CN101868061A - Three-dimensional heat source - Google Patents

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

Cubic heat source

Technical field

The present invention relates to a kind of cubic heat source, relate in particular to a kind of 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 that heating is wide, homogeneous heating and efficient is than advantages such as height.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 twine 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 oxidized easily, 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 bigger, weight is big, uses inconvenience.

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 asphalt base carbon fiber in this paper base material in a jumble.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, because the asphalt base carbon fiber in this carbon fiber paper distributes in a jumble, so the intensity of this carbon fiber paper is less, flexibility is relatively poor, breaks easily, has short shortcoming of life-span equally; 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 graphiticcarbon, Nature, Sumio Iijima with carbon nano-tube, vol 354, p56 (1991)) caused that with its particular structure and character people pay close attention to greatly for the nano material of representative.In recent years, along with deepening continuously of carbon nano-tube and nano materials research, its wide application prospect constantly displayed.People such as Fan Shoushan 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 the described flexible substrate.These a plurality of carbon nano-tube exist with powdered form, and adhesion is very weak to each other, can't form a self supporting structure with given shape.When the carbon nano-tube of this powdered form was mixed with polymer solution, the carbon nano-tube of this powdered form was very easily reunited, thereby it is inhomogeneous to cause carbon nano-tube to be disperseed in matrix.Agglomeration when in polymer solution, disperseing for fear of carbon nano-tube, on the one hand, the mixture that in the process of disperseing, needs to handle this carbon nano-tube and polymer solution by supersonic oscillations, on the other hand, the quality percentage composition of carbon nano-tube can not be too high in this thermo electric material, only is 0.1～4%.

And carbon nano-tube is through after the above-mentioned dispersion treatment, even carbon nano-tube can be in contact with one another to each other, its adhesion also a little less than, can't form the carbon nano tube structure of a self-supporting.Because content of carbon nanotubes is few, the thermal response speed of thermoelectric material is fast inadequately, and electric conversion efficiency is not high enough, so the heating temp of this thermo electric material is not high enough, has limited its range of application.In addition, for carbon nano-tube is disperseed in liquid phase, during the preparation thermo electric material, its flexible substrate can only the selective polymer material, the polymeric material heat resisting temperature is lower, and the method for this kind employing dispersing Nano carbon tubes formation thermo electric material in liquid phase has limited the selection of basis material.

Summary of the invention

In view of this, necessaryly provide a kind of electric conversion efficiency height, and the cubic heat source of heating temp wider range.

A kind of cubic heat source comprises a heating element and at least two electrodes.This heating element comprises that matrix and a plurality of carbon nano-tube are distributed in this matrix.This at least two electrode gap settings and being electrically connected with this heating element respectively.Described heating element constitutes the three-dimensional structure of a hollow, and a plurality of carbon nano-tube in this heating element are formed the carbon nano tube structure of at least one self-supporting.

A kind of cubic heat source comprises a heating element and at least two electrodes.This heating element comprises a composite structure of carbon nano tube.These at least two electrodes are electrically connected with this heating element.This heating element constitutes the three-dimensional structure of a hollow, and described composite structure of carbon nano tube comprises the carbon nano tube structure of at least one self-supporting and the matrix compound with the carbon nano tube structure of this at least one self-supporting.

A kind of cubic heat source comprises the three dimensional support structure of a hollow, a heating element and at least two electrodes.This heating element is arranged at the surface of the three dimensional support structure of this hollow.These at least two electrodes are electrically connected with this heating element.Described heating element comprises at least one carbon nano tube structure and and the compound matrix of this at least one carbon nano tube structure.

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 are directly compound, carbon nano-tube is still mutually combined keep the form of a carbon nano tube structure, thereby make in the heating element carbon nano-tube formation conductive network that can evenly distribute, be not subjected to the restriction of carbon nano-tube dispersion concentration of employed solution in the course of processing again, 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

Fig. 1 is the structural representation of the cubic heat source that first embodiment of the invention provided.

Fig. 2 is the generalized section of Fig. 1 along the II-II line.

Fig. 3 comprises that for the cubic heat source of first embodiment of the invention 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 comprises that for the cubic heat source of first embodiment of the invention 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 the basis material.

Fig. 5 comprises that for the cubic heat source of first embodiment of the invention 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 comprises that for the cubic heat source of first embodiment of the invention a plurality of wire composite structure of carbon nano tube are arranged at the schematic diagram on wire supporting construction surface.

Fig. 7 is the stereoscan photograph of the employed a kind of carbon nano-tube membrane of the cubic heat source of first embodiment of the invention.

Fig. 8 is the structural representation of the employed carbon nano-tube membrane of the cubic heat source of first embodiment of the invention.

Fig. 9 is the stereoscan photograph of the employed a kind of carbon nano-tube waddingization film of the cubic heat source of first embodiment of the invention.

Figure 10 comprises the stereoscan photograph of the carbon nano-tube laminate of the carbon nano-tube that is arranged of preferred orient along same direction for the another kind that cubic heat source adopted of first embodiment of the invention.

Figure 11 is the employed 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 of the cubic heat source of first embodiment of the invention.

Figure 12 is the stereoscan photograph of the employed a kind of non-carbon nano tube line that reverses of cubic heat source of first embodiment of the invention.

Figure 13 is the stereoscan photograph of the employed a kind of carbon nano tube line that reverses of cubic heat source of first embodiment of the invention.

Figure 14 is the employed a kind of carbon nano-tube membrane of cubic heat source of first embodiment of the invention and the cross section stereoscan photograph of the heating element that epoxy resin is compounded to form.

Figure 15 is the preparation method's of the cubic heat source among Fig. 1 a 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 among Figure 16.

Figure 18 is the cutaway view along XVIII-XVIII line among 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 among 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 elements, 104, one first electrodes 110 and one second electrode 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 second electrode 112 are electrically connected with heating element 104 respectively, thereby are used to make described heating element 104 energized to flow through electric current.

The three dimensional support structure 102 of described hollow is used to support 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 a plurality of 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 materials, it can be in pottery, glass, resin, quartz, the plastics etc. one or more.When the three dimensional support structure 102 of hollow was selected flexible materials, it can be in resin, rubber, plastics or the flexible fiber etc. one or more.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 the 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 the outer surface of the three dimensional support structure 102 of hollow by binding agent (figure does not show).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 but this three dimensional support structure is a choice structure,, can need not three dimensional support structure 102 when heating element 104 can self-supporting surrounds when forming a stereochemical structure.

