CN106395796A - A carbon nanotube wire rod, a preparing method thereof, a preparing device and applications - Google Patents
A carbon nanotube wire rod, a preparing method thereof, a preparing device and applications Download PDFInfo
- Publication number
- CN106395796A CN106395796A CN201610515797.8A CN201610515797A CN106395796A CN 106395796 A CN106395796 A CN 106395796A CN 201610515797 A CN201610515797 A CN 201610515797A CN 106395796 A CN106395796 A CN 106395796A
- Authority
- CN
- China
- Prior art keywords
- wire rod
- preparation
- cnt wire
- cnt
- carrier gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B5/00—Making ropes or cables from special materials or of particular form
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2205/00—Rope or cable materials
- D07B2205/30—Inorganic materials
- D07B2205/3007—Carbon
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2401/00—Aspects related to the problem to be solved or advantage
- D07B2401/20—Aspects related to the problem to be solved or advantage related to ropes or cables
- D07B2401/202—Environmental resistance
- D07B2401/2025—Environmental resistance avoiding corrosion
Abstract
A carbon nanotube wire rod, a preparing method thereof, a preparing device and applications are provided. The device includes a raw material liquid supplying unit used for providing a liquid mixture of a liquid-state carbon source and a catalyst, an atomization unit connected to the raw material liquid supplying unit through a raw material liquid conveying pipeline, a reacting unit connected to the atomization unit through a raw material conveying pipeline provided with a carrier gas inlet, and a heating unit used for providing heat to the reacting unit. Through the device, carbon nanotubes grow along a carrier gas flowing direction, thus facilitating increase of control of a carbon nanotube wire rod continuous production process, producing carbon nanotube wire rods meeting different requirements, and further improving comprehensive properties of the carbon nanotube wire rod, such as conductivity and tensile strength.
Description
Technical field
The present invention relates to CNT wire rod preparation field, in particular to a kind of CNT wire rod and its preparation
Method, preparation facilitiess and application.
Background technology
The product of now widely used wire rod and its correlation (includes conductive-type metal wire rod, non-conductive class hawser, hinge
Deng), because its own quality, corrosion-resistant, the wear-resisting, factor such as intensity, flexible life is so that its performance or service life are subject to
To impact.
(coiler part of wireless headset and microphone is also suitable), earphone includes taking the wired earphone extensively producing at present as a example
Connecting line (metal wire rod) and the earplug/ear being made up of with vibrating diaphragm the voice coil loudspeaker voice coil (causing vibrating diaphragm to produce the coil of sound) in permanent magnetic field
Machine.
Because earphone connecting line is repeatedly subjected to stretch and bend in use, earphone connecting line is easily damaged to fracture, and makes
The service life of earphone greatly shortens；Additionally, voice coil loudspeaker voice coil (the moving-coil class earphone accounting 90% in the market in existing moving-coil earphone
More than) thin copper wire is usually used makes.Carbon nano tube line has that resisting fatigue, wear-resisting, electrical conductivity be high and light weight (about copper line
The 1/10 of material) etc. a series of features, after using CNT material wire instead, in the service life of earphone, linear property and frequency
The aspects such as response characteristic, performance may be further improved and lifted.
Have a kind of carbon nanotube conductor of document report, this wire is three-decker：Ground floor (internal layer) increases for aramid fiber
Qiang Xin, the second layer (intermediate layer) is carbon nano-tube fibre, and third layer (outer layer) is protection jacket layer.Three-decker makes wire prepare work
Skill is relative complex, and production cost increases.Contact electricity in addition, the carbon pipe fiber of the second layer is fluff structure, between CNT
Resistance is big；And the Van der Waals between CNT and adjacent carbon nanotubes can not be made full use of, thus hold when by external force
It is also easy to produce the sliding between carbon pipe and carbon pipe.The CNT of the present invention and CNT wire rod overcome this shortcoming.
Content of the invention
Present invention is primarily targeted at providing a kind of CNT wire rod and preparation method thereof, preparation facilitiess and application,
With solve the problems, such as existing CNT have that production cost is high, complicated process of preparation and CNT poor orientation.
To achieve these goals, one aspect of the present invention provides a kind of preparation facilitiess of CNT wire rod, this preparation
Device includes：Material liquid feeding unit, for providing the mixed liquor of liquid carbon source and catalyst；Atomization unit, atomization unit with
Material liquid feeding unit passes through material liquid transfer pipeline and is connected；Reaction member, reaction member passes through feedstock transportation with atomization unit
Pipeline is connected, and feedstock transportation pipeline has carrier gas inlet；And heating unit, for providing heat to reaction member.
Further, reaction member has products export, and preparation facilitiess also include CNT wire rod collector unit, and carbon is received
Mitron wire collection unit is connected with products export.
Further, reaction member has feed(raw material)inlet, and feed(raw material)inlet is connected with atomization unit by feedstock transportation pipeline,
Preparation facilitiess also include multiphase flow rectifying device, and multiphase flow rectifying device is arranged at feed(raw material)inlet.
Further, preparation facilitiess also include stable-pressure device, and stable-pressure device is used in conjunction with CNT wire rod collector unit phase
In stablizing of holding CNT wire rod collector unit internal pressure.
