CN107057278A - One step prepares the preparation facilities and preparation method of carbon nano-tube film composite - Google Patents
One step prepares the preparation facilities and preparation method of carbon nano-tube film composite Download PDFInfo
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- CN107057278A CN107057278A CN201611054783.7A CN201611054783A CN107057278A CN 107057278 A CN107057278 A CN 107057278A CN 201611054783 A CN201611054783 A CN 201611054783A CN 107057278 A CN107057278 A CN 107057278A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
The present invention relates to technical field of nano material, and in particular to a step prepares the preparation facilities and preparation method of carbon nano-tube film composite.Wherein, preparation facilities includes reative cell and collecting chamber, collecting chamber be provided with for collect carbon nanotube agglomerate conveyer belt, infiltration part and press member that the surface of carbon nano-tube film of the macromolecule matrix to being formed on conveyer belt infiltrated can be made, macromolecule matrix is infiltrated by infiltrating part to the surface of carbon nano-tube film, while carbon nano-tube film surface is pressed press member so that carbon nano-tube film is combined with macromolecule matrix and forms fine and close carbon nano-tube film composite；Collecting chamber is additionally provided with for making the heater of carbon nano-tube film composite curing molding.The present invention solves infiltration and infiltration problem of the macromolecule matrix in carbon nano-tube film network structure, and simplifies device and production stage, and the combination property of the carbon nano-tube film composite finally prepared is significantly improved.
Description
Technical field
The present invention relates to technical field of nano material, and in particular to a step prepares the preparation of carbon nano-tube film composite
Device and preparation method.
Background technology
CNT（CNT）, since being found since 1991 under high resolution electron microscopy, just caused global extensive pass
Note and great research interest.As a kind of new nano material, due to its unique geometry and electronic band structure
Many excellent performances such as intensity is high, pyroconductivity bigger than surface is high, carrier mobility is high etc. is brought, these are excellent
Performance causes CNT to there is huge application prospect and potentiality in various fields.
Carbon nano-tube film is to realize a kind of wide variety of important macroscopic view topic form of CNT, by a large amount of carbon nanometer
Pipe is intertwined and connected mutually the thickness to be formed between several nanometers to tens nanometers of micron mm-scale of macroscopic film material, in electricity
The application study of the key areas such as son, the energy, intelligent sensing, composite, Aero-Space has obtained certain progress.The opposing party
Face, in view of the continuous improvement currently for material performance requirement in a kind of new material, it is necessary to assign and have both two or more originals
There is the advantage performance not available for single traditional material, composite just arises at the historic moment.
For carbon nano-tube film composite, it includes macromolecule matrix and CNT, the CNT with
The form of carbon nano-tube thin-film structure is arranged in macromolecule matrix.The side of this carbon nano-tube film composite is prepared at present
Method generally has two kinds：First method is that prepared by carbon nanotube dust into CNT/polymer-based composite, dispersion process
In commonly use strong acid and strong base or surfactant, complete carbon nano tube structure and length originally can be caused to a certain extent
Destroy, and surfactant can remain in carbon nano tube compound material and be difficult to remove, therefore obtained carbon nanotube composite
The mechanical performance and pliability of material are undesirable.For example：Chinese invention patent application（Publication number CN103172049A）Disclose one
The preparation method of functionalized carbon nanotubes paper and its composite is planted, its technical scheme is by CNT at -10 ~ 140 DEG C
Add 0.1 ~ 96h of intercalation in oleum, then temperature be -10 ~ 60 DEG C, under stirring condition through nitric acid oxidation handle 0.1h ~
After 480h, filtered with centrifugation or nanofiltration membrane, washed through deionized water to neutrality, produce functionalized carbon nanotubes；High-ranking military officer
Energy carbon nano tube is freely scattered in solvent, and functionalized carbon nanotubes paper is produced through suction filtration；Finally by thermosetting resin and official
Energy carbon nano tube paper realizes CNT by resin prepreg technique, prepreg hot press forming technology or powder technology
Film composite material.The defect of this method is：（1）CNT is pre-processed using sulfuric acid it is scattered to realize, during
Structure to CNT has a certain degree of damage；（2）Carbon nanotube paper after preparation or membrane structure are fine and close, and follow-up
Macromolecule matrix（Resin）It is difficult to complete wetting, is covered in carbon nanotube paper or film surface resin, obtained composite more