Described composite structure of carbon nano tube comprises a carbon nano tube structure and basis material.This carbon nano tube structure is a self supporting structure.So-called " self supporting structure " i.e. this carbon nano tube structure need not by a support body supports, also can keep self specific shape.The carbon nano tube structure of this self supporting structure comprises a plurality of carbon nano-tube, and these a plurality of carbon nano-tube attract each other by Van der Waals force, thereby makes carbon nano tube structure have specific shape.Carbon nano-tube in the described carbon nano tube structure comprises one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube and the multi-walled carbon nano-tubes.The diameter of described Single Walled Carbon Nanotube is 0.5 nanometer～50 nanometers, and the diameter of described double-walled carbon nano-tube is 1.0 nanometers～50 nanometers, and the diameter of described multi-walled carbon nano-tubes is 1.5 nanometers～50 nanometers.Among the present invention, this carbon nano tube structure is stratiform or linear structure.Because this carbon nano tube structure has self-supporting, still can keep stratiform or linear structure not by support body supports the time.Have a large amount of gaps in this carbon nano tube structure between the carbon nano-tube, thereby make this carbon nano tube structure have a large amount of 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 smaller 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 a 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 the inner surface of the three dimensional support structure 102 of hollow by binding agent or mechanical system.Different according to the complex method of carbon nano tube structure and basis material, the concrete structure of this layered carbon nano pipe composite construction comprises following two kinds of situations:

First kind of situation 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 be provided with.When the carbon nano tube structure 2044 of this stratiform comprised single liner structure of carbon nano tube, this single liner structure of carbon nano tube folded or is coiled into a stratiform self supporting structure.When the carbon nano tube structure 2044 of this stratiform comprised a plurality of liner structure of carbon nano tube, these a plurality of liner structure of carbon nano tube can parallel tight setting, arranged in a crossed manner or be woven into a stratiform self supporting structure.When the carbon nano tube structure 2044 of this stratiform comprised carbon nano-tube film and liner structure of carbon nano tube simultaneously, described liner structure of carbon nano tube was arranged at least one surface of at least one carbon nano-tube film.

Second kind of situation sees also Fig. 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 a 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 is a plurality of parallel and liner structure of carbon nano tube that be provided with at interval, this liner structure of carbon nano tube extends to second electrode 112 by 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 the 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, first electrode 110 and second electrode 112 can be electrically connected with the two ends of this single wire composite structure of carbon nano tube respectively.First electrode 110 and second electrode 112 are ring-type, also can be the structure of similar ring-types such as C shape.In the present embodiment, first electrode 110 and 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, twine or be wrapped in three dimensional support structure 102 surfaces of described hollow then.

Described carbon nano-tube film can comprise carbon nano-tube membrane, carbon nano-tube waddingization film or carbon nano-tube laminate.Described liner structure of carbon nano tube can comprise the twisted wire structure that is arranged in parallel at least one carbon nano tube line, a plurality of carbon nano tube line the fascicular texture formed or a plurality of carbon nano tube line reverse composition mutually.

Described carbon nano-tube film comprises equally distributed carbon nano-tube, combines closely by Van der Waals force between the carbon nano-tube.Carbon nano-tube in this carbon nano-tube film is unordered or orderly arrangement.The 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 twined mutually or isotropism is arranged; When carbon nano tube structure comprised orderly carbon nanotubes arranged, carbon nano-tube was arranged of preferred orient along a direction or a plurality of direction.In the present embodiment, preferably, described carbon nano tube structure comprises the carbon nano-tube film of a plurality of stacked settings, and the thickness of this carbon nano tube structure is preferably 0.5 nanometer～1 millimeter.The thermal response speed that is appreciated that carbon nano tube structure is relevant with its thickness.Under situation of the same area, the thickness of carbon nano tube structure is big more, and thermal response speed is slow more; Otherwise the thickness of carbon nano tube structure is more little, and thermal response speed is fast more.

Described carbon nano-tube membrane is for to pull the carbon nano-tube film that is obtained 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 along same direction preferred orientation and be parallel to carbon nano-tube membrane surface carbon nanotubes arranged.Join end to end by Van der Waals force between the 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.This a plurality of carbon nano-tube fragment 143 joins end to end by Van der Waals force.Each carbon nano-tube fragment 143 comprises a plurality of carbon nano-tube that are parallel to each other 145, and this a plurality of carbon nano-tube that is parallel to each other 145 closely connects 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 people such as Fan Shoushan in application on February 9th, 2007, in disclosed CN101239712A number Chinese publication application on August 13 " carbon nano-tube membrane structure and preparation method thereof " in 2008, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.Be understandable that when this carbon nano tube structure is made up of the carbon nano-tube membrane, and the thickness of carbon nano tube structure is when smaller, for example less than 10 microns, this carbon nano tube structure has good transparency, and its light transmittance can reach 90%, can be used to make a transparent thermal source.

When described carbon nano tube structure comprises carbon nano-tube membrane more than two-layer, this multilayer carbon nanotube membrane mutual superposition setting or be set up in parallel.Form an intersecting angle α between the carbon nano-tube that is arranged of preferred orient in the adjacent two layers carbon nano-tube membrane, α is more than or equal to 0 degree and smaller 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 in carbon nano tube structure, form a plurality of holes, 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, twine by Van der Waals force between the described carbon nano-tube, form network-like structure.Described carbon nano-tube waddingization film isotropism.Carbon nano-tube in the described carbon nano-tube waddingization film is evenly to distribute, and random arrangement forms a large amount of pore structures, and pore-size is approximately less than 10 microns.The length and the width of described carbon nano-tube waddingization film are not limit.See also Fig. 9, because in carbon nano-tube waddingization film, carbon nano-tube is twined mutually, so this carbon nano-tube waddingization film has good flexible, and is a self supporting structure, can bending fold becomes arbitrary shape and does not break.The area and the thickness of described carbon nano-tube waddingization film are not all limit, and thickness is 1 micron～1 millimeter, are preferably 100 microns.Described carbon nano-tube waddingization film and preparation method thereof sees also people such as Fan Shoushan in application on April 13rd, 2007, in disclosed CN101284662A number Chinese publication application on October 15 " preparation method of carbon nano-tube film " in 2008, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.

