CN102110501A - Preparation method of wire cable and cable core thereof - Google Patents
Preparation method of wire cable and cable core thereof Download PDFInfo
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- CN102110501A CN102110501A CN2010105874403A CN201010587440A CN102110501A CN 102110501 A CN102110501 A CN 102110501A CN 2010105874403 A CN2010105874403 A CN 2010105874403A CN 201010587440 A CN201010587440 A CN 201010587440A CN 102110501 A CN102110501 A CN 102110501A
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Abstract
The invention relates to a preparation method of a cable core, which comprises the following steps: providing a carbon nanotube array; drawing a carbon nanotube from the carbon nanotube array to obtain an orderly pure carbon nanotube structure; performing mechanical treatment of the orderly pure carbon nanotube structure to obtain a pure carbon nanotube linear structure; and forming at least one conducting material layer on the surface of the pure carbon nanotube linear structure to obtain the cable core. The invention further provides a preparation method of a wire cable using the cable core.
Description
Technical field
The present invention relates to the preparation method of a kind of cable and cable core thereof, relate in particular to a kind of preparation method of cable and the cable core thereof based on carbon nano-tube.
Background technology
Cable is a signal transmssion line material comparatively commonly used in the electronic industry, and the cable broader applications of micron order size are in IT product, medical instrument, Space Facilities, and large diameter cable is applied in the transmission of electric energy.Traditional cable inside is provided with two conductors, inner wire is in order to transmission of electric signals, outer conductor is enclosed in inside in order to the signal of telecommunication of shielding transmission and with it, thereby make that cable has that high-frequency loss is low, shielding and characteristic such as antijamming capability is strong, service band is wide, see also document " Electromagnetic Shielding of High-Voltage Cables " (M.De Wulf, P.Wouters et.al., Joumal of Magnetism and Magnetic Materials, 316, e908-e901 (2007)).
Generally speaking, cable structure from the inside to the outside is followed successively by cable core, the insulating medium layer that is coated on the cable core outer surface that forms inner wire, screen and the oversheath that forms outer conductor.Wherein, cable core is used for transmission of electric signals, and material is based on copper, aluminium or ormolu.Screen is woven by the multiply metal wire usually or overlays on insulating medium layer with the metallic film volume and forms outward, disturbs in order to shield electromagnetic interference or useless external signal.For the cable core that forms with metal material, when greatest problem was that alternating current transmits in metallic conductor, the current density of each several part was inhomogeneous, and conductor internal current density is little, the conductive surface current density is big, and this phenomenon is called skin effect (Skin Effect).Net sectional area when skin effect makes in the metallic conductor by electric current reduces, thereby makes the effective resistance of conductor become big, causes the efficiency of transmission of cable to reduce or transmission signals is lost.In addition, with the cable of metal material as cable core and screen, its intensity is less, and quality and diameter are bigger, can't satisfy some specified conditions, as the application of space industry, Space Facilities and superfine cable.
Carbon nano-tube is a kind of new one-dimensional nano material, and it has excellent electric conductivity, higher tensile strength and higher thermal stability, has shown wide application prospect at interdisciplinary fields such as material science, chemistry, physics.At present, have carbon nano-tube and metal mixed are formed composite material, thereby be used for making the cable core of cable.
In the prior art, the manufacture method of the cable of carbon nanotubes generally comprises following steps: a motlten metal matrix material is provided; Carbon nanotube powder is immersed in this motlten metal matrix material, forms the mixture of carbon nano-tube and metallic matrix; Under the condition that can make described motlten metal matrix material cured, from this motlten metal matrix material, pull out many fibers that permeate motlten metal matrix material, form the compound cable core of metallic matrix; Coated polymer forms insulating medium layer in the outer surface of described cable core; With the multiply metal wire directly or be coated on insulating medium layer by braiding and form screen outward or overlay on insulating medium layer and form screen outward with the metallic film volume; And coat the outer surface of an oversheath in described screen.
The cable that this method obtains is compared with the cable that adopts the simple metal cable core, has stronger mechanical performance, and lighter quality, and the conductivity of this cable also increases.Yet carbon nano-tube is unordered in the cable of this employing metallic matrix composite carbon nanometer tube cable core is dispersed in the metal, and the carbon nano-tube in this cable can't be brought into play the advantage of its axial conduction, still can't solve the skin effect problem in the above-mentioned metal cable core.And adopt to mix carbon nano-tube in motlten metal after again the method for wire drawing prepare cable, this method is comparatively complicated, and cost is higher.
In sum, necessaryly provide a kind of cable, this cable has excellent conducting performance.
Summary of the invention
In view of this, the necessary preparation method that a kind of cable and cable core thereof are provided, this cable has excellent conducting performance, and this method is comparatively simple, and cost is lower.
A kind of preparation method of cable cable core may further comprise the steps: a carbon nano pipe array is provided; From described carbon nano pipe array, pull carbon nano-tube and obtain an orderly pure nano-carbon tube structure; Above-mentioned orderly pure nano-carbon tube structure is carried out mechanical treatment, obtain a pure nano-carbon tube linear structure; And form at least one conductive material layer in above-mentioned pure nano-carbon tube linear structure surface, obtain a cable core.