The enhancing effect of carbon nanotube network and resin can not be given full play to.Second method is the carbon nanometer that will have been prepared
Pipe film forms carbon nano tube compound material precast body using the modes such as immersion, spraying and polymer-based bluk recombination, and repressurization adds
The modes such as heat, which handle the precast body, makes carbon nano-tube film be compounded to form carbon nano-tube film composite with macromolecule matrix.Example
Such as Chinese invention patent（Publication number CN101456277B）Disclose a kind of preparation method of carbon nano tube compound material, this method
Comprise the following steps：Prepare the carbon nano-tube thin-film structure of a self-supporting；One liquid thermosetting high polymer material is provided；Will be described
Liquid thermosetting high polymer material infiltrates the carbon nano-tube thin-film structure；Solidification is above-mentioned to be soaked by liquid thermosetting high polymer material
The carbon nano-tube thin-film structure of profit, obtains a carbon nano tube compound material.The defect of this method is：Due to molded carbon nanometer
The densification degree of pipe film itself is very high, and network space is less, and macromolecule matrix segment is long so that polymer-based
Body can not infiltrate in the internal structure of carbon nano-tube film well, so as to cause the defect of composite to increase, so as to drop
The low performance of composite.The presence of these defects, seriously reduce the reliability of composite, electric property, water resistance,
Against weather, chemical resistance and mechanical property etc..In addition, above two preparation method is related to equipment many, complex steps, it is difficult to
It is prepared by heavy industrialization.
The content of the invention
There is above-mentioned technical problem for prior art, carbon nano-tube film is prepared it is an object of the invention to provide a step
The preparation facilities and preparation method of composite, with solve infiltration of the macromolecule matrix in carbon nano-tube film network structure and
Problem is permeated, and simplifies device and production stage, the time is saved.
To achieve the above object, the present invention provides following technical scheme：
The preparation facilities that one step prepares carbon nano-tube film composite is provided, including for the anti-of synthesizing carbon nanotubes aggregation
Room and the collecting chamber connected with the reative cell are answered, the collecting chamber is provided with for collecting the carbon nanotube agglomerate
Conveyer belt, the conveyer belt can drivingly be moved along closed circulation track and can be along the axial movement of power transmission shaft so that described
Carbon nanotube agglomerate is wound in the surface of the conveyer belt and forms the adjustable carbon of thickness and width size with being layering
Nano-tube film；
The surface that the collecting chamber is additionally provided with the carbon nano-tube film that macromolecule matrix can be made to being formed on conveyer belt is carried out
The infiltration part of infiltration and the press member for coordinating the conveyer belt, macromolecule matrix is by the infiltration part to carbon nanometer
The surface of pipe film is infiltrated, at the same the press member to carbon nano-tube film surface press so that carbon nano-tube film with
Macromolecule matrix combines and forms fine and close carbon nano-tube film composite；
The collecting chamber is additionally provided with for making the heater of the carbon nano-tube film composite curing molding.
It is preferred that, the press member and the infiltration part set turn into the disk roller with hollow structure, the disk roller
Surface offers hole, and macromolecule matrix can flow out and to the surface of the carbon nano-tube film formed on conveyer belt from the hole
Infiltrated, at the same the disk roller to carbon nano-tube film surface rolling so that carbon nano-tube film is fully tied with macromolecule matrix
Close and form fine and close carbon nano-tube film composite.
It is preferred that, the press member is rolling device, and the infiltration part is spray equipment or apparatus for coating.
It is furthermore preferred that the press member is movably connected on the collecting chamber so that the press member and the conveyer belt
Between pressure adjustable section.
It is furthermore preferred that along transmission shafts to the width of the press member is more than the width of the carbon nano-tube film.
It is furthermore preferred that the surface of the conveyer belt and the rolling device is coated with polytetrafluoroethylmaterial material layer or institute
Conveyer belt and the rolling device are stated by polytetrafluoroethylene (PTFE) machine-shaping.
It is preferred that, the reative cell is provided with material inlet and carrier gas inlet.Reactant injects reative cell by material inlet,
Carrier gas simultaneously is passed through reative cell by carrier gas inlet, and reactant generates carbon nanotube agglomerate in reative cell, and in the work of carrier gas
It is collected with lower entrance collecting chamber.