Described carbon nano-tube laminate is by rolling the carbon nano-tube film that a carbon nano pipe array forms.This carbon nano-tube laminate comprises equally distributed carbon nano-tube, and carbon nano-tube is arranged of preferred orient along same direction or different directions.Carbon nano-tube also can be isotropic.Carbon nano-tube in the described carbon nano-tube laminate mutually part overlaps, and attracts each other by Van der Waals force, combines closely, and makes this carbon nano tube structure have good flexible, can bending fold becomes arbitrary shape and does not break.And owing to attract each other by Van der Waals force between the carbon nano-tube in the carbon nano-tube laminate, combine closely, making the carbon nano-tube laminate is the structure of a self-supporting.Described carbon nano-tube laminate can obtain by rolling a carbon nano pipe array.Carbon nano-tube in the described carbon nano-tube laminate forms an angle β with the surface of the growth substrate that forms carbon nano pipe array, wherein, β is more than or equal to 0 degree and smaller or equal to 15 degree (0≤β≤15 °), this angle β is with to be applied to the pressure that carbon nano-pipe array lists relevant, pressure is big more, this angle is more little, and preferably, the carbon nano-tube in this carbon nano-tube laminate is parallel to this growth substrate and arranges.According to the mode difference that rolls, the carbon nano-tube in this carbon nano-tube laminate has different spread patterns.See also Figure 10, when when same direction rolls, carbon nano-tube is arranged of preferred orient along a fixed-direction.See also Figure 11, when when different directions rolls, carbon nano-tube is arranged of preferred orient along different directions.When carbon nano pipe array is vertically rolled in the top of carbon nano pipe array, the carbon nano-tube laminate is isotropic.The length of carbon nano-tube is greater than 50 microns in this carbon nano-tube laminate.

The area and the thickness of this carbon nano-tube laminate are not limit, and can select the time that will heat as heating object according to actual needs.The area of this carbon nano-tube laminate and the size of carbon nano pipe array are basic identical.The height of this carbon nano-tube laminate thickness and carbon nano pipe array and the pressure that rolls are relevant, can be 1 micron～1 millimeter.The height that is appreciated that carbon nano pipe array is big more and applied pressure is more little, and then the thickness of Zhi Bei carbon nano-tube laminate is big more, otherwise the height of carbon nano pipe array is more little and applied pressure is big more, and then the thickness of Zhi Bei carbon nano-tube laminate is more little.Have certain interval between the adjacent carbon nano-tube among the described carbon nano-tube laminate, thereby form a plurality of holes in the carbon nano-tube laminate, the size of hole is approximately less than 10 microns.Described carbon nano-tube laminate and preparation method thereof sees also people such as Fan Shoushan in application on June 1st, 2007, in disclosed CN101314464A number Chinese publication application on December 3 " preparation method of carbon nano-tube film " in 2008, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd..For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.

Select liner structure of carbon nano tube for use 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 spiral winding mutually.

Described carbon nano tube line can be non-carbon nano tube line that reverses or the carbon nano tube line that reverses.This non-carbon nano tube line that reverses obtains for the carbon nano-tube membrane is handled by organic solvent.See also Figure 12, this non-carbon nano tube line that reverses comprises a plurality of along arrangement of carbon nano tube line length direction and end to end carbon nano-tube.Preferably, this non-carbon nano tube line that reverses 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.This non-carbon nano-tube line length of reversing is not limit, and diameter is 0.5 nanometer～100 micron.

The described carbon nano tube line that reverses reverses acquisition for adopting a mechanical force in opposite direction with described carbon nano-tube membrane two ends.See also Figure 13, this carbon nano tube line that reverses comprises a plurality of around carbon nano tube line axial screw carbon nanotubes arranged.Preferably, this carbon nano tube line that reverses 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 that this reverses is not limit, and diameter is 0.5 nanometer～100 micron.Described carbon nano tube line and preparation method thereof sees also people such as Fan Shoushan in application on September 16th, 2002, CN100411979C number China's bulletin patent " a kind of carbon nano-tube rope and manufacture method thereof " in bulletin on August 20th, 2008, applicant: Tsing-Hua University, Hongfujin Precise Industry (Shenzhen) Co., Ltd., and in disclosed CN1982209A number Chinese publication application " carbon nano-tube filament and preparation method thereof " on June 20 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 handle the carbon nano tube line that this reverses.Under the capillary effect that when volatile organic solvent volatilizees, produces, adjacent carbon nano-tube is combined closely by Van der Waals force in the carbon nano tube line that reverses after the processing, the diameter and the specific area of the carbon nano tube line that reverses are 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 handle above-mentioned carbon nano-tube membrane, this carbon nano-tube membrane is a self supporting structure, so this carbon nano tube line also is a self supporting structure.In addition, owing to have the gap between the adjacent carbons nanotube in this carbon nano tube line, so this carbon nano tube line has a large amount of holes, the size of hole is approximately less than 10 microns.

The carbon nano tube structure of the embodiment of the invention comprises a plurality of carbon nano-tube membranes along the stacked setting of equidirectional, and carbon nano-tube all is arranged of preferred orient along same direction in the carbon nano tube structure 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 in cellulose, polyethylene terephthalate, acryl resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, phenolic resins, epoxy resin, silica gel and the polyester etc. one or more.These nonmetallic materials can comprise one or more in glass, pottery and the semi-conducting material.

Owing to have the gap between the carbon nano-tube in the carbon nano tube structure, thereby in carbon nano tube structure, form a plurality of holes, 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 carbon nano tube structure and the compound cross-sectional view of the composite structure of carbon nano tube of formation afterwards of epoxy resin in the present embodiment.This carbon nano tube structure is a carbon nano-tube membrane.Can find, with epoxy resin compound after, carbon nano tube structure still can keep the form before compound substantially, carbon nano-tube is arranged along same direction in epoxy resin-base substantially.

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 the 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 the matrix, can save the consumption of the required carbon nano tube structure of this heating element of preparation 104.In addition, visual actual needs is arranged on the ad-hoc location of matrix with carbon nano tube structure, 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 the 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, guaranteed this heating element 104 and exterior insulation simultaneously.In addition, this matrix can further play heat conduction and make the purpose of uniform heat distribution.Further, when this carbon nano tube structure sharply heated up, 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 the flexibility and the toughness of composite structure of carbon nano tube.