A kind of preparation method of cable may further comprise the steps: a carbon nano pipe array is provided; From described carbon nano pipe array, pull carbon nano-tube and obtain an orderly pure nano-carbon tube structure; Above-mentioned orderly pure nano-carbon tube structure is carried out mechanical treatment, obtain a pure nano-carbon tube linear structure; Form at least one conductive material layer in above-mentioned pure nano-carbon tube linear structure surface, obtain a cable core; Form the outer surface of at least one insulating medium layer in described cable core; And form the outer surface of at least one screen in described insulating medium layer.
Compared with the prior art, the preparation method of cable of the present invention and cable core thereof has the following advantages: the present invention adopts the core support structure of pure nano-carbon tube linear structure preparation as cable core, has good conductivity, the advantage of light weight.In addition, owing to directly metal level is formed at the surface of pure nano-carbon tube linear structure, this method is simple, and cost is low.
Description of drawings
Fig. 1 is the cross section structure schematic diagram of the cable of the technical program first embodiment.
Fig. 2 is the structural representation of single cable core in the cable of the technical program first embodiment.
Fig. 3 is the carbon nanotube long line structural section structural representation of the technical program first embodiment.
Fig. 4 is the stereoscan photograph of the pencil carbon nanotube long line of the technical program first embodiment.
Fig. 5 is the stereoscan photograph of the twisted wire shape carbon nanotube long line of the technical program first embodiment.
Fig. 6 is the flow chart of the manufacture method of the technical program first embodiment cable.
Fig. 7 is the structural representation of the manufacturing installation of the technical program first embodiment cable.
Fig. 8 is the stereoscan photograph of the technical program first embodiment carbon nano-tube film.
Fig. 9 is the cross section structure schematic diagram of the technical program second embodiment cable.
Figure 10 is the cross section structure schematic diagram of the technical program the 3rd embodiment cable.
Embodiment
Describe structure of the technical program embodiment cable 10 and preparation method thereof in detail below with reference to accompanying drawing.
The technical program embodiment provides a kind of cable, and this cable comprises at least one cable core, is coated on the outer at least one insulating medium layer of cable core, is coated on the outer at least one electro-magnetic screen layer of insulating medium layer and is coated on the outer at least one oversheath of electro-magnetic screen layer.
See also Fig. 1, the cable 10 of the technical program first embodiment is a coaxial cable, and this coaxial cable comprises a cable core 120, be coated on the outer insulating medium layer 130 of cable core 120, be coated on the outer screen 140 of insulating medium layer 130 and be coated on the outer oversheath 150 of screen 140.Wherein, above-mentioned cable core 120, insulating medium layer 130, screen 140 and oversheath 150 are coaxial setting.
See also Fig. 2, described cable core 120 comprises a conductive material layer 110 and a carbon nanotube long line structure 100, and this conductive material layer 110 is coated on this carbon nanotube long line structure 100 outer surfaces.Particularly, this conductive material layer 110 comprises the wetting layers 112 that directly combine with carbon nanotube long line structure 100 surface, the transition zone 113 that is arranged on wetting layer 112 outer surfaces, the anti oxidation layer 115 that is arranged on the conductive layer 114 of transition zone 113 outer surfaces and is arranged on conductive layer 114 outer surfaces.This conductive material layer 110 comprises this conductive layer 114 at least, and above-mentioned wetting layer 112, transition zone 113, anti oxidation layer 115 are optional structure.The diameter of this cable core 120 is greater than 1 micron, and preferably, the diameter of this cable core 120 is 10～30 microns or 1 centimetre.
Described carbon nanotube long line structure 100 comprises at least one carbon nanotube long line 102.The diameter of this carbon nanotube long line 102 is 4.5 nanometers～100 micron.See also Fig. 3, this carbon nanotube long line structure 100 can also be the pencil or the twisted wire shape structure of a plurality of carbon nanotube long line 102 compositions.When the diameter of this carbon nanotube long line structure 100 during less than 100 microns, the cable 10 that this carbon nanotube long line structure 100 constitutes can be applicable to field of signal transmissions.When the diameter of this carbon nanotube long line structure 100 during greater than 100 microns, the cable 10 that this carbon nanotube long line structure 100 constitutes can be applicable to the electric power transfer field.
Described carbon nanotube long line 102 comprises pencil or the twisted wire shape structure of being made up of a plurality of carbon nano-tube.See also Fig. 4, the carbon nanotube long line 102 of this fascicular texture comprises a plurality of along cable core axial preferred orientation carbon nanotubes arranged bundle fragment, length and each carbon nano-tube bundle fragment that each carbon nano-tube bundle fragment has about equally are made of a plurality of carbon nano-tube bundles that are parallel to each other, carbon nano-tube bundle fragment two ends interconnect by Van der Waals force, this carbon nano-tube is intrafascicular to comprise a plurality of carbon nano-tube, and these a plurality of carbon nano-tube have common being arranged of preferred orient.In the carbon nanotube long line 102 of this fascicular texture, described carbon nano-tube is arranged along carbon nanotube long line 102 axial preferred orientations, and these a plurality of carbon nano-tube join end to end by Van der Waals force.The diameter of the carbon nanotube long line 102 of this fascicular texture is 10 microns～30 microns.