The present invention also provides the preparation method that a step prepares carbon nano-tube film composite, and the preparation method is to use
What above-mentioned preparation facilities was carried out, it comprises the following steps：
a）Reactant is injected into reative cell, while being passed through carrier gas, reactant reacts generation carbon under 1100-1600 DEG C of constant temperature and received
Mitron aggregation；The reactant includes carbon source, catalyst and accelerator；
b）The carbon nanotube agglomerate of step a generations enters collecting chamber in the presence of carrier gas, and deposition is on a moving belt, with
The movement of conveyer belt, carbon nanotube agglomerate is wrapped in the surface of conveyer belt and formed with certain thickness single-layer carbon nano-tube
Film, and by adjusting axial movement distance of the conveyer belt along power transmission shaft, obtain the single-layer carbon nano-tube with one fixed width thin
Film；
c）The macromolecule matrix configured is soaked by infiltrating part to the single-layer carbon nano-tube film surface that step b is obtained
Profit, while press member is fitted with conveyer belt and pressed with the movement of conveyer belt to carbon nano-tube film, so that carbon is received
Mitron film and macromolecule matrix further combined with and form fine and close single-layer carbon nano-tube film composite material；
d）The single-layer carbon nano-tube film composite material that step c is obtained passes through heating devices heat curing molding；
e）With conveyer belt moving along closed circulation track, by being layering, finally give thickness and size is adjustable
Carbon nano-tube film composite.
It is preferred that, in step a, the carbon source is at least one of methanol, ethanol, isopropanol；
The catalyst is at least one of ferrocene and dicyclopentadienyl nickel, and it accounts for the 0.1-3% of reactant gross mass；
The accelerator is at least one of thiophene and sulphur simple substance, and it accounts for the 0.1-3% of reactant gross mass；
The carrier gas is the mixed gas of hydrogen, nitrogen or hydrogen and inert gas, wherein the percent by volume of the hydrogen
For 10 ~ 100%, the inert gas is argon gas or helium；The gas flow of the carrier gas is 1 ~ 10L/min.
It is preferred that, the macromolecule matrix is thermosetting or thermoplastic resin.If mobility is good under macromolecule matrix normal temperature
It is good then without adding solvent, need to add organic solvent to dissolve if mobility under macromolecule matrix normal temperature is bad to increase high score
The mobility of subbase body, and organic solvent is volatile solvent, optional solvent is ethanol, methanol, acetone or two chloroethenes
Alkane, or other kinds of volatile solvent.
It is furthermore preferred that the macromolecule matrix is epoxy resin and solvent according to mass ratio 1:（4~19）The mixing being made is molten
Liquid, the solvent is ethanol, methanol, acetone or dichloroethanes；In step d, the temperature that is heating and curing is 110 ~ 130 DEG C.
Beneficial effects of the present invention：
Compared with prior art, the preparation facilities and preparation method of the carbon nano-tube film composite in the present invention have following
Advantage：
（1）The carbon nano-tube film of the present invention is directly collected carbon nanotube agglomerate by conveyer belt and formed in transmission belt surface
, eliminate prior art and CNT is pre-processed to realize scattered surface treatment process, so as to avoid to carbon
The destruction of nano tube structure；
（2）During collection, each layer of carbon nano-tube film with macromolecule matrix direct invasion, solve CNT thin
Compact texture after film shaping is unfavorable for the technical barrier of macromolecule matrix infiltration, the three-dimensional network for being connected with each other CNT
Structure, which is obtained, have been made full use of, and wherein macromolecule matrix is uniformly coated between CNT and tube bank, and good infiltration simultaneously can be very
Three-dimensional network gap is filled well；In addition continuous of the press member during carbon nano-tube film stacked in multi-layers makes to be formed
Carbon nano tube compound material it is finer and close；Pass through follow-up heater again so that macromolecule matrix is during collection
Being fixed on around CNT and its tube bank avoids solution flowing from coming off, and each CNT can be filled with macromolecule matrix
Divide and combine, so that the combination property such as conduction, heat conduction of carbon nano-tube film composite for finally preparing is significantly improved；
（3）Using the preparation facilities of the present invention, a step can complete the preparation to carbon nano-tube film composite, preparation method
Simply, applicability is wide, with low cost, saves cumbersome step, and simplifies manufacturing equipment, with suitable large-scale production
Advantage.
