CN107057278B - Preparation device and preparation method for preparing carbon nano tube film composite material in one step - Google Patents
Preparation device and preparation method for preparing carbon nano tube film composite material in one step Download PDFInfo
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- CN107057278B CN107057278B CN201611054783.7A CN201611054783A CN107057278B CN 107057278 B CN107057278 B CN 107057278B CN 201611054783 A CN201611054783 A CN 201611054783A CN 107057278 B CN107057278 B CN 107057278B
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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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
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Abstract
The invention relates to the technical field of nano materials, in particular to a preparation device and a preparation method for preparing a carbon nano tube film composite material in one step. The preparation device comprises a reaction chamber and a collection chamber, wherein the collection chamber is provided with a conveyor belt for collecting carbon nanotube aggregates, an infiltration part and a pressing part, wherein the infiltration part is used for enabling a polymer matrix to infiltrate the surface of a carbon nanotube film formed on the conveyor belt, the polymer matrix infiltrates the surface of the carbon nanotube film through the infiltration part, and meanwhile the pressing part presses the surface of the carbon nanotube film to enable the carbon nanotube film to be combined with the polymer matrix to form a compact carbon nanotube film composite material; the collecting chamber is also provided with a heating device for curing and forming the carbon nanotube film composite material. The invention solves the difficult problems of infiltration and permeation of the polymer matrix in the carbon nanotube film network structure, simplifies the device and the production steps, and obviously improves the comprehensive performance of the finally prepared carbon nanotube film composite material.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation device and a preparation method for preparing a carbon nano tube film composite material in one step.
Background
Carbon Nanotubes (CNTs) have attracted extensive attention and considerable research interest worldwide since their discovery under high resolution electron microscopy in 1991. As a novel nano material, the unique geometric structure and the electronic energy band structure bring a plurality of excellent properties such as high strength, large specific surface area, high thermal conductivity, high carrier mobility and the like, and the excellent properties lead the carbon nano tube to have huge application prospect and potential in a plurality of fields.
The carbon nanotube film is an important macroscopic problem form for realizing the wide application of carbon nanotubes, and a macroscopic film material with the thickness of several nanometers to several micrometers and several tens of nanometers formed by mutually winding and connecting a large number of carbon nanotubes has been developed in the application research of important fields such as electronics, energy sources, intelligent sensing, composite materials, aerospace and the like. On the other hand, in view of the current increasing demands on material properties, there is a need to impart and combine in one new material the advantageous properties that two or more original single conventional materials do not possess, and composite materials have developed.
The carbon nanotube film composite material comprises a polymer matrix and carbon nanotubes, wherein the carbon nanotubes are arranged in the polymer matrix in the form of a carbon nanotube film structure. There are two general methods for preparing such carbon nanotube film composites: the first method is to prepare the carbon nanotube/polymer matrix composite from the carbon nanotube powder, strong acid, strong alkali or surfactant is commonly used in the dispersion process, the original complete structure and length of the carbon nanotube can be damaged to a certain extent, and the surfactant can remain in the carbon nanotube composite and is difficult to remove, so that the obtained carbon nanotube composite is not ideal in mechanical property and flexibility. For example: the Chinese patent application (publication No. CN 103172049A) discloses a preparation method of functionalized carbon nanotube paper and a composite material thereof, which has the technical scheme that carbon nanotubes are added into fuming sulfuric acid at the temperature of-10-140 ℃ for intercalation for 0.1-96 h, then are subjected to nitric acid oxidation treatment for 0.1-480 h under the stirring condition at the temperature of-10-60 ℃, and are filtered by a centrifugal separation or nanofiltration membrane, and are washed to be neutral by deionized water, so that the functionalized carbon nanotubes are obtained; freely dispersing the functionalized carbon nano tube in a solvent, and obtaining the functionalized carbon nano tube paper through suction filtration; finally, the thermosetting resin and the functionalized carbon nanotube paper are subjected to a resin presoaking process, a presoaking material hot-press molding process or a powder molding process to realize the carbon nanotube film composite material. The method has the defects that: (1) The carbon nano tube is pretreated by sulfuric acid to realize