See also Fig. 5, the carbon nanotube long line 102 of described twisted wire shape structure comprises a plurality of carbon nano-tube along the arrangement of carbon nanotube long line 102 axial screw shapes, and these a plurality of carbon nano-tube join end to end by Van der Waals force.The diameter of this twisted wire shape carbon nanotube long line 102 is 10 microns～30 microns.
Carbon nano-tube in the carbon nanotube long line structure 100 comprises Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes, the diameter of described Single Walled Carbon Nanotube is 0.5 nanometer～50 nanometers, the diameter of double-walled carbon nano-tube is 1 nanometer～50 nanometers, and the diameter of multi-walled carbon nano-tubes is 1.5 nanometers～50 nanometers.
Acting as of above-mentioned wetting layer 112 makes conductive layer 114 better combine with carbon nanotube long line structure 100 surfaces.The material that forms this wetting layer 112 can be metal or its alloys good with the carbon nano-tube wetability such as nickel, palladium or titanium, and the thickness of this wetting layer 112 is 1～10 nanometer.In the present embodiment, the material of this wetting layer 112 is a nickel, and thickness is about 2 nanometers.Be appreciated that but this wetting layer 112 is choice structure.
Acting as of above-mentioned transition zone 113 makes wetting layer 112 better combine with conductive layer 114.The material that forms this transition zone 113 can be gold, silver or copper etc. and wetting layer 112 materials and equal metal or its alloy that can better combine of conductive layer 114 materials, and the thickness of this transition zone 113 is 1～10 nanometer.In the present embodiment, the material of this transition zone 113 is a copper, and thickness is 2 nanometers.Be appreciated that but this transition zone 113 is choice structure.
Acting as of above-mentioned conductive layer 114 makes cable core 110 have electric conductivity preferably.The material that forms this conductive layer 114 can be metal or its alloy of good conductivity such as copper, silver or gold, and the thickness of this conductive layer 114 is 1～20 nanometer.In the present embodiment, the material of this conductive layer 114 is a silver, and thickness is about 5 nanometers.
Acting as of above-mentioned anti oxidation layer 115 prevents that conductive layer 114 is oxidized in air in the manufacture process of cable 10, thereby the electric conductivity of cable core 120 is descended.The material that forms this anti oxidation layer 115 can be difficult for stable metal or its alloy of oxidation for gold or platinum etc. in air, the thickness of this anti oxidation layer 115 is 1～10 nanometer.In the present embodiment, the material of this anti oxidation layer 115 is a platinum, and thickness is 2 nanometers.Be appreciated that but this anti oxidation layer 115 is choice structure.
Further, for improving the intensity of cable 10, a strengthening layer 116 can be set further outside this conductive material layer 110.The material that forms this strengthening layer 116 can be polyvinyl alcohol (PVA), polyhenylene benzene and two oxazoles (PBO), polyethylene (PE) or the higher polymer of polyvinyl chloride (PVC) equal strength, and the thickness of this strengthening layer 116 is 0.1～1 micron.In the present embodiment, the material of this strengthening layer 116 is polyvinyl alcohol (PVA), and thickness is 0.5 micron.Be appreciated that but this strengthening layer 116 is choice structure.
Above-mentioned insulating medium layer 130 is used for electric insulation, can select polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, foamed polyethylene composition or nanoclay-polymer composite for use.Nanoclay is the silicate mineral of nanoscale stratiform structure in nanoclay-polymer composite, form by multiple hydrosilicate and a certain amount of aluminium oxide, alkali metal oxide and alkaline earth oxide, good characteristics such as tool fire resistant flame retardant are as nano kaoline or nano imvite.Macromolecular material can be selected silicones, polyamide, polyolefin such as polyethylene or polypropylene etc. for use, but not as limit.Present embodiment insulating medium layer 130 preferred foams polyethylene compositions.
Above-mentioned screen 140 is formed by an electric conducting material, disturbs in order to shield electromagnetic interference or useless external signal.Particularly, screen 140 can overlay on insulating medium layer 130 outer formation by the braiding of multiply metal wire or with the metallic film volume, also can overlay on insulating medium layer 130 outer formation, or can directly be coated on insulating medium layer 130 surfaces by the composite material that contains carbon nano-tube by carbon nano tube structure winding or volume.
Wherein, the material of described metallic film or metal wire can be chosen as metal or its alloy of good conductivity such as copper, gold or silver.Described carbon nano tube structure comprises continuous carbon nano-tube film or carbon nanotube long line.The described composite material that contains carbon nano-tube can be the composite material of metal and carbon nano-tube or the composite material of polymer and carbon nano-tube.This polymeric material can be chosen as PETG (Polyethylene Terephthalate, PET), Merlon (Polycarbonate, PC), acrylonitrile-butadiene propylene-styrene copolymer (Acrylonitrile-Butadiene Styrene Terpolymer, ABS), polycarbonate/acrylonitrile-butadiene-phenylethene copolymer macromolecular materials such as (PC/ABS).When this composite material is the composite material of polymer and carbon nano-tube, even carbon nanotube can be scattered in the solution of above-mentioned polymeric material, and the solution of the polymeric material of this carbon nanotubes evenly is coated on insulating medium layer 130 surfaces, form a screen 140 that comprises polymer and carbon nano-tube after cooling.Further, this screen 140 also can be constituted outside insulating medium layer 130 by above-mentioned multiple material.The technical program embodiment adopts carbon nano tube structure to form screen 140, thereby makes this screen 140 have stronger shield effectiveness because of carbon nano-tube has excellent conducting performance.