Brief description of the drawings
Fig. 1 prepares the structural representation of the preparation facilities of carbon nano-tube film composite for a step of embodiment 1.
Fig. 2 prepares the structural representation of the disk roller of the preparation facilities of carbon nano-tube film composite for a step of embodiment 1
Figure
Reference：
Reative cell 1, collecting chamber 2, conveyer belt 3, driving wheel 4, driven pulley 5, disk roller 6, hole 61, heater 7, CNT aggregation
Body 8, support arm 9.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, the present invention is described in detail.
Embodiment 1：
One step prepares the preparation facilities of carbon nano-tube film composite, as shown in figure 1, including for synthesizing carbon nanotubes aggregation
The reative cell 1 of body 8 and the collecting chamber 2 connected with reative cell 1.Reative cell 1 could be arranged to vertical or bedroom reacting furnace knot
Structure, using floating catalytic chemical vapour deposition technique synthesizing carbon nanotubes aggregation 8, reative cell 1 is provided with material inlet and carrier gas
Import, reactant injects reative cell 1 by material inlet, while carrier gas is passed through reative cell 1 by carrier gas inlet, reactant is in reative cell
Generation carbon nanotube agglomerate 8 in 1, carbon nanotube agglomerate 8 is collected in the presence of carrier gas into collecting chamber 2.
Collecting chamber 2 is provided with the conveyer belt 3 for collecting carbon nanotube agglomerate 8, and the CNT that reative cell 1 is synthesized gathers
Collective 8 enters collecting chamber 2 and is deposited on conveyer belt 3, and conveyer belt 3 is connected by driving wheel 4 and the tensioning of driven pulley 5, driving wheel 4
Power transmission shaft connection motor（Do not represented in figure）.During collection, motor driving driving wheel 4 at the uniform velocity rotates, and then drives biography
Send band 3 to be moved along closed circulation track, carbon nanotube agglomerate 8 is wound in surface and the formation of conveyer belt 3 with being layering
Certain thickness carbon nano-tube film.The thickness of every layer of carbon nano-tube film is only several nanometers of thickness（Such as 1 ~ 9nm）.Pass
Moving axis can be axially moveable in which be controlled, and then drive conveyer belt 3 to be axially moveable, to realize in the axial direction to different in width
The collection of carbon nano-tube film.
The surface that collecting chamber 2 is additionally provided with the carbon nano-tube film that macromolecule matrix can be made to being formed on conveyer belt 3 is entered
The infiltration part of row infiltration and the press member for coordinating conveyer belt 3, macromolecule matrix are thin to CNT by infiltrating part
The surface of film is infiltrated, while press member coordinates conveyer belt 3 to press so that CNT is thin carbon nano-tube film surface
Film is combined and formed the carbon nano-tube film composite of densification with macromolecule matrix.Infiltration part and press member are arranged on and leaned on
The collecting terminal of nearly conveyer belt 3.
In the present embodiment, as shown in Fig. 2 press member and infiltration part set turn into the disk roller 6 with hollow structure, disk roller
6 surface offers hole, and the quantity in hole is preferably multiple, and multiple holes are evenly distributed on the surface of disk roller 6.Disk roller 6 connects syringe,
Pre-configured macromolecule matrix is injected into disk roller 6, then macromolecule matrix can flow out and to conveyer belt 3 from hole
The surface of the carbon nano-tube film of upper formation is infiltrated, while disk roller 6 coordinates conveyer belt 3 to carbon nano-tube film surface rolling
So that carbon nano-tube film is fully combined and formed the carbon nano-tube film composite of densification with macromolecule matrix.
Disk roller 6 is movably connected on the top of collecting chamber 2 by support arm 9, and the spacing of disk roller 6 and conveyer belt 3 is adjustable, so that roller
Pressure adjustable section between wheel 6 and conveyer belt 3.
Along the axial direction of power transmission shaft（I.e. perpendicular to the direction of plane where Fig. 1）, the width of disk roller 6 is more than single-layer carbon nano-tube
The width of film, so that the surface of each layer of carbon nano-tube film is uniform and is fully combined with macromolecule matrix.