Directly be compounded to form heating element 104 by carbon nano tube structure, carbon nano-tube is evenly distributed in heating element 104, and the content of carbon nano-tube reaches 99%, improved the heating temp of cubic heat source 100 matrix and self-supporting.Because this carbon nano tube structure is a self supporting structure, and carbon nano-tube evenly distributes in carbon nano tube structure, the carbon nano tube structure and the matrix of this self-supporting is directly compound, carbon nano-tube is still mutually combined keep the form of a carbon nano tube structure, thereby make in the heating element 104 the carbon nano-tube formation conductive network that can evenly distribute, be not subjected to carbon nano-tube in solution, to disperse the restriction of concentration again, make the quality percentage composition of carbon nano-tube in composite structure of carbon nano tube can reach 99%.

Described first electrode 110 and second electrode 112 are made by electric conducting material, and the shape of this first electrode 110 and second electrode 112 is not limit, and can be conducting film, sheet metal or metal lead wire.Preferably, first electrode 110 and 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 first electrode 110 and second electrode 112 is the Metal Palladium film, and thickness is 5 nanometers.Described Metal Palladium and carbon nano-tube have wetting effect preferably, help forming good electrical contact between described first electrode 110 and second electrode 112 and the described heating element 104, reduce ohmic contact resistance.

Described first electrode 110 and second electrode 112 are electrically connected with carbon nano tube structure in the heating element 104.Wherein, first electrode 110 and second electrode 112 are provided with at interval, avoid short circuit phenomenon to produce so that heating element 104 inserts certain resistance when being applied to cubic heat source 100.

When matrix only is filled in the hole of this carbon nano tube structure, because the part carbon nano-tube partly is exposed to heating element 104 surfaces in this carbon nano tube structure, this first electrode 110 and second electrode 112 can be arranged on the surface of heating element 104, thereby this first electrode 110 and second electrode 112 are electrically connected with carbon nano tube structure.This first electrode 110 and 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 coats whole carbon nano tube structure in this heating element 104, for this first electrode 110 and second electrode 112 are electrically connected with this carbon nano tube structure, this first electrode 110 and 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 second electrode 112 and external power source conducting, this first electrode 110 and second electrode 112 can partly be exposed to outside the heating element 104; Perhaps, this cubic heat source 100 can further comprise two lead-in wires, is electrically connected with this first electrode 110 and second electrode 112 respectively, and draws from this matrix inside.

When carbon nano-tube was arranged in order in this carbon nano tube structure, the orientation of this carbon nano-tube can be along extending from first electrode, 110 to second electrodes, 112 directions.Described first electrode 110 and second electrode 112 can be arranged at this heating element 104 or carbon nano tube structure surface by a conductive adhesive (figure does not show), conductive adhesive can also be fixed in described first electrode 110 and second electrode 112 on the surface of carbon nano tube structure when realizing that first electrode 110 and 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 first electrode 110 and second electrode 112 is not all limit, and it is provided with purpose is that carbon nano tube structure flows through electric current in the described heating element 104 in order to make.Therefore, 112 needs of described first electrode 110 and second electrode conduction, and and described heating element 104 in form between the carbon nano tube structure and electrically contact all in protection scope of the present invention.The particular location of described first electrode 110 and second electrode 112 is not limit, and only need guarantee that first electrode 110 is electrically connected with heating element 104 respectively with 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, first electrode 110 and second electrode 112 should be electrically connected with carbon nano tube structure.Described cubic heat source 100 can comprise that also a plurality of electrodes are electrically connected with described heating element 104, and its quantity is not limit, and realizes selectively each zone of heating of heating element 104 by controlling different electrodes.Any two electrodes can be electrically connected with external circuit respectively in these a plurality of electrodes, 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 with external power source respectively by external wire (figure does not show), 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 to reflect the heat that heating element 104 is sent, and it is heated three dimensional support structure 102 inner spaces of hollow effectively.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 the 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 promptly heating element 104 is arranged between the three dimensional support structure 102 and heat-reflecting layer 108 of hollow.In the present embodiment, because heating element 104 is arranged at the outer surface of the three dimensional support structure 102 of hollow, 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 (Al, and its thickness is 100 microns～0.5 millimeter.Be appreciated that but this heat-reflecting layer 108 is a choice structure, when cubic heat source 100 did not comprise heat-reflecting layer, this cubic heat source 100 also can be used for external heating.

Described cubic heat source 100 further comprises an insulating protective layer (figure does not show).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 the 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 but described insulating protective layer 106 is a choice 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 the surface of heating element 104 by the method for coating or sputter.In the present embodiment, because heating element 104 is arranged between the three dimensional support structure 102 and heat-reflecting layer 108 of hollow, so need not insulating protective layer.

Present embodiment provides a kind of method of using above-mentioned cubic heat source 100 heating objects, and it may further comprise the 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 that lead inserts 1 volt～20 volts by first electrode 110 with second electrode 112, 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, heats is can be because of the distance of various piece in the heated material and cubic heat source 100 not different and produce bigger differently, can realize the even heating to heated material.For object with black matrix structure, when being 200 ℃～450 ℃, its pairing temperature just can send thermal radiation invisible to the human eye (infrared ray), and the thermal radiation of this moment is the most stable, most effective, the thermal radiation heat maximum that is produced.

This cubic heat source 100 can directly contact it or itself and heated object are provided with at interval with body surface to be heated 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 invention further provides a kind of preparation method of above-mentioned cubic heat source 100, and it may further comprise the 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 the liner structure of carbon nano tube, so the corresponding respectively above-mentioned four kinds of structures of the preparation method of carbon nano tube structure are divided into four kinds of methods.

(1) preparation method of carbon nano-tube membrane may further comprise the steps:

At first, provide a carbon nano pipe array to be formed at a growth substrate, this array is the carbon nano pipe array of super in-line arrangement.