Above-mentioned oversheath 150 is made by insulating material, can select the composite material of nanoclay-macromolecular material for use, wherein nanoclay can be nano kaoline or nano imvite, macromolecular material can be silicones, polyamide, polyolefin such as polyethylene or polypropylene etc., but not as limit.Present embodiment oversheath 150 preferred nano imvite-composite polyethylene materials; it has favorable mechanical performance, fire resistant flame retardant performance, low smoke and zero halogen performance; not only can provide protection for cable 10; effectively resist external damages such as machinery, physics or chemistry, can also satisfy requirement on environmental protection simultaneously.
Described cable 10 is owing to adopt carbon nanotube long line structure 100 and conductive material layer 110 as cable core 120, it has the following advantages: one, carbon nanotube long line structure 100 in this cable core 10 comprises a plurality of orderly carbon nanotubes arranged, it has lighter quality, and higher mechanical strength, therefore, this cable 10 that contains carbon nanotube long line structure 100 has higher mechanical strength and lighter quality than the cable that adopts metallic matrix composite carbon nanometer tube cable core, be fit to special dimension, as the application of space industry and Space Facilities.Its two, therefore in carbon nanotube long line structure 100, carbon nano-tube is arranged in order, has better conductivity than the cable core that adopts the formation of metallic matrix composite carbon nanometer tube.They are three years old, this carbon nanotube long line structure 100 comprises a plurality of carbon nano-tube that joined end to end and be arranged of preferred orient by Van der Waals force, because carbon nano-tube is a tubular structure, in this carbon nanotube long line structure 100, electric current is propagated along the tube wall of a plurality of end to end carbon nano-tube, the current spread net sectional area is constant, and electric current can not produce skin effect substantially by conductive material layer the time, thereby has reduced signal decay in the transmission course in cable.
See also Fig. 6 and Fig. 7, the preparation method of the technical program first embodiment cable 10 mainly may further comprise the steps:
Step 1: a carbon nano pipe array 216 is provided, and preferably, this carbon nano pipe array 216 is super in-line arrangement carbon nano pipe array.
This carbon nano pipe array 216 is a single-wall carbon nanotube array, the double-walled carbon nano-tube array, and array of multi-walled carbon nanotubes in one or more.In the present embodiment, the preparation method of being somebody's turn to do super in-line arrangement carbon nano pipe array adopts chemical vapour deposition technique, its concrete steps comprise: a smooth substrate (a) is provided, this substrate can be selected P type or N type silicon base for use, or select for use the silicon base that is formed with oxide layer, present embodiment to be preferably and adopt 4 inches silicon base; (b) evenly form a catalyst layer at 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 substrate that is formed with catalyst layer was annealed in 700～900 ℃ air about 30 minutes～90 minutes; (d) 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 5～30 minutes, and growth obtains super in-line arrangement carbon nano pipe array, and it highly is 200～400 microns.Should super in-line arrangement carbon nano-pipe array classify as a plurality of parallel to each other and perpendicular to the pure nano-carbon tube array of the carbon nano-tube formation of substrate grown.By above-mentioned control growing condition, do not contain impurity substantially in this super in-line arrangement carbon nano pipe array, as agraphitic carbon or residual catalyst metal particles etc.The carbon nano-tube of being somebody's turn to do in the super in-line arrangement carbon nano pipe array closely contacts the formation array by Van der Waals force each other.The area and the above-mentioned area of base that are somebody's turn to do super in-line arrangement carbon nano pipe array are basic identical.
Carbon source gas can be selected the more active hydrocarbons of chemical property such as acetylene, ethene, methane for use in the present embodiment, and protective gas is nitrogen or inert gas.The preferred carbon source gas of present embodiment is acetylene, and preferred protective gas is an argon gas.
Step 2: adopt a stretching tool from described carbon nano pipe array 216, to pull and obtain an ordered carbon nanotube structure 214.
The preparation method of described ordered carbon nanotube structure 214 may further comprise the steps: (a) a plurality of carbon nano-tube bundle fragments of selected certain width from above-mentioned carbon nano pipe array 216, present embodiment are preferably and adopt an adhesive tape or a needle point with certain width to contact a plurality of carbon nano-tube bundle fragments of carbon nano pipe array 216 with selected certain width; (b) be basically perpendicular to these a plurality of carbon nano-tube bundle fragments of direction stretching that carbon nano pipe array 216 is grown with the certain speed edge, to form a continuous ordered carbon nanotube structure 214.