The surface of conveyer belt 3 and disk roller 6 is coated with polytetrafluoroethylmaterial material layer, or conveyer belt 3 and disk roller 6 by poly-
Tetrafluoroethene machine-shaping, to reduce the model ylid bloom action power between carbon nano-tube film and conveyer belt 3 or the surface of disk roller 6,
There can be the material layer of equivalent effect using other.
In this implementation, collecting chamber 2 is additionally provided with for making the heater of carbon nano-tube film composite curing molding
7.Heater 7 can arbitrarily adjust temperature and time according to the condition difference of different macromolecule matrix curing moldings.Heating dress
Put 7 at least one, collecting box afterbody can be arranged on（Side away from collecting terminal in Fig. 1）Or other positions, heater 7
Can be the forms such as single sided board, upper and lower panel, semiclosed casing.
The present invention preparation facilities solve infiltration of the prior art macromolecule matrix in carbon nano-tube thin-film structure and
Permeate in problem, the carbon nano-tube film composite finally given, macromolecule matrix is uniform between CNT and tube bank
Parcel, well infiltrates and fills in the three-dimensional network gap being connected with each other to CNT, so that carbon nano-tube film is compound
The combination property of material is significantly improved.
Embodiment 2：
One step prepares the preparation facilities of carbon nano-tube film composite, the main technical schemes and embodiment 1 of the present embodiment
Identical, difference is：
Press member is disk roller or the rolling device of other forms, and infiltration part is spray equipment, and spray equipment is connected to contain
Put the container of macromolecule matrix.
During collection, macromolecule matrix is sprayed by spray equipment to be infiltrated in the surface of nano thin-film, is rolled simultaneously
Pressure device coordinate conveyer belt 3 to the surface rolling of carbon nanocapsule thin film carbon nano-tube film so that carbon nanocapsule thin film carbon nano-tube film with
Macromolecule matrix combines and forms fine and close carbon nano-tube film composite.
Embodiment 3：
One step prepares the preparation facilities of carbon nano-tube film composite, the main technical schemes and embodiment 1 of the present embodiment
Identical, difference is：
Press member is disk roller or the rolling device of other forms, and infiltration part is apparatus for coating, and macromolecule matrix passes through coating
The surface that device is coated on nano thin-film is infiltrated, while rolling device coordinates conveyer belt 3 to carbon nanocapsule thin film CNT
Film surface is rolled so that carbon nanocapsule thin film carbon nano-tube film is combined with macromolecule matrix and it is thin to form fine and close CNT
Film composite material.
Embodiment 4：
The preparation method that one step prepares carbon nano-tube film composite is carried out using the preparation facilities of embodiment 1 to embodiment 3,
Comprise the following steps：
a）Reactant is injected into reative cell 1, while being passed through carrier gas, reactant reacts generation CNT under 1400 DEG C of constant temperature
Aggregation 8.Specifically, using floating catalytic chemical vapour deposition technique synthesizing carbon nanotubes aggregation 8, reactant include carbon source,
Catalyst, accelerator.Wherein：
Carbon source is that catalyst and accelerator are dissolved with methanol, methanol, and the content of catalyst accounts for the 1% of reactant gross mass, promotion
Agent accounts for the 2% of reactant gross mass, and catalyst is ferrocene, and accelerator is thiophene, and carrier gas is hydrogen, and the gas flow of carrier gas is
1L/min。
b）The carbon nanotube agglomerate 8 of step a generations enters collecting chamber 2 in the presence of carrier gas, and is deposited on conveyer belt 3
On, with the movement of conveyer belt 3, carbon nanotube agglomerate 8 is wrapped in the surface of conveyer belt 3 and formed with certain thickness list
Layer carbon nano-tube film, and by adjusting axial movement distance of the conveyer belt 3 along power transmission shaft, obtain the individual layer with one fixed width
Carbon nano-tube film.
c）The macromolecule matrix configured is entered by infiltrating part to the single-layer carbon nano-tube film surface that step b is obtained
Row infiltration, while press member is fitted with conveyer belt 3 and as the movement of conveyer belt 3 presses to carbon nano-tube film, with
Make carbon nano-tube film and macromolecule matrix further combined with and form fine and close single-layer carbon nano-tube film composite material.High score
Subbase body is thermosetting or thermoplastic resin, without adding solvent if good fluidity under macromolecule matrix normal temperature, if high score
Mobility is bad under subbase body normal temperature, needs to add organic solvent to dissolve to increase the mobility of macromolecule matrix, and organic molten
Agent is volatile solvent, and optional solvent is ethanol, methanol, acetone either dichloroethanes or other kinds of volatilizable
Property solvent.
d）The single-layer carbon nano-tube film composite material that step c is obtained is heating and curing shaping by heater 7.
e）With the moving along closed circulation track of conveyer belt 3, by being layering for certain time, thickness is finally given
With the adjustable carbon nano-tube film composite of size.