Further, CNT wire rod collector unit is provided with air vent, and it is defeated that air vent and carrier gas inlet pass through tail gas
Pipeline is sent to be connected, preferably preparation facilitiess also include exhaust gas processing device, and exhaust gas processing device is arranged on exhaust pipe road.
Another invention of the present invention additionally provides a kind of preparation method of CNT wire rod, and preparation method includes：By liquid
Carbon source is mixed with catalyst, forms material liquid；Material liquid is atomized, atomized raw material；And using carrier gas to atomized feed
Flow direction guides, and makes atomized feed carry out catalytic reaction under conditions of heating, continuously generates CNT wire rod.
Further, liquid carbon source is selected from one or more of dimethylbenzene, ethanol, benzene, normal hexane and oxolane；Urge
Agent is metallorganics, and the metallic element in this metallorganic is ferrum, cobalt, nickel and/or yttrium；Preferably, catalyst is two
Luxuriant ferrum or iron pentacarbonyl.
Further, catalyst and the amount ratio of liquid carbon source are 5～200mg/mL.
Further, the temperature of catalytic reaction is 750～1450 DEG C.
Further, carrier gas is selected from one or more of hydrogen, argon and nitrogen it is preferable that carrier gas is argon and hydrogen
The mixed gas of gas, it is highly preferred that argon and the volume ratio of hydrogen are 2～10 in mixed gas:1.
Further, the step of the CNT wire rod obtained by preparation method also includes collecting, and in the process collected
Middle holding pressure is constant.
Further, the step that preparation method also includes vent gas treatment, this step includes discharging catalytic reaction process
Tail gas carries out the step separating, proportioning reuses after processing as carrier gas.
Another aspect of the invention additionally provides a kind of CNT wire rod, and this CNT wire rod adopts above-mentioned preparation method
It is prepared from, or the density of CNT wire rod is 0.4～1.8 × 103kg/m3, tensile break strength is more than or equal to
1.0GPa, electrical conductivity is better than 106S·m-1, maximum current load-carrying ability is more than or equal to 103A/mm2.
Another aspect of the invention provides a kind of carbon nanotube conductor, and including CNT wire rod, CNT wire rod is
Above-mentioned CNT wire rod.
Another aspect of the invention provides a kind of electronic product, and including wire, this wire is above-mentioned carbon nanotube conductor.
Further, above-mentioned electronic product is earphone.
Another aspect of the invention provides a kind of hawser, and hawser includes above-mentioned CNT wire rod.
Application technical scheme, liquid carbon source and catalyst is formed and carries out carbon nano tube line material after mixed liquor
Preparation reaction is conducive to making reaction raw materials mix more uniform, thus being conducive to improving the stability of above-mentioned reaction and controlled
Property.Using atomization unit by material liquid carry out atomization be conducive to making above-mentioned reaction carry out more abundant, thus improving carbon nanometer
The production rate of pipe.By means of carrier gas will be atomized after atomized feed send into heating after reaction member can make CNT along
The direction of flow of air is grown, thus being conducive to improving the orientation of CNT wire rod, and then improves CNT wire rod
Electric conductivity, the combination property such as tensile strength.
Brief description
The Figure of description constituting the part of the application is used for providing a further understanding of the present invention, and the present invention shows
Meaning property embodiment and its illustrate for explaining the present invention, does not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 shows the structural representation of a kind of typical CNT wire rod preparation facilitiess according to the present invention.
Wherein, above-mentioned accompanying drawing includes the following drawings labelling：
10th, material liquid feeding unit；101st, material liquid transfer pipeline；20th, atomization unit；201st, feedstock transportation pipeline；21、
Carrier gas inlet；30th, reaction member；40th, heating unit；50th, CNT wire rod collector unit；501st, exhaust pipe road；51、
Air vent；52nd, receive silk device；53rd, collect roller；60th, multiphase flow rectifying device；70th, stable-pressure device；80th, exhaust gas processing device；
81st, flow controller.
Specific embodiment
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can phases
Mutually combine.To describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
As described by background technology, existing preparation method of carbon nano-tube has that production cost is high, preparation technology is multiple
Miscellaneous and CNT orientation controls the problem of difference.In order to solve above-mentioned technical problem, the invention provides a kind of carbon nanometer
The preparation facilitiess of tube wire, as shown in figure 1, this device includes material liquid feeding unit 10, atomization unit 20, reaction member 30 and
Heating unit 40.Material liquid feeding unit 10 is used for providing the mixed liquor of liquid carbon source and catalyst；Atomization unit 20 and raw material
Liquid feeding unit 10 passes through material liquid transfer pipeline 101 and is connected；Reaction member 30 passes through feedstock transportation pipeline with atomization unit 20
201 are connected, and feedstock transportation pipeline 201 has carrier gas inlet 21, and heating unit 40 is used for providing heat for reaction member 30.