In above-mentioned drawing process, these a plurality of carbon nano-tube bundle fragments are when tension lower edge draw direction breaks away from substrate gradually, because Van der Waals force effect, should selected a plurality of carbon nano-tube bundle fragments be drawn out continuously end to end with other carbon nano-tube bundle fragment respectively, thereby form an ordered carbon nanotube structure 214.This ordered carbon nanotube structure 214 comprises a plurality of carbon nano-tube bundles that join end to end and align.The orientation of carbon nano-tube is basically parallel to the draw direction of ordered carbon nanotube structure 214 in this ordered carbon nanotube structure 214.
This ordered carbon nanotube structure 214 is a carbon nano-tube film or a carbon nanotube long line.Particularly, when the width of selected a plurality of carbon nano-tube bundle fragments was big, the ordered carbon nanotube structure 214 that is obtained was a carbon nano-tube film, and its microstructure sees also Fig. 8; When the width of selected a plurality of carbon nano-tube bundle fragments hour, the ordered carbon nanotube structure 214 that is obtained is a carbon nanotube long line.
Directly the thickness of the ordered carbon nanotube structure 214 of stretching acquisition is even, and carbon nano-tube evenly distributes in this carbon nano tube structure 214.The method of the acquisition ordered carbon nanotube structure 214 that should directly stretch is simply quick, the suitable industrial applications of carrying out.
Step 3: above-mentioned ordered carbon nanotube structure 214 is carried out mechanical treatment, obtain a carbon nanotube long line structure 100.
When above-mentioned ordered carbon nanotube structure 214 is the bigger carbon nano-tube film of a width, thereby it is carried out the step that mechanical treatment obtains a carbon nanotube long line can realize by following three kinds of modes: described ordered carbon nanotube structure 214 is reversed, formed twisted wire shape carbon nanotube long line; Cut described ordered carbon nanotube structure 214, form the pencil carbon nanotube long line; Ordered carbon nanotube structure 214 is soaked into the processing after-contraction through an organic solvent become a pencil carbon nanotube long line.
Described ordered carbon nanotube structure 214 is reversed, the step that forms carbon nanotube long line can realize by following dual mode: one, be fixed on the electric rotating machine by the stretching tool that will adhere to above-mentioned ordered carbon nanotube structure 214 1 ends, reverse this ordered carbon nanotube structure 214, thereby form a carbon nanotube long line.They are two years old, provide an afterbody can cling the spinning axle of ordered carbon nanotube structure 214, with after ordered carbon nanotube structure 214 combines, make this spinning spool reverse this ordered carbon nanotube structure 214 in rotary manner the afterbody of this spinning axle, form a carbon nanotube long line.The rotation mode that is appreciated that above-mentioned spinning axle is not limit, and can just change, and can reverse, and perhaps rotates and reverse to combine.Preferably, the described step of this ordered carbon nanotube structure 214 of reversing is for to reverse the draw direction of described ordered carbon nanotube structure 214 along ordered carbon nanotube structure 214 in a spiral manner.Reversing the formed carbon nanotube long line in back is the hank line structure, and its stereoscan photograph sees also Fig. 5.
The orderly carbon nano tube structure 214 of described cutting, the step that forms carbon nanotube long line is: the draw direction along ordered carbon nanotube structure 214 cuts described ordered carbon nanotube structure 214, forms a plurality of carbon nanotube long line.
It is fascicular texture that ordered carbon nanotube structure 214 is soaked into the carbon nanotube long line of handling the after-contraction acquisition through an organic solvent, and its stereoscan photograph sees also Fig. 4.Described organic solvent is a volatile organic solvent.Described volatile organic solvent is selected from ethanol, methyl alcohol, acetone, dichloroethanes and chloroform, this volatile organic solvent preferred alcohol in the present embodiment.
When carbon nanotube long line structure 100 comprised a carbon nanotube long line, the carbon nanotube long line that said method obtains was a carbon nanotube long line structure 100.
When carbon nanotube long line structure 100 comprised a plurality of carbon nanotube long line, can further be arranged in parallel bunchy or mutually twine of above-mentioned a plurality of carbon nanotube long line reversed, to form a carbon nanotube long line structure 100 that comprises a plurality of carbon nanotube long line.
Be appreciated that the technical program is not limited to said method and obtains carbon nanotube long line structure 100, as long as can make described ordered carbon nanotube structure 214 form the method for carbon nanotube long line structure 100 all within the protection range of the technical program.
Step 4: form at least one conductive material layer 110 in above-mentioned carbon nanotube long line structure 100 surfaces, obtain a cable core 120.
Present embodiment adopts physical vaporous deposition (PVD), as method deposits conductive material layers 110 such as vacuum vapour deposition or ion sputtering method or galvanoplastic.Preferably, present embodiment adopts vacuum vapour deposition to form layer of conductive material layer 110 at least.