dispersion, and the structure of the carbon nano tube is damaged to a certain extent in the process; (2) The prepared carbon nanotube paper or film has compact structure, is difficult to be fully infiltrated with a subsequent polymer matrix (resin), and the resin is mostly covered on the surface of the carbon nanotube paper or film, so that the obtained composite material can not fully exert the reinforcing effect of the carbon nanotube network structure and the resin. The second method is to compound the prepared carbon nano tube film with the polymer matrix by means of soaking, spraying and the like to form a carbon nano tube composite material preform, and then to treat the preform by means of pressurizing, heating and the like to compound the carbon nano tube film with the polymer matrix to form the carbon nano tube film composite material. For example, chinese patent (publication No. CN 101456277B) discloses a method for preparing a carbon nanotube composite material, which comprises the steps of: preparing a self-supporting carbon nanotube film structure; providing a liquid thermosetting polymer material; impregnating the carbon nano tube film structure with the liquid thermosetting polymer material; and curing the carbon nano tube film structure infiltrated by the liquid thermosetting polymer material to obtain the carbon nano tube composite material. The method has the defects that: because the formed carbon nanotube film has high densification degree, less network gaps and longer polymer matrix chain segments, the polymer matrix cannot well infiltrate into the internal structure of the carbon nanotube film, so that defects of the composite material are increased, and the performance of the composite material is reduced. The presence of these defects severely reduces the reliability, electrical properties, water resistance, weatherability, chemical resistance, mechanical properties, etc. of the composite material. In addition, the two preparation methods involve more equipment and complicated steps, and are difficult to realize large-scale industrialized preparation.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a preparation device and a preparation method for preparing a carbon nano tube film composite material in one step, so as to solve the difficult problems of infiltration and permeation of a polymer matrix in a carbon nano tube film network structure, simplify the device and the production steps and save the time.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation device for preparing the carbon nanotube film composite material in one step comprises a reaction chamber for synthesizing carbon nanotube aggregates and a collection chamber communicated with the reaction chamber, wherein the collection chamber is provided with a conveyor belt for collecting the carbon nanotube aggregates, and the conveyor belt can be driven to move along a closed circulation track and can move along the axial direction of a transmission shaft so as to enable the carbon nanotube aggregates to be wound on the surface of the conveyor belt layer by layer in a superposition manner and form carbon nanotube films with adjustable thickness and width;
the collecting chamber is also provided with an infiltration component which can infiltrate the surface of the carbon nano tube film formed on the conveyor belt by the macromolecule matrix and a pressing component matched with the conveyor belt, the macromolecule matrix infiltrates the surface of the carbon nano tube film through the infiltration component, and meanwhile, the pressing component presses the surface of the carbon nano tube film to combine the carbon nano tube film and the macromolecule matrix to form a compact carbon nano tube film composite material;
the collecting chamber is also provided with a heating device for solidifying and forming the carbon nano tube film composite material.
Preferably, the pressing component and the impregnating component are integrated into a roller with a hollow structure, the surface of the roller is provided with holes, the polymer base can flow out of the holes and infiltrate the surface of the carbon nanotube film formed on the conveying belt, and meanwhile, the roller rolls the surface of the carbon nanotube film to enable the carbon nanotube film to be fully combined with the polymer base to form the compact carbon nanotube film composite material.
Preferably, the pressing component is a rolling device, and the wetting component is a spraying device or a coating device.
More preferably, the pressing member is movably connected to the collecting chamber such that a pressure between the pressing member and the conveyor belt is adjustable.
More preferably, the width of the pressing member is greater than the width of the carbon nanotube film along the axial direction of the driving shaft.
More preferably, the surfaces of the conveyor belt and the rolling device are both coated with a polytetrafluoroethylene material layer or the conveyor belt and the rolling device are both formed by polytetrafluoroethylene.
Preferably, the reaction chamber is provided with a raw material inlet and a carrier gas inlet. The reactant is injected into the reaction chamber from the raw material inlet, meanwhile, the carrier gas is introduced into the reaction chamber from the carrier gas inlet, and the reactant generates carbon nanotube aggregates in the reaction chamber and enters the collecting chamber to be collected under the action of the carrier gas.