The preparation carrying out CNT after liquid carbon source and catalyst formation mixed liquor is reacted and is conducive to making reaction raw materials
Mix is more uniform, thus being conducive to improving stability and the controllability of above-mentioned reaction.Using atomization unit 20 by material liquid
Carry out atomization be conducive to making above-mentioned reaction carry out more abundant, thus improving the production rate of CNT.Will by means of carrier gas
The reaction member 30 that atomized feed after atomization is sent into after heating can make CNT be given birth to along the direction of carrier gas
Long, thus being conducive to improving the orientation of CNT wire rod, and then improve the electric conductivity of CNT wire rod, tensile strength
Etc. combination property.
Using above-mentioned CNT wire rod preparation facilitiess, can produce that orientation is good, electric conductivity is excellent and tension
The big CNT wire rod of intensity.In a kind of preferred embodiment, as shown in figure 1, reaction member 30 has products export, system
Standby device also includes CNT wire rod collector unit 50, and CNT wire rod collector unit 50 is connected with products export.Work as carbon
After reaction member 30 output, the temperature in CNT wire rod collector unit 50 is less than in reaction member 30 nanometer tube wire
Temperature, in the presence of CNT wire rod collector unit 50, enables to be shrunk to, by CNT wire rod, the carbon more compacting
Nanometer tube wire, is then collected in an orderly manner, is grouped and woven.As shown in figure 1, preferred CNT wire rod collector unit 50
Including receiving silk device 52 and collecting roller 53, receive silk device 52 and be used for the continuous CNT wire rod accepted and be obtained, collect roller
53 are used for for CNT wire rod collecting rolling, consequently facilitating storage, transport and subsequent applications.
In another kind of preferred embodiment, preferably as shown in figure 1, above-mentioned reaction member 30 has atomized feed entrance,
Atomized feed entrance is connected with atomization unit 20 by feedstock transportation pipeline 201, and above-mentioned preparation facilitiess also include multiphase flow rectification
Device 60, multiphase flow rectifying device 60 is arranged at feed(raw material)inlet.At feed(raw material)inlet, setting multiphase flow rectifying device 60 can
Irregular multiphase flow flowing is made to be changed into the multiphase flow flowing of rule, thus being conducive to make carbon source and catalyst when reacting to divide
Cloth is more uniform.The shape of preferably multiphase flow rectifying device 60 is including but not limited to poroid, palisade or latticed.
In another preferred embodiment, preferably as shown in figure 1, above-mentioned preparation facilitiess also include stable-pressure device 70, surely
Pressure device 70 is connected for keeping CNT wire rod collector unit 50 internal pressure with CNT wire rod collector unit 50
Stable.Stable-pressure device 70 be provided with beneficial to stablize in whole reaction member 30 multiphase flow flowing (include reactant, carrier gas,
Product etc.), and then be conducive to improving the homogeneity of the CNT wire rod caliber generating and orientation.
In another kind of preferred embodiment, as shown in figure 1, above-mentioned CNT wire rod collector unit 50 is provided with aerofluxuss
Mouth 51, air vent 51 is connected by exhaust pipe road 501 with carrier gas inlet 21, and above-mentioned preparation facilitiess also include vent gas treatment dress
Put 80, exhaust gas processing device 80 is arranged on exhaust pipe road 501.The setting of exhaust gas processing device 80 can be to single from reaction
The tail gas of unit 30 discharge is carried out after separation is processed with proportioning as carrier gas recycling, also advantageously improves the conversion effect of carbon simultaneously
Rate, reduces carrier gas consumption, saves production cost, so that the preparation of CNT is more economical, efficient and reduces disposal of pollutants,
It is allowed to be suitable for commercially producing.
Further preferably above-mentioned preparation facilitiess also include flow controller 81, as shown in figure 1, above-mentioned flow controller 81
On the exhaust pipe road 501 between exhaust gas processing device 80 and carrier gas inlet 21.Being provided with of above-mentioned flow controller 81
Ratio beneficial to the tail gas controlling after purifying and fresh carrier gas.
In another kind of typical embodiment of the application, there is provided a kind of preparation method of CNT wire rod, this system
Preparation Method includes：Liquid carbon source is mixed with catalyst, forms material liquid；Material liquid is atomized, atomized raw material；And utilize
Carrier gas guides to the flow direction of atomized feed, and makes atomized feed carry out catalytic reaction under conditions of heating, continuously
Generate CNT wire rod.
The preparation principle of CNT is that liquid carbon source resolves into atomic carbon simultaneously under the collective effect of heating and catalyst
Separate out in catalyst surface, generate CNT.
The preparation carrying out CNT after liquid carbon source and catalyst formation mixed liquor is reacted and is conducive to making reaction raw materials
Mix is more uniform, thus being conducive to improving stability and the controllability of above-mentioned reaction.Material liquid is carried out atomization be conducive to
Above-mentioned reaction is made to carry out more abundant, thus improving the production rate of CNT.With the flow direction to atomized feed for the carrier gas
Guide and make atomized feed carry out catalytic reaction, CNT can be made to be grown along the direction of carrier gas, thus
Be conducive to improving the orientation of CNT, and then improve the combination properties such as the electric conductivity of CNT wire rod, tensile strength.
In actual use, preferably use ultrasound atomizer and carry out above-mentioned atomization process, its frequency is for 200Hz extremely
Between 15MHz, power is 1～200W；Actual atomization power can be adjusted according to volume of production.