During the collection being layering, each layer of carbon nano-tube film with macromolecule matrix direct invasion, solve
Compact texture after carbon nano-tube film shaping is unfavorable for the technical barrier of macromolecule matrix infiltration, the CNT is mutually interconnected
The three-dimensional net structure connect, which is obtained, have been made full use of, and wherein macromolecule matrix is uniformly coated between CNT and tube bank, well
Infiltrate and three-dimensional network gap can be filled well；In addition press member holding during carbon nano-tube film stacked in multi-layers
Continuous pressure makes the carbon nano tube compound material to be formed finer and close；Pass through follow-up heater 7 again so that during collection
Macromolecule matrix is to be fixed on around CNT and its tube bank to avoid solution flowing from coming off, and allows each CNT can be with
Macromolecule matrix is fully combined, so that the combination property such as conduction, heat conduction of carbon nano-tube film composite for finally preparing
It is significantly improved.
Embodiment 5：
One step prepares the preparation method of carbon nano-tube film composite, the main technical schemes and embodiment 4 of the present embodiment
Identical, difference is：
In step a, reactant reacts generation carbon nanotube agglomerate 8 under 1100 DEG C of constant temperature.Carbon source is molten in ethanol, ethanol
Solution has catalyst and accelerator, and the content of catalyst accounts for the 2% of reactant gross mass, and accelerator accounts for the 3% of reactant gross mass, urges
Agent is dicyclopentadienyl nickel, and accelerator is thiophene, and carrier gas is the mixed gas of hydrogen and helium, and wherein hydrogen volume percentage is 30%；
The gas flow of carrier gas is 5L/min.
Reactant also includes adjuvant, and adjuvant accounts for the 1% of reactant gross mass, specifically, adjuvant is water, its conduct
Oxidant is used.
In step c, macromolecule matrix is the epoxy resin solution that epoxy resin and acetone are made, and its epoxy resin contains
Measure as 10%.In step d, the temperature setting that is heating and curing is 120 DEG C.
Embodiment 6：
One step prepares the preparation method of carbon nano-tube film composite, the main technical schemes and embodiment 5 of the present embodiment
Identical, difference is：
In step a, reactant reacts generation carbon nanotube agglomerate 8 under 1600 DEG C of constant temperature.Carbon source is isopropanol, isopropanol
In be dissolved with catalyst and accelerator, the content of catalyst accounts for the 3% of reactant gross mass, and accelerator accounts for reactant gross mass
1%, catalyst is ferrocene, and accelerator is sulphur simple substance, and carrier gas is helium, and the gas flow of carrier gas is 8L/min.
Reactant also includes adjuvant, and adjuvant accounts for the 1% of reactant gross mass, specifically, adjuvant is hetero atom forerunner
Body.
In step c, macromolecule matrix is the epoxy resin solution that epoxy resin and acetone are made, and its epoxy resin contains
Measure as 5%.In step d, the temperature setting that is heating and curing is 110 DEG C.
Embodiment 7：
One step prepares the preparation method of carbon nano-tube film composite, the main technical schemes and embodiment 5 of the present embodiment
Identical, difference is：
In step a, reactant reacts generation carbon nanotube agglomerate 8 under 1200 DEG C of constant temperature.Carbon source is molten in ethanol, ethanol
Solution has catalyst and accelerator, and the content of catalyst accounts for the 2% of reactant gross mass, and accelerator accounts for the 2% of reactant gross mass, urges
Agent is dicyclopentadienyl nickel, and accelerator is sulphur simple substance, and carrier gas is the mixed gas of hydrogen and argon gas, and wherein hydrogen volume percentage is
60%；The gas flow of carrier gas is 10L/min.