The preparation method of this carbon nano pipe array adopts chemical vapour deposition technique, its concrete steps comprise: a smooth growth substrate (a) is provided, this growth substrate can be selected P type or the substrate of N type silicon growth for use, or select for use the silicon growth substrate that is formed with oxide layer, the embodiment of the invention to be preferably and adopt 4 inches silicon growth substrate; (b) evenly form a catalyst layer on the growth substrate surface, this catalyst layer material can be selected one of alloy of iron (Fe), cobalt (Co), nickel (Ni) or its combination in any for use; (c) the above-mentioned growth substrate that is formed with catalyst layer was annealed in 700 ℃～900 ℃ air about 30 minutes～90 minutes; (d) growth substrate that will handle places reacting furnace, is heated to 500 ℃～740 ℃ under the protective gas environment, feeds carbon-source gas then and reacts about 5 minutes～30 minutes, and growth obtains carbon nano pipe array.This carbon nano-pipe array is classified a plurality of pure nano-carbon tube arrays parallel to each other and that form perpendicular to the growth substrate carbon nanotubes grown as.By above-mentioned control growing condition, do not contain impurity in this carbon nano pipe array that aligns substantially, as agraphitic carbon or residual catalyst metal particles etc.

The carbon nano-pipe array that the embodiment of the invention provides is classified a kind of in single-wall carbon nanotube array, double-walled carbon nano-tube array and the array of multi-walled carbon nanotubes as.The diameter of described carbon nano-tube is 1～50 nanometer, and length is 50 nanometers～5 millimeter.In the present embodiment, the length of carbon nano-tube is preferably 100～900 microns.

Carbon source gas can be selected the more active hydrocarbons of chemical property such as acetylene, ethene, methane for use in the embodiment of the invention, and the preferred carbon source gas of the embodiment of the invention is acetylene; Protective gas is nitrogen or inert gas, and the preferred protective gas of the embodiment of the invention is an argon gas.

Be appreciated that the carbon nano pipe array that the embodiment of the invention provides is not limited to above-mentioned preparation method, also can be graphite electrode Constant Electric Current arc discharge sedimentation, laser evaporation sedimentation etc.

Secondly, adopt a stretching tool from carbon nano pipe array, to pull carbon nano-tube and obtain at least one carbon nano-tube membrane, it specifically may further comprise the steps: (a) from described super in-line arrangement carbon nano pipe array selected one or have a plurality of carbon nano-tube of certain width, present embodiment is preferably and adopts adhesive tape, tweezers or clip contact carbon nano pipe array with certain width with selected one or have a plurality of carbon nano-tube of certain width; (b) with certain speed this selected carbon nano-tube that stretches, thereby form end to end a plurality of carbon nano-tube fragment, and then form a continuous carbon nano-tube membrane.This pulls direction along the direction of growth that is basically perpendicular to carbon nano pipe array.

In above-mentioned drawing process, these a plurality of carbon nano-tube fragments are when tension lower edge draw direction breaks away from growth substrate gradually, because Van der Waals force effect, should selected a plurality of carbon nano-tube fragments be drawn out continuously end to end with other carbon nano-tube fragment respectively, thereby form one continuously, evenly and have a carbon nano-tube 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 may further comprise the steps:

At first, provide a carbon nanometer tube material.

Described carbon nanometer tube material can be the carbon nano-tube by prepared in various methods such as chemical vapour deposition technique, graphite electrode Constant Electric Current arc discharge sedimentation or laser evaporation sedimentations.

In the present embodiment, adopt blade or other instruments that the above-mentioned carbon nano pipe array that aligns is scraped from substrate, obtain a carbon nanometer tube material.Preferably, in the described carbon nanometer tube material, the length of carbon nano-tube is greater than 100 microns.

Secondly, add to above-mentioned carbon nanometer tube material in one solvent and wadding a quilt with cotton processing obtains a carbon nanotube flocculent structure, above-mentioned carbon nanotube flocculent structure is separated from solvent, and this carbon nanotube flocculent structure typing is handled to obtain a carbon nano-tube waddingization film.

In the embodiment of the invention, the optional water of solvent, volatile organic solvent etc.The waddingization processing can be by adopting methods such as ultrasonic wave dispersion treatment or high strength stirring.Preferably, the embodiment of the invention adopts ultrasonic wave to disperse 10 minutes～30 minutes.Because carbon nano-tube has great specific area, has bigger Van der Waals force between the carbon nano-tube of twining mutually.Above-mentioned wadding processing can't be dispersed in the carbon nano-tube in this carbon nanometer tube material in the solvent fully, attracts each other, twines by Van der Waals force between the carbon nano-tube, forms network-like structure.

In the embodiment of the invention, the method for described separating carbon nano-tube flocculent structure specifically may further comprise the steps: pour the above-mentioned solvent that contains carbon nanotube flocculent structure into one and be placed with in the funnel of filter paper; Thereby standing and drying a period of time obtains a carbon nanotube flocculent structure of separating.

In the embodiment of the invention, the typing processing procedure of described carbon nanotube flocculent structure specifically may further comprise the steps: above-mentioned carbon nanotube flocculent structure is placed a container; This carbon nanotube flocculent structure is spread out according to reservation shape; Apply certain pressure in the carbon nanotube flocculent structure of spreading out; And, with the oven dry of solvent residual in this carbon nanotube flocculent structure or the equal solvent acquisition one carbon nano-tube waddingization film afterwards that volatilize naturally.

Be appreciated that the embodiment of the invention can control the thickness and the surface density of this carbon nano-tube waddingization film by controlling area that this carbon nanotube flocculent structure spreads out.The area that carbon nanotube flocculent structure is spread out is big more, and then the thickness of this carbon nano-tube waddingization film and surface density are just more little.

In addition, the step that carbon nanotube flocculent structure is handled in above-mentioned separation and typing also can be directly mode by suction filtration realize, specifically may further comprise the steps: a 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 dry back obtain a carbon nano-tube waddingization film.This hole filter membrane is a smooth surface, be of a size of 0.22 micron filter membrane.Because suction filtration mode itself will provide a bigger gas pressure in this carbon nanotube flocculent structure, this carbon nanotube flocculent structure can directly form a uniform carbon nano-tube waddingization film through suction filtration.And because hole filter membrane smooth surface, this carbon nano-tube waddingization film is peeled off easily, obtains the carbon nano-tube waddingization film of a self-supporting.

Be appreciated that this carbon nano-tube waddingization film has certain thickness, and by controlling the thickness that area that this carbon nanotube flocculent structure spreads out and pressure size can controlling carbon nanotube waddingization films.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 may further comprise the steps:

At first, provide a carbon nano pipe array to be formed at a growth substrate, this array is the carbon nano pipe array that aligns.

Described carbon nano pipe array is preferably the carbon nano pipe array that surpasses in-line arrangement.Described carbon nano pipe array is identical with the preparation method of above-mentioned carbon nano pipe array.