In above-mentioned preparation method, the flow of carrier gas can be adjusted according to actual needs.In one kind side of being preferably carried out
In formula, the flow of carrier gas is 100～10000 ml/min.The flow restriction of carrier gas is conducive to making reaction within the above range
During the flowing of gas be in closely stratospheric state, prepare CNT in the above-described state and be conducive to improving further carbon
The orientation of nanotube, and then be conducive to improving the combination property of CNT wire rod.
In above-mentioned preparation method, liquid carbon source can be from species commonly used in the art.In one kind preferred embodiment
In, liquid carbon source includes but is not limited to one or more of dimethylbenzene, ethanol, benzene, normal hexane and oxolane.Above-mentioned substance
Source is wide, cheap thus the preparation cost that advantageously reduces CNT wire rod from above-mentioned liquid carbon source.Simultaneously above-mentioned
In material, the degree of carbon is higher, is used above-mentioned substance to also advantageously improve the life of CNT as liquid carbon source
One-tenth rate.
Preferred catalyst is metallorganics, and the metallic element in this metallorganic is ferrum, cobalt, nickel and/or yttrium.Preferably
Above-mentioned catalyst is ferrocene and/or pentacarbonyl-iron.Catalyst includes but is not limited to above-mentioned substance, from above two catalysis
Agent is conducive to improving the reactivity of carbon nanometer pipe catalytic reaction further.
In above-mentioned preparation method, those skilled in the art can adjust the use of catalyst and liquid carbon source according to actual needs
Amount ratio.In a preferred embodiment, catalyst and the amount ratio of liquid carbon source are 5～200mg/mL.By catalyst and
The amount ratio of liquid carbon source limits within the above range, is conducive to lifting the utilization ratio of catalyst further.
In above-mentioned preparation method, the temperature of catalytic reaction can select the reaction temperature during CNT preparation of this area.
In a preferred embodiment, the temperature of catalytic reaction is 750～1450 DEG C.By the limit temperature of catalytic reaction above-mentioned
In the range of be conducive to improving the production rate of CNT further.In real process, above-mentioned catalytic reaction can be in normal pressure or negative pressure
Under carry out.
In above-mentioned preparation method, carrier gas can select carrier gas commonly used in the art.In a preferred embodiment, carry
Gas includes but is not limited to one or more of hydrogen, argon and nitrogen, is conducive to dropping as carrier gas from above-mentioned several gases
The preparation cost of low-carbon nano tube wire.
In above-mentioned preparation method, in carrier gas, the proportionate relationship between the composition of gas and each component can be according to actual needs
It is adjusted.Preferably, carrier gas is the mixed gas of argon and hydrogen.It is highly preferred that in mixed gas argon and hydrogen stream
Amount ratio is 2～10:1.The proportionate relationship of argon in carrier gas and hydrogen is limited and is conducive within the above range improving carbon further
The production rate of nanotube.
In a kind of preferred embodiment, preparation method also includes the step collecting generated CNT wire rod, and
Keep pressure constant during collecting.Collect process in CNT wire rod and keep that pressure is constant to be conducive to improving whole reaction
During multiphase flow flowing stability (including reactant, carrier gas, product etc.), and then be conducive to improving the nanotube generating
The homogeneity of wire rod caliber.
In a preferred embodiment, the step that preparation method also includes tail gas recycle, this step includes being catalyzed
The step that the tail gas that course of reaction is discharged reuses as carrier gas after carrying out separation and proportioning process.Tail gas recycle is conducive to reality
Recycling of existing tail gas, also advantageously improves charcoal percent conversion simultaneously, reduces carrier gas consumption, saves preparation cost, so that
The preparation of CNT wire rod is more economical, efficient and reduces disposal of pollutants, is allowed to be suitable for commercially producing.
Another aspect of the present invention additionally provides a kind of CNT wire rod, and this CNT wire rod adopts above-mentioned preparation side
Method is made or the density of this CNT wire rod is 0.4～1.8 × 103kg/m3, tensile break strength is more than or equal to 1.0GPa, electric
Conductance is more than or equal to 106S·m-1, maximum current load is more than or equal to 103A/mm2.
Because the CNT that the application provides has preferable orientation, thus the adjacent carbons in CNT wire rod is received
Mitron spacing is less, and mutual Van der Waals for is larger, so that CNT wire rod has stronger tension failure
Intensity, simultaneously the good orientation of CNT also make CNT wire rod have good electrical conductivity and maximum current to carry
Lotus.CNT wire rod also has the less advantage of density simultaneously.
The product of now widely used wire rod and its correlation (includes conductive-type metal wire rod, non-conductive class hawser, hinge
Deng), because its own quality, corrosion-resistant, the wear-resisting, factor such as intensity, flexible life is so that its performance or service life are subject to
To impact.Another aspect of the present invention provides a kind of carbon nanotube conductor, including the carbon in CNT wire rod, and above-mentioned wire rod
The CNT wire rod that nanometer tube wire provides for the application.Due to the application provide CNT wire rod conductive good,
The advantages of maximum current load is high, tensile break strength is big, density is little, the CNT that the application is provided is made after wire,
Its weight and stretch-proof fracture strength can be greatly reduced；Can also keep suitable with conventional superior metal wire rod simultaneously
Conductive capability, and maximum current load is far above conventional metal wire rod.In actual use, above-mentioned carbon nano tube line
Material can make ultra micro wire and conventional wires, such as a diameter of 5～80 microns of ultra micro wires and micro- with diameter greater than equal to 80
The conventional wires of rice.