The invention also provides a preparation method for preparing the carbon nanotube film composite material in one step, which is carried out by adopting the preparation device and comprises the following steps:
a) Injecting reactants into a reaction chamber, and simultaneously introducing carrier gas, wherein the reactants react at the constant temperature of 1100-1600 ℃ to generate carbon nano tube aggregates; the reactants comprise a carbon source, a catalyst and a promoter;
b) The carbon nanotube aggregate generated in the step a enters a collecting chamber under the action of carrier gas and is deposited on a conveyor belt, the carbon nanotube aggregate is wound on the surface of the conveyor belt along with the movement of the conveyor belt to form a single-layer carbon nanotube film with a certain thickness, and the single-layer carbon nanotube film with a certain width is obtained by adjusting the axial movement distance of the conveyor belt along a transmission shaft;
c) C, infiltrating the surface of the single-layer carbon nanotube film obtained in the step b through an infiltration component by the prepared polymer matrix, attaching a pressing component to a conveyor belt, and pressing the carbon nanotube film along with the movement of the conveyor belt, so that the carbon nanotube film and the polymer matrix are further combined to form a compact single-layer carbon nanotube film composite material;
d) C, heating, solidifying and forming the single-layer carbon nano tube film composite material obtained in the step c through a heating device;
e) And along with the movement of the conveyor belt along the closed circulation track, the carbon nano tube film composite material with adjustable thickness and area is finally obtained through layer-by-layer superposition.
Preferably, in the step a, the carbon source is at least one of methanol, ethanol and isopropanol;
the catalyst is at least one of ferrocene and nickel dichloride, and accounts for 0.1-3% of the total mass of the reactants;
the accelerator is at least one of thiophene and elemental sulfur, and accounts for 0.1-3% of the total mass of the reactants;
the carrier gas is hydrogen, nitrogen or mixed gas of hydrogen and inert gas, wherein the volume percentage of the hydrogen is 10-100%, and the inert gas is argon or helium; the gas flow of the carrier gas is 1-10L/min.
Preferably, the polymer matrix is a thermosetting or thermoplastic resin. If the fluidity of the polymer matrix is good at normal temperature, no solvent is added, and if the fluidity of the polymer matrix is poor at normal temperature, an organic solvent is added to dissolve the polymer matrix to increase the fluidity of the polymer matrix, wherein the organic solvent is a volatile solvent, and the optional solvent is ethanol, methanol, acetone or dichloroethane or other types of volatile solvents.
More preferably, the polymer matrix is a mixed solution prepared from epoxy resin and a solvent according to the mass ratio of (4-19), and the solvent is ethanol, methanol, acetone or dichloroethane; in the step d, the heating curing temperature is 110-130 ℃.
The invention has the beneficial effects that:
compared with the prior art, the preparation device and the preparation method of the carbon nanotube film composite material have the following advantages:
(1) The carbon nanotube film is directly formed on the surface of the conveyor belt by collecting the carbon nanotube aggregates through the conveyor belt, so that the pretreatment of the carbon nanotubes in the prior art to realize the dispersed surface treatment process is omitted, and the damage to the structure of the carbon nanotubes is avoided;
(2) In the collecting process, each layer of carbon nano tube film is directly infiltrated with a polymer matrix, so that the technical problem that a compact structure formed by the carbon nano tube film is unfavorable for the infiltration of the polymer matrix is solved, the three-dimensional network structure formed by mutually connecting carbon nano tubes is fully utilized, wherein the polymer matrix is uniformly coated between the carbon nano tubes and the tube bundles, and the carbon nano tube film is well infiltrated and can well fill the three-dimensional network gaps; the continuous pressure of the pressing part in the stacking process of the carbon nano tube thin films layer by layer is added to enable the formed carbon nano tube composite material to be more compact; the subsequent heating device is used for fixing the polymer matrix around the carbon nano tubes and the tube bundles thereof in the collecting process to prevent the solution from flowing and falling off, so that each carbon nano tube can be fully combined with the polymer matrix, and the comprehensive properties of electric conduction, heat conduction and the like of the finally prepared carbon nano tube film composite material are obviously improved;
(3) The preparation device can be used for preparing the carbon nanotube film composite material in one step, has the advantages of simple preparation method, wide applicability and low cost, saves complicated steps, simplifies manufacturing equipment and is suitable for large-scale production.
Drawings
Fig. 1 is a schematic structural diagram of a preparation apparatus for preparing a carbon nanotube film composite material in one step of example 1.