Secondly, adopt a device for exerting, push above-mentioned carbon nano pipe array and obtain a carbon nano-tube laminate, its detailed process is:

This device for exerting applies certain pressure and lists in above-mentioned carbon nano-pipe array.In the process of exerting pressure, the effect that carbon nano-pipe array is listed in pressure can separate with growth substrate down, thereby form the carbon nano-tube laminate of forming by a plurality of carbon nano-tube, and described a plurality of carbon nano-tube goes up surperficial parallel with the carbon nano-tube laminate substantially with self supporting structure.

In the embodiment of the invention, device for exerting is a pressure head, pressure head smooth surface, the arrangement mode of carbon nano-tube in the carbon nano-tube laminate of the shape of pressure head and direction of extrusion decision preparation.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 isotropism carbon nanotubes arranged laminate; When adopting roller bearing shape pressure head when a certain fixed-direction rolls, can obtain the carbon nano-tube laminate of carbon nano-tube along this fixed-direction orientations; When adopting roller bearing shape pressure head when different directions rolls, can obtain the carbon nano-tube laminate of carbon nano-tube along the different directions orientations.

Be appreciated that, when adopting above-mentioned different modes to push above-mentioned carbon nano pipe array, carbon nano-tube can be toppled under the effect of pressure, and attracts each other, is connected to form the carbon nano-tube laminate of being made up of a plurality of carbon nano-tube with self supporting structure with adjacent carbon nano-tube by Van der Waals force.

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 extruding back carbon nano pipe array carbon nano pipe array when not being extruded) relevant with the size of pressure, pressure is big more, and the inclination angle is big more.The thickness of the carbon nano-tube laminate of preparation depends on the height and the pressure size of carbon nano pipe array.The height of carbon nano pipe array is big more and applied pressure is more little, and then the thickness of Zhi Bei carbon nano-tube laminate is big more; Otherwise the height of carbon nano pipe array is more little and applied pressure is big more, and then the thickness of Zhi Bei carbon nano-tube laminate is more little.The width of this carbon nano-tube laminate is relevant with the size of the substrate that carbon nano pipe array is grown, and the length of this carbon nano-tube laminate is not limit, and can make according to the actual requirements.

Be appreciated that this carbon nano-tube laminate has certain thickness, and can control its thickness by the height and the pressure size of carbon nano pipe array.So this carbon nano-tube laminate can directly be used as a carbon nano tube structure.In addition, can or be arranged side by side formation one carbon nano tube structure with the stacked setting of two-layer at least carbon nano-tube laminate.

(4) preparation method of liner structure of carbon nano tube may further comprise the steps:

At first, provide at least one carbon nano-tube membrane.

The formation method of this carbon nano-tube membrane is identical with the formation method of carbon nano-tube membrane in ().

Secondly, handle this carbon nano-tube membrane, form at least one carbon nano tube line.

The step of this processing carbon nano-tube membrane can be handled this carbon nano-tube membrane for adopting organic solvent, thereby obtains a non-carbon nano tube line that reverses, or for the employing mechanical external force reverses this carbon nano-tube membrane, thereby obtain a carbon nano tube line that reverses.

It is similar that this employing organic solvent is handled the method for the viscosity that adopts organic solvent reduction carbon nano-tube membrane among method that carbon nano-tube membrane forms the non-carbon nano tube line that reverses and (one), its difference is, when needs form the non-carbon nano tube line that reverses, the two ends of carbon nano-tube membrane are unfixing, promptly the carbon nano-tube membrane are not arranged on substrate surface or the frame structure.

The step that adopts mechanical external force to reverse this carbon nano-tube membrane forms the carbon nano tube line that reverses for adopting a mechanical force that described carbon nano-tube film two ends are reversed in opposite direction.Further, can adopt a volatile organic solvent to handle the carbon nano tube line that this reverses.Under the capillary effect that when volatile organic solvent volatilizees, produces, adjacent carbon nano-tube is combined closely by Van der Waals force in the carbon nano tube line that reverses after the processing, the specific area of the carbon nano tube line that reverses is reduced, viscosity reduces, and specific density and intensity all increase mutually with the carbon nano tube line of handling without organic solvent that reverses.

Once more, utilize above-mentioned carbon nano tube line to prepare at least one liner structure of carbon nano tube, and obtain a carbon nano tube structure.

Above-mentioned carbon nano tube line that reverses or the non-carbon nano tube line that reverses are a self supporting structure, can directly use as a carbon nano tube structure.In addition, a plurality of carbon nano tube lines can be arranged in parallel into a pencil liner structure of carbon nano tube, perhaps a plurality of carbon nano tube lines that this is 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 preparation carbon nano tube structures in above-mentioned carbon nano-tube membrane, carbon nano-tube waddingization film, carbon nano-tube laminate and the 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 to support carbon nano tube structure, and its material can be hard material, as: pottery, glass, resin, quartz etc., can also select flexible material, as: plastics or flexible fiber etc.The three dimensional support structure 102 of the preferred hollow of 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: a carbon nano tube structure directly can be twined or is wrapped in three dimensional support structure 102 outer surfaces of 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 the adjacent two layers carbon nano-tube membrane is 90 degree.The thickness of these 100 layers of carbon nano-tube membranes is 300 microns.Utilize the viscosity of carbon nano tube structure itself, this carbon nano tube structure is wrapped in the surface of the three dimensional support structure 102 of described hollow.

Step 3 forms one first electrode 110 and one second electrode 112 at interval, and first electrode 110 and one second electrode 112 are electrically connected with this carbon nano tube structure formation respectively.

The set-up mode of described two first electrodes 110 and second electrode 112 is relevant with carbon nano tube structure, needs the part carbon nano-tube in the assurance carbon nano tube structure to extend to the direction of second electrode 112 along first electrode 110.

Described first electrode 110 and second electrode 112 can be arranged on the same surface of carbon nano tube structure or on the different surfaces, and first electrode 110 and second electrode 112 are around the surface that is arranged at carbon nano tube structure.Wherein, the setting of being separated by between first electrode 110 and second electrode 112 avoids short circuit phenomenon to produce so that carbon nano tube structure inserts certain resistance when being applied to cubic heat source 100.Carbon nano tube structure itself has good adhesiveness and conductivity, thus first electrode 110 and second electrode 112 can and carbon nano tube structure between form and well electrically contact.