In step c, macromolecule matrix is the epoxy resin solution that epoxy resin and acetone are made, and its epoxy resin contains
Measure as 20%.In step d, the temperature setting that is heating and curing is 130 DEG C.
Embodiment 8：
One step prepares the preparation method of carbon nano-tube film composite, the main technical schemes and embodiment 5 of the present embodiment
Identical, difference is：
In step a, reactant reacts generation carbon nanotube agglomerate 8 under 1500 DEG C of constant temperature.Carbon source is that ethanol and methanol are pressed
According to volume ratio 1：Catalyst and accelerator are dissolved with 1 mixed solution, ethanol, the content of catalyst accounts for reactant gross mass
3%, accelerator accounts for the 2% of reactant gross mass, and catalyst is dicyclopentadienyl nickel and ferrocene according to volume ratio 2:1 mixed solution, promotees
It is thiophene and sulphur simple substance according to volume ratio 1 to enter agent:2 mixed solution, carrier gas is the mixed gas of hydrogen and argon gas, wherein hydrogen
Percent by volume is 80%,；The gas flow of carrier gas is 3L/min.
In step c, macromolecule matrix is the epoxy resin solution that epoxy resin and methanol are made, and its epoxy resin contains
Measure as 15%.In step d, the temperature setting that is heating and curing is 125 DEG C.
Embodiment 9：
One step prepares the preparation method of carbon nano-tube film composite, the main technical schemes and embodiment 5 of the present embodiment
Identical, difference is：
In step a, carbon source is ethanol and methanol according to volume ratio 1：Catalyst and promotion are dissolved with 1 mixed solution, ethanol
Agent, the content of catalyst accounts for the 3% of reactant gross mass, and accelerator accounts for the 2% of reactant gross mass, and catalyst is dicyclopentadienyl nickel and two
Luxuriant iron is according to volume ratio 2:1 mixed solution, accelerator is thiophene and sulphur simple substance according to volume ratio 1:2 mixed solution, carrier gas
For the mixed gas of hydrogen and helium, wherein hydrogen volume percentage is 10%；The gas flow of carrier gas is 3L/min.
In step c, macromolecule matrix is the epoxy resin solution that epoxy resin and ethanol are made, and its epoxy resin contains
Measure as 15%.In step d, the temperature setting that is heating and curing is 120 DEG C.
Embodiment 10：
One step prepares the preparation method of carbon nano-tube film composite, the main technical schemes and embodiment 5 of the present embodiment
Identical, difference is：
In step a, reactant reacts generation carbon nanotube agglomerate 8 under 1300 DEG C of constant temperature.Carbon source is ethanol and isopropanol
According to volume ratio 2：Catalyst and accelerator are dissolved with 1 mixed solution, carbon source, the content of catalyst accounts for reactant gross mass
1%, accelerator accounts for the 2% of reactant gross mass, and catalyst is ferrocene, and accelerator is thiophene and sulphur simple substance according to volume ratio 2:
1 mixed solution, carrier gas is nitrogen；The gas flow of carrier gas is 6L/min.
In step c, macromolecule matrix is the epoxy resin solution that epoxy resin and ethanol are made, and its epoxy resin contains
Measure as 20%.In step d, the temperature setting that is heating and curing is 120 DEG C.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than to present invention guarantor
The limitation of scope is protected, although being explained with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Work as understanding, technical scheme can be modified or equivalent substitution, without departing from the reality of technical solution of the present invention
Matter and scope.
Claims (10)
1. a step prepares the preparation facilities of carbon nano-tube film composite, it is characterised in that：Including for synthesizing carbon nanotubes
The reative cell of aggregation and the collecting chamber connected with the reative cell, the collecting chamber are provided with for collecting the carbon nanometer
The conveyer belt of pipe aggregation, the conveyer belt can drivingly be moved along closed circulation track and can moved along the axial direction of power transmission shaft
Move so that the carbon nanotube agglomerate is wound in the surface of the conveyer belt and forms thickness and width size with being layering
Adjustable carbon nano-tube film；
The surface that the collecting chamber is additionally provided with the carbon nano-tube film that macromolecule matrix can be made to being formed on conveyer belt is carried out
The infiltration part of infiltration and the press member for coordinating the conveyer belt, macromolecule matrix is by the infiltration part to carbon nanometer
The surface of pipe film is infiltrated, at the same the press member to carbon nano-tube film surface press so that carbon nano-tube film with
Macromolecule matrix combines and forms fine and close carbon nano-tube film composite；
The collecting chamber is additionally provided with for making the heater of the carbon nano-tube film composite curing molding.