FIG. 2 is a schematic structural diagram of a roller of a device for preparing a carbon nanotube film composite material in one step of example 1
Reference numerals:
reaction chamber 1, collection chamber 2, conveyer belt 3, action wheel 4, follow driving wheel 5, running roller 6, hole 61, heating device 7, carbon nanotube aggregate 8, support arm 9.
Detailed Description
The present invention will be described in detail with reference to specific embodiments and drawings.
Example 1:
the preparation device for preparing the carbon nanotube film composite material in one step is shown in fig. 1, and comprises a reaction chamber 1 for synthesizing a carbon nanotube aggregate 8 and a collection chamber 2 communicated with the reaction chamber 1. The reaction chamber 1 can be arranged as a vertical or bedroom reaction furnace structure, the carbon nanotube aggregate 8 is synthesized by adopting a floating catalytic chemical vapor deposition method, the reaction chamber 1 is provided with a raw material inlet and a carrier gas inlet, reactants are injected into the reaction chamber 1 from the raw material inlet, meanwhile, the carrier gas is introduced into the reaction chamber 1 from the carrier gas inlet, the reactants generate the carbon nanotube aggregate 8 in the reaction chamber 1, and the carbon nanotube aggregate 8 enters the collecting chamber 2 to be collected under the action of the carrier gas.
The collecting chamber 2 is provided with a conveyor belt 3 for collecting the carbon nanotube aggregates 8, the carbon nanotube aggregates 8 synthesized by the reaction chamber 1 enter the collecting chamber 2 and are deposited on the conveyor belt 3, the conveyor belt 3 is in tensioning connection with the driven wheel 5 through a driving wheel 4, and a transmission shaft of the driving wheel 4 is connected with a motor (not shown in the figure). In the collecting process, the motor drives the driving wheel 4 to rotate at a constant speed, and then drives the conveyor belt 3 to move along a closed circulation track, so that the carbon nanotube aggregate 8 is wound on the surface of the conveyor belt 3 layer by layer in a superposition manner, and a carbon nanotube film with a certain thickness is formed. The thickness of each carbon nano tube film is only a few nanometers (such as 1-9 nm). The transmission shaft can be controlled to move along the axial direction so as to drive the conveyor belt 3 to move along the axial direction, so that the collection of carbon nanotube films with different widths in the axial direction is realized.
The collecting chamber 2 is further provided with an infiltration part which can infiltrate the surface of the carbon nanotube film formed on the conveyor belt 3 by a polymer matrix and a pressing part matched with the conveyor belt 3, the polymer matrix infiltrates the surface of the carbon nanotube film by the infiltration part, and meanwhile, the pressing part is matched with the conveyor belt 3 to press the surface of the carbon nanotube film so that the carbon nanotube film is combined with the polymer matrix to form a compact carbon nanotube film composite material. The wetting member and the pressing member are disposed near the collecting end of the conveyor belt 3.
In this embodiment, as shown in fig. 2, the pressing component and the impregnating component are integrated into a roller 6 with a hollow structure, holes are formed on the surface of the roller 6, and the number of the holes is preferably a plurality of holes, and the plurality of holes are uniformly distributed on the surface of the roller 6. The roller 6 is connected with an injector, a pre-configured polymer matrix is injected into the roller 6, then the polymer matrix can flow out of the holes and infiltrate the surface of the carbon nanotube film formed on the conveyor belt 3, and simultaneously the roller 6 is matched with the conveyor belt 3 to roll the surface of the carbon nanotube film so that the carbon nanotube film and the polymer matrix are fully combined to form a compact carbon nanotube film composite material.
The roller 6 is movably connected to the top of the collecting chamber 2 through a supporting arm 9, and the distance between the roller 6 and the conveyor belt 3 is adjustable, so that the pressure between the roller 6 and the conveyor belt 3 is adjustable.
The width of the roller 6 is greater than the width of the single-layer carbon nanotube film along the axial direction of the transmission shaft (i.e., the direction perpendicular to the plane of fig. 1), so that the surface of each layer of carbon nanotube film is uniformly and fully combined with the polymer matrix.
The surfaces of the conveyor belt 3 and the roller 6 are respectively coated with a polytetrafluoroethylene material layer, or the conveyor belt 3 and the roller 6 are respectively formed by polytetrafluoroethylene processing, so that van der Waals acting force between the carbon nanotube film and the surface of the conveyor belt 3 or the roller 6 can be reduced, and other material layers with the same function can be adopted.