Described employing vacuum vapour deposition forms at least, and the process of layer of conductive material layer 110 may further comprise the steps: at first, one vacuum tank 210 is provided, this vacuum tank 210 has at least one crystallizing field, this crystallizing field bottom and top are placed to few evaporation source 212 respectively, successively along the draw direction setting of ordered carbon nanotube structure 214, and each evaporation source 212 all can be by a heater (figure does not show) heating by the sequencing that forms layer of conductive material layer at least for this at least one evaporation source 212.Above-mentioned carbon nanotube long line structure 100 is arranged at evaporation source 212 middle and certain distances with interval up and down, and wherein carbon nanotube long line structure 100 is over against evaporation source 212 settings up and down.This vacuum tank 210 can bleeding reaches predetermined vacuum degree by an external vacuum pump (figure does not show).Described evaporation source 212 materials are electric conducting material to be deposited.Secondly,, make after its fusion evaporation or distillation form electric conducting material steam, after this electric conducting material steam runs into cold carbon nanotube long line structure 100,, form conductive material layer in the cohesion of carbon nanotube long line structure 100 upper and lower surfaces by heating described evaporation source 212.Owing to have the gap between the carbon nano-tube on carbon nanotube long line structure 100 surfaces, electric conducting material can penetrate in the gap between the carbon nanotube long line structure 100 surface carbon nanotubes, thereby well is deposited on the surface of carbon nanotube long line structure 100.
Be appreciated that by regulating carbon nanotube long line structure 100 and the distance of each evaporation source 212 and the distance between the evaporation source 212, can make each evaporation source 212 have a crystallizing field.When needs deposit multilayer conductive material layer 120, a plurality of evaporation sources 212 can be heated simultaneously, make carbon nanotube long line structure 100 pass through the crystallizing field of a plurality of evaporation sources continuously, thereby realize deposit multilayer conductive material layer 110.
For improving the electric conducting material vapour density and preventing that electric conducting material is oxidized, vacuum degree should reach more than 1 handkerchief (Pa) in the vacuum tank 210.Among the technical program embodiment, the vacuum degree in the vacuum tank 210 is 4 * 10
-4Pa.
Among the technical program embodiment, the method that described employing vacuum vapour deposition forms at least one conductive material layer 110 specifically may further comprise the steps: form one deck wetting layer 112 in described carbon nanotube long line structure 100 surfaces; Form one deck transition zone 113 in the outer surface of described wetting layer 112; Form one deck conductive layer 114 in the outer surface of described transition zone 113; Form one deck anti oxidation layer 115 in the outer surface of described conductive layer 114.Wherein, the step of above-mentioned formation wetting layer 112, transition zone 113 and anti oxidation layer 115 is selectable step.Particularly, above-mentioned carbon nanotube long line structure 100 can be passed through continuously the crystallizing field of the formed evaporation source 212 of above-mentioned layers of material.
By above-mentioned steps, can form at least one conductive material layer 110 on carbon nanotube long line structure 100 surfaces, thereby obtain the cable core 120 of cable 10.Prepared cable core 120 can further be collected on one first reel 224.Collection mode is for to be wrapped in cable core 120 on described first reel 224.
In addition, described formation at least layer of conductive material layer 110 after described carbon nanotube long line structure 100 surfaces, can further be included in the steps that described carbon nanotube long line structure 100 surfaces form strengthening layers 116.The process of described formation strengthening layer 116 specifically may further comprise the steps: the carbon nanotube long line structure 100 that will be formed with one deck conductive material layer 110 at least is by a device 220 that polymer solution is housed, make polymer solution soak into whole carbon nanotube long line structure 100, this polymer solution adheres to the outer surface of described at least one conductive material layer 110 by intermolecular force; And solidified polymeric, form a strengthening layer 116.
Step 5: form at least one insulating medium layer 130 in the outer surface of described cable core 120.
Described insulating medium layer 130 can be coated on the outer surface of described cable core 120 by one first pressurizing unit 230, and this first pressurizing unit 230 is coated in polymer melt composition on the surface of described cable core 120.Among the technical program embodiment, described polymer melt composition is preferably the foamed polyethylene composition.In case cable core 120 leaves described first pressurizing unit 230, polymer melt composition reduces to expand because of pressure, thereby forms insulating medium layer 130 in the outer surface of described cable core 120.
When described insulating medium layer 130 is two-layer or two-layer when above, can repeat above-mentioned steps.
Step 6: form at least one screen 140 in the outer surface of described insulating medium layer 130.
One mask tape 242 is provided, and this mask tape 242 is provided by one second reel 244.This mask tape 242 is covered around insulating medium layer 130 volumes, so that form screen 140.Mask tape 242 can be selected linear structures such as a metallic film, carbon nano tube structure or metal wire for use.In addition, described mask tape 242 also can be made of jointly the braid that above-mentioned multiple material forms, and by binding agent bonding or directly be wrapped in described insulating medium layer 130 outer surfaces.
Among the technical program embodiment, described screen 140 is made up of a plurality of carbon nanotube long line structures, and this carbon nanotube long line structure directly or be woven into netted being wrapped in outside the described insulating medium layer.Each carbon nanotube long line structure comprises a plurality of carbon nano-tube bundle fragments of pulling out from carbon nano pipe array, length and each carbon nano-tube bundle fragment that each carbon nano-tube bundle fragment has about equally are made of a plurality of carbon nano-tube bundles that are parallel to each other, wherein, carbon nano-tube bundle fragment two ends interconnect by Van der Waals force.The technical program embodiment adopts carbon nano tube structure to form screen 140, thereby makes this screen 140 have stronger shield effectiveness because of carbon nano-tube has excellent conducting performance.