2. a step according to claim 1 prepares the preparation facilities of carbon nano-tube film composite, it is characterised in that：Institute
Stating press member and the infiltration part set turns into the disk roller with hollow structure, and the surface of the disk roller offers hole, high score
Subbase body can flow out from the hole and the surface of carbon nano-tube film to being formed on conveyer belt infiltrates, while described
Disk roller is to carbon nano-tube film surface rolling so that carbon nano-tube film is fully combined and formed the carbon of densification with macromolecule matrix
Nano-tube film composite.
3. a step according to claim 1 prepares the preparation facilities of carbon nano-tube film composite, it is characterised in that：Institute
Press member is stated for rolling device, the infiltration part is spray equipment or apparatus for coating.
4. the step according to Claims 2 or 3 prepares the preparation facilities of carbon nano-tube film composite, its feature exists
In：The press member is movably connected on the collecting chamber so that pressure adjustable between the press member and the conveyer belt
Section.
5. the step according to Claims 2 or 3 prepares the preparation facilities of carbon nano-tube film composite, its feature exists
In：Along transmission shafts to the width of the press member is more than the width of the carbon nano-tube film.
6. a step according to claim 4 prepares the preparation facilities of carbon nano-tube film composite, it is characterised in that：Institute
The surface for stating conveyer belt and the rolling device is coated with polytetrafluoroethylmaterial material layer or the conveyer belt and the rolling
Device is by polytetrafluoroethylene (PTFE) machine-shaping.
7. a step prepares the preparation method of carbon nano-tube film composite, it is characterised in that：The preparation method is using power
Profit requires what the preparation facilities described in 1 to 6 any one was carried out, and it comprises the following steps：
a）Reactant is injected into reative cell, while being passed through carrier gas, reactant reacts generation carbon under 1100-1600 DEG C of constant temperature and received
Mitron aggregation；The reactant includes carbon source, catalyst and accelerator；
b）The carbon nanotube agglomerate of step a generations enters collecting chamber in the presence of carrier gas, and deposition is on a moving belt, with
The movement of conveyer belt, carbon nanotube agglomerate is wrapped in the surface of conveyer belt and formed with certain thickness single-layer carbon nano-tube
Film, and by adjusting axial movement distance of the conveyer belt along power transmission shaft, obtain the single-layer carbon nano-tube with one fixed width thin
Film；
c）The macromolecule matrix configured is soaked by infiltrating part to the single-layer carbon nano-tube film surface that step b is obtained
Profit, while press member is fitted with conveyer belt and pressed with the movement of conveyer belt to carbon nano-tube film, so that carbon is received
Mitron film and macromolecule matrix further combined with and form fine and close single-layer carbon nano-tube film composite material；
d）The single-layer carbon nano-tube film composite material that step c is obtained passes through heating devices heat curing molding；
e）With conveyer belt moving along closed circulation track, by being layering, finally give thickness and size is adjustable
Carbon nano-tube film composite.
8. preparation method according to claim 7, it is characterised in that：In step a, the carbon source is methanol, ethanol, isopropyl
At least one of alcohol；
The catalyst is at least one of ferrocene and dicyclopentadienyl nickel, and it accounts for the 0.1-3% of reactant gross mass；
The accelerator is at least one of thiophene and sulphur simple substance, and it accounts for the 0.1-3% of reactant gross mass；
The carrier gas is the mixed gas of hydrogen, nitrogen or hydrogen and inert gas, wherein the percent by volume of the hydrogen
For 10 ~ 100%, the inert gas is argon gas or helium；The gas flow of the carrier gas is 1 ~ 10L/min.
9. preparation method according to claim 7, it is characterised in that：In step c, the macromolecule matrix be thermosetting or
Thermoplastic resin.
10. preparation method according to claim 9, it is characterised in that：The macromolecule matrix is epoxy resin and solvent
According to mass ratio 1:（4~19）The mixed solution being made, the solvent is ethanol, methanol, acetone or dichloroethanes；Step d
In, the temperature that is heating and curing is 110 ~ 130 DEG C.
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