In addition above-mentioned carbon nanotube conductor has excellent electric conductivity, thus a kind of electronics of another aspect of the present invention produces
Product, the above-mentioned carbon nanotube conductor providing for the application including wire, this wire.Preferably above-mentioned electronic product is earphone.
Because the CNT wire rod that the application provides is made after wire, weight, the reduction of wire can be greatly reduced
Produce and cost of use, lifting conductive capability；Above-mentioned wire also has higher tensile strength, corrosion resistance and use simultaneously
The advantages of life-span.Thus the weight of the electronic product being obtained using above-mentioned wire also can be mitigated significantly, service life also can simultaneously
More permanent.
Because the CNT wire rod that the application provides has above-mentioned advantage, thus can use it for making function admirable
The fine coil of long distance powedr transmission cable, high-performance, CNT wire rod earphone, microphone (wired and wireless) and connecting line are accurate
The coil of sensor, in wearable electronic product adopt CNT wire rod connecting line, CNT wire rod weave cotton cloth electric heating protect
Warm clothing, CNT wire rod is weaved cotton cloth electric blanket, for the CNT wire rod connecting line of precision instrument, medical detecting Instrument etc.
And the coil of patch plug and sophisticated sensor etc..
Tensile break strength due to the above-mentioned CNT wire rod of the application offer is more than or equal to 1.0GPa, and density is little
(0.4～1.8 × 103kg/m3), thus another aspect of the present invention additionally provides a kind of hawser, this hawser includes above-mentioned CNT
Wire rod.Have that tensile strength is big, corrosion resistance strong using the hawser of above-mentioned CNT wire rod preparation, long service life and weight
The advantages of measure light.
Below in conjunction with specific embodiment, the present invention is described in further detail, these embodiments are it is not intended that limit this
Invent scope required for protection.
Embodiment 1 to 6 and comparative example 1 prepare CNT wire rod using the device described in Fig. 1；
In embodiment 1 to 6 and comparative example 1 to 2, the performance parameter of CNT wire rod records by the following method：
Using model AUW220D electronic balance weighing length be 10 meters CNT wire rod weight；Using sweeping
Retouch ultramicroscope measurement to average no less than the diameter of wire rod at 5；Thus calculate the density of CNT wire rod；
Using the universal material test machine of Instron company 5943Q model, in accordance with ASTM C1557 standard, (this standard is fitted
Be less than or equal to 250 microns of wire rod for diameter) and ASTM A931 standard (this standard is used for measurement diameter in this patent
Wire rod more than 250 microns) mechanical properties such as the Young's moduluss of CNT wire rod and tensile break strength are detected；
Using the multifunctional power ammeter of Keithley 4200CSC model, in accordance with ASTM B193 standard, using four probes
Method of attachment (eliminating contact resistance impact) is detected to the electrical conductivity of CNT wire rod；
Using the multifunctional power ammeter of Keithley 2420 model, using two Probe ligation methods, (wire rod starts to fuse
When load electric current divided by wire rod cross-sectional area) the maximum current load-carrying ability of CNT wire rod is detected.
Embodiment 1
By liquid carbon source oxolane and catalyst ferrocene, according to 150 milligram of two cyclopentadienyl of addition in every milliliter of oxolane
The ratio of iron catalyst is mixed and made into material liquid.
Above-mentioned raw materials liquid is atomized under 50kHz, atomized raw material.
(argon is 3 with the flow-rate ratio of hydrogen for the carrier gas being 9000 ml/min in speed:1) guiding and temperature 1450
DEG C, under conditions of normal pressure, make above-mentioned atomized feed carry out catalytic reaction, obtain CNT wire rod.
Using CNT wire rod collection device, above-mentioned CNT wire rod is collected.Wherein CNT wire rod
Density is 900kg/m3, Young's moduluss are 250GPa, and electrical conductivity is 1.0 × 107S·m-1, maximum current load is 6000A/mm2,
Tensile break strength is 1.5GPa.
Embodiment 2
By liquid carbon source dimethylbenzene and catalyst ferrocene, it is catalyzed according to adding 50 milligrams of ferrocene in every milliliter of dimethylbenzene
The ratio of agent is mixed and made into material liquid.
Above-mentioned raw materials liquid is atomized under 50kHz, atomized raw material.
(argon is 3 with the flow-rate ratio of hydrogen for the carrier gas being 9000 ml/min in speed:1) guiding and temperature 1150
DEG C, under conditions of normal pressure, make above-mentioned atomized feed carry out catalytic reaction, obtain CNT wire rod.
Using CNT wire rod collection device, above-mentioned CNT wire rod is collected.Wherein CNT wire rod
Density is 750kg/m3, Young's moduluss are 180GPa, and electrical conductivity is 8 × 106S·m-1, maximum current load is 5500A/mm2, draw
Stretching fracture strength is 1.35GPa.
