality percentage composition of carbon nano-tube in heating element can reach 99%, make this cubic heat source have higher electric conversion efficiency.The second, because carbon nano-tube has intensity and toughness preferably, the intensity of carbon nano tube structure is larger, and is better flexible, is difficult for breaking, and makes cubic heat source have long useful life.The 3rd, the kind of this basis material is not limited to polymer, and temperature range is wide, makes the range of application of this thermal source more extensive.The 4th, the unit are thermal capacitance of this carbon nano tube structure is less, less than 2 * 10 -4Every square centimeter of Kelvin of joule, carbon nano tube structure can heat up faster and heat be passed, and therefore, this cubic heat source has the characteristics rapid, that thermo-lag is little, rate of heat exchange is fast, radiation efficiency is high that heat up.
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 is within all should being included in the present invention's scope required for protection.

Claims (14)

1. the preparation method of a cubic heat source, it comprises the following steps:
The carbon nano tube structure of one self-supporting is provided, and it comprises a plurality of carbon nano-tube, and these a plurality of carbon nano-tube attract each other by Van der Waals force, so that carbon nano tube structure has specific shape, still can keep specific shape not by support body supports the time;
The three dimensional support structure of one hollow is provided, this carbon nano tube structure is arranged at the surface of the three dimensional support structure of this hollow;
Form one first electrode and one second electrode in the two ends of this carbon nano tube structure, this first electrode and the second electrode form with this carbon nano tube structure and are electrically connected to;
One basis material precast body is provided, this basis material precast body and carbon nano tube structure is compound, form a composite structure of carbon nano tube, carbon nano tube structure described in this composite structure of carbon nano tube keeps compound shape before substantially.
2. the preparation method of cubic heat source as claimed in claim 1, it is characterized in that, described carbon nano tube structure comprises at least one carbon nano-tube film, or described carbon nano tube structure comprises that at least one liner structure of carbon nano tube or described carbon nano tube structure comprise the combination of carbon nano-tube film and liner structure of carbon nano tube.
3. the preparation method of cubic heat source as claimed in claim 1, is characterized in that, described carbon nano tube structure is arranged at the surface of the three dimensional support structure of this hollow by self viscosity, binding agent or mechanical means.
4. the preparation method of cubic heat source as claimed in claim 1, it is characterized in that, described the first electrode and one second electrode are conductive film, and this conductive film is formed at the carbon nano tube structure surface by plating, chemical plating, sputter, vacuum evaporation, physical vaporous deposition, chemical vapour deposition technique or painting method.
5. the preparation method of cubic heat source as claimed in claim 1, is characterized in that, described the first electrode and one second electrode are sheet metal or metal lead wire, and this sheet metal or metal lead wire are fixed in the carbon nano tube structure surface by conductive adhesive.
6. the preparation method of cubic heat source as claimed in claim 1, is characterized in that, this basis material precast body is compound by one or more methods and carbon nano tube structure in coating, deposition, dipping, printing and spraying.
7. the preparation method of cubic heat source as claimed in claim 1, is characterized in that, described basis material precast body and the compound method of carbon nano tube structure comprised the following steps: a liquid thermosetting macromolecular material is provided; Adopt this liquid thermosetting macromolecular material to infiltrate described carbon nano tube structure; And solidify liquid thermoset macromolecule material.
8. the preparation method of cubic heat source as claimed in claim 7, is characterized in that, the method that this liquid thermosetting macromolecular material of described employing infiltrates described carbon nano tube structure comprises the following steps:
One mould is provided, the three dimensional support structure that is provided with the hollow of carbon nano tube structure is placed in this mould; And
Described liquid thermosetting macromolecular material is injected in described mould, infiltrates described carbon nano tube structure.
9. the preparation method of cubic heat source as claimed in claim 8, is characterized in that, the method for the liquid thermoset macromolecule material of described curing comprises the following steps:
, kept at this temperature 1 hour~3 hours this mold heated to 50 ℃~70 ℃ by a heater;
Heat this mould to 80 ℃~100 ℃, kept at this temperature 1 hour~3 hours;
Heat this mould to 110 ℃~150 ℃, kept at this temperature 2 hours~20 hours; And
Stopped heating, after this mould is cooled to room temperature, the demoulding.
10. the preparation method of a cubic heat source comprises the following steps:
The carbon nano tube structure of one self-supporting and the three dimensional support structure of a hollow are provided, this carbon nano tube structure comprises a plurality of carbon nano-tube, these a plurality of carbon nano-tube attract each other by Van der Waals force, so that carbon nano tube structure has specific shape, still can keep specific shape not by support body supports the time;
This carbon nano tube structure is arranged at the surface of the three dimensional support structure of this hollow;
One basis material precast body is provided, and basis material precast body and carbon nano tube structure is compound, forming a composite structure of carbon nano tube, carbon nano tube structure described in this composite structure of carbon nano tube keeps compound shape before substantially; And,
The space forms two electrodes, avoiding producing short circuit phenomenon between two electrodes, and with these two electrodes respectively with this composite structure of carbon nano tube in carbon nano tube structure form and be electrically connected to.
11. the preparation method of cubic heat source as claimed in claim 10, it is characterized in that, before described interval forms two electrodes, further comprise the step of this composite structure of carbon nano tube of cutting, make this carbon nano tube structure partly be exposed to this composite structure of carbon nano tube surperficial.
12. the preparation method of a cubic heat source comprises the following steps:
The carbon nano tube structure of one self-supporting is provided, and it comprises a plurality of carbon nano-tube, and these a plurality of carbon nano-tube attract each other by Van der Waals force, so that carbon nano tube structure has specific shape, still can keep specific shape not by support body supports the time;
The one prefabricated body of flexible substrate is provided, and the prefabricated body of this flexible substrate and carbon nano tube structure is compound, forming a flexible carbon nano tube composite construction, carbon nano tube structure described in this flexible carbon nano tube composite construction keeps compound shape before substantially;
The three dimensional support structure of one hollow is provided, and this flexible carbon nano tube composite construction is arranged at the surface of the three dimensional support structure of this hollow; And,
The interval forms two electrodes in the two ends of this flexible carbon nano tube composite construction, and with these two electrodes respectively with this flexible carbon nano tube composite construction in carbon nano tube structure form and be electrically connected to.
13. the preparation method of cubic heat source as claimed in claim 12 is characterized in that, this flexible composite structure of carbon nano tube is arranged at outer surface or the inner surface of the three dimensional support structure of this hollow.
14. the preparation method of cubic heat source as claimed in claim 13 is characterized in that, this flexible composite structure of carbon nano tube is arranged at three dimensional support structure outer surface or the inner surface of this hollow by binding agent or mechanical means.
CN 200910106809 2008-06-07 2009-04-20 Preparation method of three-dimensional heat source Active CN101868058B (en)

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CN 200910106809 CN101868058B (en) 2009-04-20 2009-04-20 Preparation method of three-dimensional heat source
US12/655,507 US20100122980A1 (en) 2008-06-13 2009-12-31 Carbon nanotube heater
US12/658,237 US20100154975A1 (en) 2008-06-13 2010-02-04 Carbon Nanotube heater
US12/658,184 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
US12/660,356 US20110024410A1 (en) 2008-06-13 2010-02-25 Carbon nanotube heater
US12/660,820 US20100163547A1 (en) 2008-06-13 2010-03-04 Carbon nanotube heater
US12/661,133 US20100200568A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,150 US20100170890A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,165 US20100170891A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,115 US20100200567A1 (en) 2008-06-13 2010-03-11 Carbon nanotube heater
US12/661,110 US20100218367A1 (en) 2008-06-13 2010-03-11 Method for making 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
JP2010097289A JP5457259B2 (en) 2009-04-20 2010-04-20 Manufacturing method of hollow heat source

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