Preferably, parcel is axially twined around cable core 120 in the mask tape 242 of described strip shape film structures, so that shield cable core 120 fully.The mask tape 242 of linear structures such as described carbon nanotube long line structure or metal wire can directly or be woven into the netted outer surface that is wrapped in described insulating medium layer 130.Particularly, described many carbon nanotube long line structures or metal wire can be wound on the outer surface of described insulating medium layer 130 by a plurality of drum stands 246 along the different hand of spiral.
Be appreciated that when described screen 140 during, can repeat above-mentioned steps for two-layer or two-layer above structure.
Step 7: form an oversheath 150 in the outer surface of described screen 140.
Described oversheath 150 can be coated to described screen 140 outer surfaces by one second pressurizing unit 250, this second pressurizing unit 250 is coated in polymer melt composition on the surface of screen 140, the outer surface that described polymer melt is centered around described screen 140 is extruded, and the cooling back forms oversheath 150.Present embodiment forms the preferred nano imvite-composite polyethylene material of polymer melt of oversheath 150; it has favorable mechanical performance, fire resistant flame retardant performance, low smoke and zero halogen performance; not only can provide protection for cable 10; effectively resist external damages such as machinery, physics or chemistry, can also satisfy requirement on environmental protection simultaneously.
Further, the cable 10 of manufacturing can be collected on the triple barrel 260, so that store and shipment.
See also Fig. 9, the technical program second embodiment provides a kind of cable 30, comprises a plurality of cable cores 320 (showing seven cable cores among Fig. 9 altogether), insulating medium layer 330 of each cable core 320 outer covering, is coated on a screen 340 and an oversheath 350 that is coated on screen 340 outer surfaces outside a plurality of cable cores 320.But fill insulant in the gap of screen 340 and insulating medium layer 330.Wherein, structure, material and the preparation method of structure, material and the preparation method of each cable core 320 and insulating medium layer 330, screen 340 and oversheath 350 and the cable core 120 among first embodiment, insulating medium layer 130, screen 140 and oversheath 150 are basic identical.
See also Figure 10, the technical program the 3rd embodiment provides a kind of cable 40 to comprise a plurality of cable cores 420 (showing five cable cores among Figure 10 altogether), each cable core 420 outer insulating medium layer 430 of covering and a screen 440 and the oversheath 450 that is coated on a plurality of cable core 420 outer surfaces.The effect of screen 440 is each cable core 440 is carried out independent shielding, can prevent from so not only that foeign element from causing to disturb but also can prevent to the signal of telecommunication of cable core 420 internal transmission to disturb mutually between the different electrical signals of transmission in each cable core 420.Wherein, structure, material and the preparation method of structure, material and the preparation method of each cable core 420, insulating medium layer 430, screen 440 and oversheath 450 and the cable core 120 among first embodiment, insulating medium layer 130, screen 140 and oversheath 150 are basic identical.
The preparation method of the cable core that comprises carbon nanotube long line and conductive material layer that the technical program embodiment provides has the following advantages: one, because carbon nanotube long line is to make by carbon nano-tube film being rotated or directly pulling from carbon nano pipe array, this method is simple, cost is lower.Its two, described from carbon nano pipe array, pull the step that obtains the ordered carbon nanotube structure and form at least the step of layer of conductive material layer all can in a vacuum tank, carry out, help the large-scale production of cable core, thereby help the large-scale production of cable.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and these variations of doing according to spirit of the present invention certainly all should be included in the present invention's scope required for protection.
Claims (22)
1. the preparation method of a cable cable core may further comprise the steps:
One carbon nano pipe array is provided;
From described carbon nano pipe array, pull carbon nano-tube and obtain an orderly pure nano-carbon tube structure;
Above-mentioned orderly pure nano-carbon tube structure is carried out mechanical treatment, obtain a pure nano-carbon tube linear structure; And
Form the surface of at least one conductive material layer, obtain a cable cable core in above-mentioned pure nano-carbon tube linear structure.
2. the preparation method of cable cable core as claimed in claim 1 is characterized in that, described carbon nano-pipe array is classified super in-line arrangement carbon nano pipe array as, and this super in-line arrangement carbon nano pipe array grows in a substrate surface by chemical vapour deposition technique.
3. the preparation method of cable cable core as claimed in claim 2 is characterized in that, this super in-line arrangement carbon nano-pipe array is classified as a plurality of parallel to each other and form perpendicular to the carbon nano-tube of substrate grown, and these a plurality of carbon nano-tube closely contact by Van der Waals force each other.
4. the preparation method of cable cable core as claimed in claim 3 is characterized in that, the preparation method of described orderly pure nano-carbon tube structure may further comprise the steps: selected a plurality of carbon nano-tube from above-mentioned carbon nano pipe array; Along these a plurality of carbon nano-tube of direction stretching that are basically perpendicular to the carbon nano pipe array growth, to form a continuous orderly pure nano-carbon tube structure.
5. the preparation method of cable cable core as claimed in claim 1 is characterized in that, described orderly pure nano-carbon tube structure is joined end to end to align along equidirectional by Van der Waals force by a plurality of carbon nano-tube and forms.