Described first electrode 110 and 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 first electrode 110 and second electrode 112, then these two palladium films are electrically connected with a conductive lead wire respectively.

Described first electrode 110 and 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 two ends along three dimensional support structure 102 length directions of hollow respectively as first electrode 110 and second electrode 112.

Be appreciated that in the present embodiment, can also form earlier two parallel and first electrode 110 and second electrodes 112 that be provided with at interval, and this first electrode 110 and second electrode 112 are electrically connected with carbon nano tube structure on the surface of carbon nano tube structure.Then, the carbon nano tube structure that this is formed with first electrode 110 and second electrode 112 is arranged at the surface of the three dimensional support structure 102 of above-mentioned hollow.After forming first electrode 110 and second electrode 112, can further form two conductive lead wires, lead to external circuit from first electrode 110 and 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 the thermosetting polymer, so this basis material precast body can be for generating the polymer monomer solution of this thermoplastic polymer or thermosetting polymer, or this thermoplastic polymer or thermosetting polymer dissolves the mixed liquor of back formation in volatile organic solvent.These nonmetallic materials can comprise one or more in glass, pottery and the semi-conducting material, so the slurry that this basis material precast body can be made for the nonmetallic materials particle, prepare the reacting gas of these nonmetallic materials or be these nonmetallic materials of gaseous state.Particularly, can adopt the method for vacuum evaporation, sputter, chemical vapor deposition (CVD) and physical vapor deposition (PVD) to form the basis material precast body of gaseous state, and make this basis material precast body be deposited on the carbon nano tube surface of carbon nano tube structure.In addition, a large amount of nonmetallic materials particles can be disperseed in solvent, form a slurry as this basis material precast body.

When this basis material precast body is liquid state, can be by soaking into this carbon nano tube structure and solidify this basis material precast body by liquid state basis material precast body, thereby this basis material is infiltrated in the 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 the 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.

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 this method specifically may further comprise the steps:

(1) provides a liquid thermosetting macromolecular material.

The viscosity of described liquid thermosetting macromolecular material was lower than for 5 handkerchief seconds, and can at room temperature keep this viscosity more than 30 minutes.The embodiment of the invention preferably prepares the liquid thermosetting macromolecular material with epoxy resin, and it specifically may further comprise the steps:

At first, the mixture of glycidol ether type epoxy and glycidyl ester type epoxy is placed a container, be heated to 30 ℃～60 ℃, and the mixture of type epoxy of glycidol ether described in the container and glycidyl ester type epoxy stirred 10 minutes, till the mixture of described glycidol ether type epoxy and glycidyl ester type epoxy mixes.

Secondly, fatty amine and diglycidyl ether are joined in the mixture of described glycidol ether type epoxy that stirs and glycidyl ester type epoxy and carry out chemical reaction.

At last, the mixture of described glycidol ether type epoxy and glycidyl ester type epoxy is heated to 30 ℃～60 ℃, thereby obtains a liquid thermosetting macromolecular material that contains epoxy resin.

(2) adopt described liquid thermosetting macromolecular material to soak into described carbon nano tube structure.

Adopt the method that described liquid thermosetting macromolecular material soaks into described carbon nano tube structure may further comprise the steps:

At first, the three dimensional support structure 102 that is provided with the hollow of carbon nano tube structure is placed a mould;

Secondly, described liquid thermosetting macromolecular material is injected in the described mould, soaks into described carbon nano tube structure.In order to allow the liquid thermosetting macromolecular material fully soak into described carbon nano tube structure, the time of soaking into described carbon nano tube structure can not be less than 10 minutes.

In the present embodiment 100 layers of stacked surface that is wrapped in ceramic bar of carbon nano-tube membrane are placed in the mould.Liquid thermosetting macromolecular material with epoxy resin is injected in the described mould then, soaks into described carbon nano tube structure 20 minutes.

Be appreciated that, the method that described liquid thermosetting macromolecular material is soaked into described carbon nano tube structure is not limit the method for injection, described liquid thermosetting macromolecular material can also be inhaled in the described carbon nano tube structure by capillarity, soak into described carbon nano tube structure, perhaps described carbon nano tube structure is immersed in the described liquid thermosetting macromolecular material.

(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 may further comprise the steps:

At first, with this mold heated to 50 ℃～70 ℃, the thermoset macromolecule material that contains epoxy resin under this temperature was kept this temperature 1 hour～3 hours for liquid, made this thermoset macromolecule material continue heat absorption to increase its curing degree by a heater.

Secondly, continue this mould to 80 of heating ℃～100 ℃, under this temperature, kept 1 hour～3 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.

Once more, continue this mould to 110 of heating ℃～150 ℃, under this temperature, kept 2 hours～20 hours, make described thermoset macromolecule material continue heat absorption to increase its curing degree.

At last, stop the heating, treat that this mould is cooled to room temperature after, the demoulding can get a carbon nano-tube macromolecular material composite construction.

The application number that the concrete steps of above-mentioned preparation composite structure of carbon nano tube can be applied on December 14th, 2007 referring to people such as Fan Shoushan is 200710125109.8 China's Mainland patent application " preparation method of carbon nano tube compound material ".For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.

Be appreciated that the above-mentioned curing that contains the thermoset macromolecule material of epoxy resin also can adopt the method that once heats up, directly temperature risen to 150 ℃, the thermoset macromolecule material heat absorption is solidified.

Be appreciated that in the above-mentioned steps three that the step that forms first electrode 110 and 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 that first electrode 110 and second electrode 112 directly are formed at this composite structure of carbon nano tube surface and be electrically connected with carbon nano tube structure formation with step 3.When this basis material all coats this carbon nano tube structure, can adopt a step of cutting to cut this composite structure of carbon nano tube, thereby make this carbon nano tube structure be exposed to the composite structure of carbon nano tube surface, and then the employing method identical with step 3 is electrically connected this first electrode 110 and 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, can be in solvent with the Dispersion of Particles of this slaine or metal oxide, form a slurry, and with this slurry coating or silk screen printing in the three dimensional support structure surface 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 invention adopts physical vaporous deposition at ceramic base plate surface deposition one deck alundum (Al 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 (Al, 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 in the first embodiment of the invention 104 was a flexible carbon nano tube composite construction, this line heat source 100 can prepare by the following method, specifically may further comprise the steps:

At first, provide a carbon nano tube structure.