Embodiment 3
By liquid carbon source dimethylbenzene and catalyst ferrocene, it is catalyzed according to adding 2 milligrams of ferrocene in every milliliter of dimethylbenzene
The ratio of agent is mixed and made into material liquid.
Above-mentioned raw materials liquid is atomized under 37kHz, atomized wire raw material wire rods.
(argon is 3 with the flow-rate ratio of hydrogen for the carrier gas being 9000 ml/min in speed:1) guiding and temperature 600
DEG C, under conditions of normal pressure, make above-mentioned atomized feed carry out catalytic reaction, obtain CNT.
Using CNT wire rod collection device, above-mentioned CNT wire rod is collected.Wherein CNT wire rod
Density is 400kg/m3, Young's moduluss are 100GPa, and electrical conductivity is 1.1 × 106S·m-1, maximum current load is 1100A/mm2,
Tensile break strength is 1.05GPa.
Embodiment 4
By liquid carbon source dimethylbenzene and catalyst ferrocene, it is catalyzed according to adding 20 milligrams of ferrocene in every milliliter of dimethylbenzene
The ratio of agent is mixed and made into material liquid.
Above-mentioned raw materials liquid is atomized under 15MHz, atomized raw material.
(argon is 3 with the flow-rate ratio of hydrogen for the carrier gas being 9000 ml/min in speed:1) guiding and temperature 800
DEG C, under conditions of normal pressure, make above-mentioned atomized feed carry out catalytic reaction, obtain CNT wire rod.
Using CNT wire rod collection device, above-mentioned CNT wire rod is collected.Wherein CNT wire rod
Density is 700kg/m3, Young's moduluss are 175GPa, and electrical conductivity is 2.4 × 106S·m-1, maximum current load is 3500A/mm2,
Tensile break strength is 1.08GPa.
Embodiment 5
By liquid carbon source dimethylbenzene and catalyst ferrocene, it is catalyzed according to adding 20 milligrams of ferrocene in every milliliter of dimethylbenzene
The ratio of agent is mixed and made into material liquid.
Above-mentioned raw materials liquid is atomized under 1MHz, atomized raw material.
(argon is 3 with the flow-rate ratio of hydrogen for the carrier gas being 9000 ml/min in speed:1) guiding and temperature 1350
DEG C, under conditions of normal pressure, make above-mentioned atomized feed carry out catalytic reaction, obtain CNT wire rod.
Using CNT wire rod collection device, above-mentioned CNT wire rod is collected.Wherein CNT wire rod
Density is 750kg/m3, Young's moduluss are 185GPa, and electrical conductivity is 4 × 106S·m-1, maximum current load is 3200A/mm2, draw
Stretching fracture strength is 1.15GPa.
Embodiment 6
By liquid carbon source dimethylbenzene and catalyst ferrocene, it is catalyzed according to adding 20 milligrams of ferrocene in every milliliter of dimethylbenzene
The ratio of agent is mixed and made into material liquid.
Above-mentioned raw materials liquid is atomized under 1MHz, atomized raw material.
(argon is 3 with the flow-rate ratio of hydrogen for the carrier gas being 50 ml/min in speed:1) guiding and 1350 DEG C of temperature,
Under conditions of normal pressure, make above-mentioned atomized feed carry out catalytic reaction, obtain CNT wire rod.
Using CNT wire rod collection device, above-mentioned CNT wire rod is collected.Wherein CNT wire rod
Density is 600kg/m3, Young's moduluss are 132GPa, and electrical conductivity is 1.8 × 106S·m-1, maximum current load is 1800A/mm2,
Tensile break strength is 1.05GPa.
Comparative example 1
By liquid carbon source oxolane and catalyst ferrocene, according to 100 milligrams of ferrocene of addition in every milliliter of dimethylbenzene
The ratio of catalyst is mixed and made into material liquid.
Above-mentioned raw materials liquid is atomized under 200KHz, atomized raw material.
Make above-mentioned atomized feed carry out catalytic reaction, obtain CNT wire rod.
Using CNT wire rod collection device, above-mentioned CNT wire rod is collected.Wherein CNT wire rod
Density is 400kg/m3, Young's moduluss are 80GPa, and electrical conductivity is 1.2 × 105S·m-1, maximum current load is 600A/mm2, draw
Stretching fracture strength is 0.56GPa.
Comparative example 2
By liquid carbon source dimethylbenzene and catalyst ferrocene, it is catalyzed according to adding 50 milligrams of ferrocene in every milliliter of dimethylbenzene
The ratio of agent is mixed and made into material liquid.
By above-mentioned raw materials liquid heating evaporation, obtain unstripped gas.
Make above-mentioned raw materials gas carry out catalytic reaction at 1150 DEG C, obtain CNT wire rod.
Using CNT wire rod collection device, above-mentioned CNT wire rod is collected.Wherein CNT wire rod
Density is 200kg/m3, Young's moduluss are 56GPa, and electrical conductivity is 5.5 × 104S·m-1, maximum current load is 120A/mm2, draw
Stretching fracture strength is 0.4GPa.