6. the preparation method of cable cable core as claimed in claim 1 is characterized in that, the step of described preparation pure nano-carbon tube linear structure realizes by described orderly pure nano-carbon tube structure is prepared into carbon nano tube line.
7. the preparation method of cable cable core as claimed in claim 6 is characterized in that, described carbon nano tube line obtains by the method for reversing described ordered carbon nanotube structure.
8. the preparation method of cable cable core as claimed in claim 6 is characterized in that, described carbon nano tube line forms by the described orderly pure nano-carbon tube structure of cutting.
9. the preparation method of cable cable core as claimed in claim 6 is characterized in that, described carbon nano tube line soaks into through a volatile organic solvent by described orderly pure nano-carbon tube structure handles after-contraction formation.
10. the preparation method of cable cable core as claimed in claim 9 is characterized in that, described volatile organic solvent is ethanol, methyl alcohol, acetone, dichloroethanes or chloroform.
11. the preparation method of cable cable core as claimed in claim 6 is characterized in that, described pure nano-carbon tube linear structure is reversed and is formed by parallel bunchy of a plurality of carbon nano tube lines or mutual the winding.
12. the preparation method of cable cable core as claimed in claim 1 is characterized in that, described conductive material layer forms by vacuum vapour deposition or ion sputtering method.
13. the preparation method of cable cable core as claimed in claim 12 is characterized in that, the method for at least one conductive material layer of described formation specifically may further comprise the steps: form one deck wetting layer in described pure nano-carbon tube linear structure surface; Form one deck transition zone in the outer surface of described wetting layer; Form one deck conductive layer in the outer surface of described transition zone; Form one deck anti oxidation layer in the outer surface of described conductive layer.
14. the preparation method of cable cable core as claimed in claim 13 is characterized in that, the material of described wetting layer is nickel, palladium, titanium or its alloy, and thickness is 1 nanometer～10 nanometers.
15. the preparation method of cable cable core as claimed in claim 13 is characterized in that, the material of described transition zone is copper, silver or its alloy, and thickness is 1 nanometer～10 nanometers.
16. the preparation method of cable cable core as claimed in claim 13 is characterized in that, the material of described anti oxidation layer is gold, platinum or its alloy, and thickness is 1 nanometer～10 nanometers.
17. the preparation method of cable cable core as claimed in claim 13 is characterized in that, further comprises forming a strengthening layer in the step on described anti oxidation layer surface.
18. the preparation method of cable cable core as claimed in claim 17 is characterized in that, the material of described strengthening layer is polyvinyl alcohol, polyhenylene Ben Bing Er oxazole, polyethylene or polyvinyl chloride, and thickness is 0.1 micron～1 micron.
19. the preparation method of a cable cable core may further comprise the steps:
One carbon nano pipe array is provided;
From described carbon nano pipe array, pull and handle carbon nano-tube, obtain a pure nano-carbon tube linear structure; And
Form the surface of at least one conductive material layer, obtain a cable cable core in above-mentioned pure nano-carbon tube linear structure.
20. the preparation method of a cable may further comprise the steps:
The cable core of at least one preparation method's preparation as each cable cable core in the claim 1 to 19 is provided;
Form the outer surface of at least one insulating medium layer in described cable core; And
Form the outer surface of at least one screen in described insulating medium layer.
21. the preparation method of cable as claimed in claim 20, the material of described at least one insulating medium layer is polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, foamed polyethylene composition or nanoclay-polymer composite.
22. the preparation method of cable as claimed in claim 20 is characterized in that, described at least one screen is that carbon nano tube structure is coated on the formation of insulating medium layer outer surface.
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| CN103093856A (en) * | 2011-10-28 | 2013-05-08 | 清华大学 | Electrode wire and pacemaker using the same |
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| CN100411979C (en) * | 2002-09-16 | 2008-08-20 | 清华大学 | Carbon nano pipe rpoe and preparation method thereof |
| US20060142458A1 (en) * | 2003-06-09 | 2006-06-29 | Pang Kawai P | Strippable semi-conductive insulation shield |
| WO2005084167A2 (en) * | 2003-09-05 | 2005-09-15 | Research Foundation Of Suny | Nanocomposite fibers and films containing polyolefin and surface-modified carbon nanotubes |
| CN1302486C (en) * | 2003-09-15 | 2007-02-28 | 北京大学 | Conducting polymer carbon nanotube nano cable and preparation method thereof |
| JP4729751B2 (en) * | 2004-04-06 | 2011-07-20 | 株式会社潤工社 | coaxial cable |
| CN108425170B (en) * | 2004-11-09 | 2021-02-26 | 得克萨斯大学体系董事会 | Manufacture and use of nanofiber yarns, tapes and sheets |
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| CN1992099B (en) * | 2005-12-30 | 2010-11-10 | 鸿富锦精密工业（深圳）有限公司 | Conductive composite material and electric cable containing same |
| CN101090011B (en) * | 2006-06-14 | 2010-09-22 | 北京富纳特创新科技有限公司 | Electromagnetic shielded cable |
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