Secondly, provide a flexible substrate prefabricated body, and prefabricated body of flexible substrate and carbon nano tube structure is compound, form a flexible carbon nano tube composite construction.

Once more, 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, form at interval first electrode 111 and second electrode 112, and with this first electrode 111 and second electrode 112 respectively with this flexible carbon nano tube composite construction in carbon nano tube structure form and be electrically connected.When carbon nano tube structure is coated by basis material fully, can further make this carbon nano tube structure partly be exposed to the flexible carbon nano tube composite structure surface, thereby guarantee that first electrode 111 and second electrode 112 are electrically connected with carbon nano tube structure by modes such as cuttings.

Be appreciated that also can be pre-formed first electrode 111 and second electrode 112 is electrically connected with carbon nano tube structure, again carbon nano tube structure and the prefabricated bluk recombination of flexible substrate formed composite structure of carbon nano tube.

See also Figure 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, first electrode 210 and second electrode 212.This heating element 204 constitutes the three-dimensional structure of a hollow.This first electrode 210 and second electrode 212 are electrically connected with heating element 204 respectively, thereby are used to make described heating element 204 energized to flow through electric current.Described heating element 204 is folded to form the hollow three-dimensional structure of a cube shaped.Described first electrode 210 and second electrode 212 are provided with at interval, are arranged at respectively on the opposed side edges of hollow three-dimensional structure of heating element 204 formed cube shaped, and can play the effect of supporting heating element 204.Described first electrode 210 and 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, is supporter with these a plurality of electrodes, 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.The cubic heat source 200 and first embodiment in the present embodiment are basic identical, and its difference is that the cubic heat source 200 of this enforcement in upright adopts electrodes to be used to support 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 elements, 304, one first electrodes 310 and one second electrode 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 second electrode 312 also are electrically connected with heating element 104 respectively, establish at interval to place on the outer surface of heating element 204, thereby are used to make described heating element 104 energized to flow through electric current.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, form one hemispherical, or semielliptical shape structure.First electrode 310 is a point-like, is positioned at the bottom of heating element 302, and second electrode 312 is a 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 second electrode 312 are arranged at the outer surface of heating element 304.The cubic heat source 300 and first embodiment in the present embodiment are basic identical, and its difference is that the cubic heat source 300 of this enforcement in upright 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 CNT evenly distributes in carbon nano tube structure, carbon nano tube structure and matrix direct combination with this self-supporting, CNT is still mutually combined keep the form of a carbon nano tube structure, thereby make in the heating element heater CNT formation conductive network that can evenly distribute, be not subjected to again CNT in solution, to disperse the restriction of concentration, make the quality percentage composition of CNT in heating element heater can reach 99%, make this cubic heat source have higher electric conversion efficiency. The second, because CNT has preferably intensity and toughness, the intensity of carbon nano tube structure is bigger, and is better flexible, is difficult for breaking, and makes cubic heat source have long service life. The 3rd, the kind of this matrix material is not limited to polymer, and temperature range is wide, makes the range of application of this thermal source more extensive. The 4th, the unit are thermal capacitance of this carbon nano tube structure is littler, less than 2 * 10^-4Every square centimeter of Kelvin of joule, carbon nano tube structure can heat up and heat be passed faster, 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 all should be included in the present invention's range required for protection.

Claims (14)

1. cubic heat source, it comprises:

A heating element, this heating element are a composite structure of carbon nano tube, and it comprises a matrix and a plurality of carbon nano-tube that is distributed in this matrix; And

At least two electrode gap settings also are electrically connected with described heating element,

It is characterized in that described heating element constitutes the three-dimensional structure of a hollow, a plurality of carbon nano-tube in the described heating element are twined the carbon nano tube structure of forming at least one self-supporting mutually.

2. cubic heat source as claimed in claim 1 is characterized in that described carbon nano tube structure comprises at least one carbon nano-tube film.

3. cubic heat source as claimed in claim 2 is characterized in that, described carbon nano-tube film comprises a plurality of equally distributed carbon nano-tube, attracts each other, twines by Van der Waals force between the carbon nano-tube, forms network configuration.

4. cubic heat source as claimed in claim 2 is characterized in that, the random arrangement of the carbon nano-tube in the described carbon nano-tube film forms a plurality of holes, and the diameter of hole is less than 10 microns.

5. cubic heat source as claimed in claim 2 is characterized in that, the thickness of described carbon nano-tube film is 1 micron～1 millimeter.

6. cubic heat source as claimed in claim 1 is characterized in that described composite structure of carbon nano tube comprises the carbon nano tube structure of a plurality of self-supportings, this carbon nano tube structure space or being arranged in the described matrix of being in contact with one another.

7. cubic heat source as claimed in claim 1 is characterized in that, the material of described matrix is macromolecular material or Inorganic Non-metallic Materials.

8. cubic heat source as claimed in claim 1 is characterized in that described cubic heat source further comprises a heat-reflecting layer, and described heat-reflecting layer is arranged at the periphery of heating element.

9. cubic heat source, it comprises:

A heating element; And

At least two electrode gap settings also are electrically connected with described heating element,

It is characterized in that, described heating element constitutes the three-dimensional structure of a hollow, described heating element comprises the carbon nano tube structure of at least one self-supporting, and the basis material compound with this at least one carbon nano tube structure, and this carbon nano tube structure comprises the carbon nano-tube of a plurality of mutual windings.

10. cubic heat source as claimed in claim 9 is characterized in that described carbon nano tube structure has a plurality of holes, and described basis material evenly is compound in the hole of described carbon nano tube structure.

11. cubic heat source as claimed in claim 10 is characterized in that, the diameter of described hole is less than 10 microns.

12. a cubic heat source, it comprises:

The three dimensional support structure of a hollow;

One heating element, this heating element is arranged at the surface of this three dimensional support structure; And

At least two electrodes, and described electrode is electrically connected with described heating element;

It is characterized in that described heating element comprises a composite structure of carbon nano tube, this composite structure of carbon nano tube is composited by the carbon nano tube structure of a matrix and at least one self-supporting, and this carbon nano tube structure comprises the carbon nano-tube of a plurality of mutual windings.

13. cubic heat source as claimed in claim 12 is characterized in that, described heating element is arranged at the inner surface or the outer surface of this three dimensional support structure.

14. cubic heat source as claimed in claim 12 is characterized in that, described heating element is arranged at the inner surface or the outer surface of this three dimensional support structure by binding agent or mechanical means.

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