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect：By liquid carbon
Source and catalyst carry out carbon nano tube line material preparation after forming mixed liquor is reacted and is conducive to making reaction raw materials mix more equal
Even, thus being conducive to improving stability and the controllability of above-mentioned reaction.Using atomization unit, material liquid is carried out atomization to be conducive to
Above-mentioned reaction is made to carry out more abundant, thus improving the production rate of CNT.By means of carrier gas, the raw material after being atomized is sent
Entering the reaction member after heating can make CNT continuously be grown along the direction of carrier gas, thus being conducive to improving
The orientation of CNT, and then improve the combination properties such as the electric conductivity of CNT wire rod, tensile strength.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (17)
1. a kind of preparation facilitiess of CNT wire rod are it is characterised in that described preparation facilitiess include：
Material liquid feeding unit (10), for providing the mixed liquor of liquid carbon source and catalyst；
Atomization unit (20), described atomization unit (20) passes through material liquid transfer pipeline with described material liquid feeding unit (10)
(101) it is connected；
Reaction member (30), described reaction member (30) is connected by feedstock transportation pipeline (201) with described atomization unit (20),
Described feedstock transportation pipeline (201) has carrier gas inlet (21)；And
Heating unit (40), for providing heat to described reaction member (30).
2. preparation facilitiess according to claim 1 are it is characterised in that described reaction member (30) has products export, institute
State preparation facilitiess and also include CNT wire rod collector unit (50), described CNT wire rod collector unit (50) and described product
Product outlet is connected.
3. preparation facilitiess according to claim 1 and 2 are it is characterised in that described reaction member (30) has feed(raw material)inlet,
Described feed(raw material)inlet is connected with described atomization unit (20) by described feedstock transportation pipeline (201), and described preparation facilitiess also wrap
Include multiphase flow rectifying device (60), described multiphase flow rectifying device (60) is arranged at described feed(raw material)inlet.
4. preparation facilitiess according to claim 2 are it is characterised in that described preparation facilitiess also include stable-pressure device (70),
Described stable-pressure device (70) is connected with described CNT wire rod collector unit (50) for keeping described CNT wire rod to receive
Collect stablizing of unit (50) internal pressure.
5. the preparation facilitiess according to any one of claim 2 to 4 are it is characterised in that described CNT wire rod is collected
Unit (50) is provided with air vent (51), and described air vent (51) passes through exhaust pipe road with described carrier gas inlet (21)
(501) it is connected,
Preferably described preparation facilitiess also include exhaust gas processing device (80), and described exhaust gas processing device (80) is arranged at described tail gas
On transfer pipeline (501).
6. a kind of preparation method of CNT wire rod is it is characterised in that described preparation method includes：
Liquid carbon source is mixed with catalyst, forms material liquid；
Described material liquid is atomized, atomized raw material；And
Using carrier gas, the flow direction of described atomized feed is guided, and so that described atomized feed is entered under conditions of heating
Row catalytic reaction, continuously generates described CNT wire rod.
7. preparation method according to claim 6 it is characterised in that described liquid carbon source be selected from dimethylbenzene, ethanol, benzene,
One or more of normal hexane and oxolane；Described catalyst is metallorganics, the metal in described metallorganics
Element is ferrum, cobalt, nickel and/or yttrium；Preferably, described catalyst is ferrocene or iron pentacarbonyl.
8. preparation method according to claim 6 is it is characterised in that the amount ratio of described catalyst and described liquid carbon source
For 5～200mg/mL.
9. preparation method according to claim 6 is it is characterised in that the temperature of described catalytic reaction is 750～1450 DEG C.
10. preparation method according to claim 6 is it is characterised in that described carrier gas is selected from hydrogen, argon and nitrogen
One or more,
Preferably, described carrier gas is the mixed gas of argon and hydrogen,
It is highly preferred that argon and the volume ratio of hydrogen are 2～10 in described mixed gas:1.
11. preparation methoies according to claim 6 it is characterised in that described preparation method also include collect obtained by
The step of CNT wire rod, and keep pressure constant during described collection.
12. preparation methoies according to claim 6 are it is characterised in that described preparation method also includes the step of vent gas treatment
Suddenly, the tail gas that this step includes discharging described catalytic reaction process carries out separation, proportioning repeats as described carrier gas after processing
Using step.
A kind of 13. CNT wire rods are it is characterised in that described CNT wire rod adopts any one of claim 6 to 12
Described preparation method is prepared from, or the density of described CNT wire rod is 0.4～1.8 × 103kg/m3, tension failure
Intensity is more than or equal to 1.0GPa, and electrical conductivity is better than 106S·m-1, maximum current load-carrying ability is more than or equal to 103A/mm2.
A kind of 14. carbon nanotube conductors, including CNT wire rod it is characterised in that described CNT wire rod will for right
Seek the CNT wire rod described in 13.
A kind of 15. electronic products, including wire it is characterised in that described wire is led for the CNT described in claim 14
Line.
16. electronic products according to claim 15 are it is characterised in that described electronic product is earphone.
A kind of 17. hawsers are it is characterised in that described hawser includes the CNT wire rod described in claim 13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610515797.8A CN106395796A (en) | 2016-07-01 | 2016-07-01 | A carbon nanotube wire rod, a preparing method thereof, a preparing device and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610515797.8A CN106395796A (en) | 2016-07-01 | 2016-07-01 | A carbon nanotube wire rod, a preparing method thereof, a preparing device and applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106395796A true CN106395796A (en) | 2017-02-15 |
Family
ID=58006857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610515797.8A Pending CN106395796A (en) | 2016-07-01 | 2016-07-01 | A carbon nanotube wire rod, a preparing method thereof, a preparing device and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106395796A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108408716A (en) * | 2018-03-26 | 2018-08-17 | 苏州捷迪纳米科技有限公司 | System for manufacturing carbon nm tube |
| CN114477143A (en) * | 2022-03-25 | 2022-05-13 | 江西省纳米技术研究院 | Reaction furnace tube of carbon nanotube material, and growth device and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435029A (en) * | 2013-09-05 | 2013-12-11 | 武汉博力信纳米科技有限公司 | Device and method for preparing continuous carbon nanotube aggregate by assistance of ultrasonic atomization |
| CN203820461U (en) * | 2013-09-27 | 2014-09-10 | 武汉博力信纳米科技有限公司 | Device for preparing continuous carbon nano tube fibers by carrying out box-sealed chemical gas-phase reaction |
| CN104641028A (en) * | 2013-06-18 | 2015-05-20 | Lg化学株式会社 | Device for manufacturing carbon nanotube fibers and method for manufacturing carbon nanotube fibers using same |
-
2016
- 2016-07-01 CN CN201610515797.8A patent/CN106395796A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104641028A (en) * | 2013-06-18 | 2015-05-20 | Lg化学株式会社 | Device for manufacturing carbon nanotube fibers and method for manufacturing carbon nanotube fibers using same |
| CN103435029A (en) * | 2013-09-05 | 2013-12-11 | 武汉博力信纳米科技有限公司 | Device and method for preparing continuous carbon nanotube aggregate by assistance of ultrasonic atomization |
| CN203820461U (en) * | 2013-09-27 | 2014-09-10 | 武汉博力信纳米科技有限公司 | Device for preparing continuous carbon nano tube fibers by carrying out box-sealed chemical gas-phase reaction |
Non-Patent Citations (1)
| Title |
|---|
| 刘玉军: "《纺粘和熔喷非织造布手册》", 30 April 2014, 北京：中国纺织出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108408716A (en) * | 2018-03-26 | 2018-08-17 | 苏州捷迪纳米科技有限公司 | System for manufacturing carbon nm tube |
| CN114477143A (en) * | 2022-03-25 | 2022-05-13 | 江西省纳米技术研究院 | Reaction furnace tube of carbon nanotube material, and growth device and method |
| CN114477143B (en) * | 2022-03-25 | 2023-09-22 | 江西省纳米技术研究院 | Reaction furnace tube of carbon nano tube material and growth device and method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9556542B2 (en) | Device for manufacturing carbon nanotube fibers and method for manufacturing carbon nanotube fibers using same | |
| FI121334B (en) | Method and apparatus for making carbon nanotubes | |
| CN102333906B (en) | Low temperature CNT growth using gas-preheat method | |
| KR100933028B1 (en) | Carbon nanotube manufacturing facility and manufacturing method of carbon nanotube using the same | |
| CN102648088B (en) | The metallic fiber material that CNT is incorporated to and method thereof | |
| EP3214212A1 (en) | Device for producing carbon nanotube fibers and method for producing carbon nanotube fibers using same | |
| JP6339742B2 (en) | Carbon nanotube fiber manufacturing equipment | |
| CA2561917C (en) | Ultrathin carbon fibers with various structures | |
| US20100000754A1 (en) | Carbon nanotube-based coaxial electrical cables and wiring harness | |
| CN101573467A (en) | Plasma surface treatment using dielectric barrier discharges | |
| CN106395796A (en) | A carbon nanotube wire rod, a preparing method thereof, a preparing device and applications | |
| CN107815755B (en) | Preparation device and preparation method for preparing carbon nanotube graphene composite fiber through multiple tubes | |
| US20090087638A1 (en) | Fine carbon fibrous structure | |
| CN108408716B (en) | Carbon nanotube preparation system | |
| CN110589805A (en) | Device and method for preparing carbon aerogel through CVD after carbon nanotubes are activated by electric arc | |
| US10889918B2 (en) | Method for controlling strength of carbon nanotube fiber aggregate | |
| AU2013230042A1 (en) | Resistance measurement system and method of using the same | |
| CN105070366B (en) | A kind of carbon nano-fiber cable and preparation method thereof | |
| KR20170061995A (en) | Device for manufacturing carbon nanotube aggregates and carbon nanotube aggregates manufactured using same | |
| EP3517658B1 (en) | Method for preparing carbon nanotube fiber having enhanced tensile strength | |
| CN205953534U (en) | Device of preparation graphite alkene | |
| CN115477300B (en) | Carbon nanotube, fluidized bed preparation process thereof and conductive agent | |
| KR20170059761A (en) | Device for manufacturing carbon nanotube aggregates and carbon nanotube aggregates manufactired using same | |
| US20210163252A1 (en) | Collection device and preparation system | |
| KR101951368B1 (en) | Apparatus for preparing carbon nanotube fiber and process for preparing carbon nanotube fiber using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170215 |