In this embodiment, the collection chamber 2 is further provided with a heating device 7 for curing and molding the carbon nanotube film composite material. The heating device 7 can adjust the temperature and time according to different conditions of curing and forming the polymer matrix. At least one heating device 7 can be arranged at the tail part (the side far away from the collecting end in fig. 1) of the collecting box or at other positions, and the heating device 7 can be in the forms of a single panel, an upper panel, a lower panel, a semi-closed box body and the like.
The preparation device solves the difficult problems of infiltration and permeation of the polymer matrix in the carbon nano tube film structure in the prior art, and the polymer matrix is uniformly wrapped between the carbon nano tubes and the tube bundles in the finally obtained carbon nano tube film composite material, well infiltrates and fills the carbon nano tube bundles into the three-dimensional network gaps which are mutually connected with the carbon nano tubes, so that the comprehensive performance of the carbon nano tube film composite material is obviously improved.
Example 2:
the main technical scheme of the preparation device for preparing the carbon nanotube film composite material in one step is the same as that of the embodiment 1, and the difference is that:
the pressing part is a roller or other forms of rolling devices, the soaking part is a spraying device, and the spraying device is connected with a container for containing the polymer matrix.
In the collecting process, the macromolecule matrix is sprayed on the surface of the nanometer film through a spraying device to be infiltrated, and meanwhile, a rolling device is matched with a conveying belt 3 to roll the surface of the carbon nanometer film and the carbon nanometer tube film, so that the carbon nanometer film and the macromolecule matrix are combined to form a compact carbon nanometer tube film composite material.
Example 3:
the main technical scheme of the preparation device for preparing the carbon nanotube film composite material in one step is the same as that of the embodiment 1, and the difference is that:
the pressing part is a roller or other forms of rolling devices, the impregnating part is a coating device, the polymer matrix is coated on the surface of the nano film through the coating device for impregnating, and meanwhile, the rolling device is matched with the conveyor belt 3 to roll the surface of the carbon nano film carbon nano tube film so as to combine the carbon nano film carbon nano tube film with the polymer matrix to form the compact carbon nano tube film composite material.
Example 4:
the preparation method for preparing the carbon nanotube film composite material in one step by using the preparation device of the embodiment 1 to the embodiment 3 comprises the following steps:
a) Reactants are injected into the reaction chamber 1, and meanwhile, carrier gas is introduced, and the reactants react at the constant temperature of 1400 ℃ to generate the carbon nanotube aggregate 8. Specifically, the floating catalytic chemical vapor deposition method is adopted to synthesize the carbon nanotube aggregate 8, and reactants comprise a carbon source, a catalyst and an accelerator. Wherein:
the carbon source is methanol, a catalyst and an accelerator are dissolved in the methanol, the content of the catalyst is 1% of the total mass of the reactants, the accelerator is 2% of the total mass of the reactants, the catalyst is ferrocene, the accelerator is thiophene, the carrier gas is hydrogen, and the gas flow of the carrier gas is 1L/min.
b) The carbon nanotube aggregate 8 generated in the step a enters the collecting chamber 2 under the action of carrier gas and is deposited on the conveyor belt 3, the carbon nanotube aggregate 8 is wound on the surface of the conveyor belt 3 along with the movement of the conveyor belt 3 to form a single-layer carbon nanotube film with a certain thickness, and the single-layer carbon nanotube film with a certain width is obtained by adjusting the axial movement distance of the conveyor belt 3 along the transmission shaft.
c) And d, infiltrating the surface of the single-layer carbon nanotube film obtained in the step b through the allocated polymer matrix through an infiltration component, attaching a pressing component to the conveyor belt 3, and pressing the carbon nanotube film along with the movement of the conveyor belt 3, so that the carbon nanotube film and the polymer matrix are further combined to form a compact single-layer carbon nanotube film composite material. The polymer matrix is thermosetting or thermoplastic resin, if the fluidity of the polymer matrix is good at normal temperature, no solvent is added, if the fluidity of the polymer matrix is poor at normal temperature, an organic solvent is added to dissolve the polymer matrix to increase the fluidity of the polymer matrix, the organic solvent is a volatile solvent, and the optional solvent is ethanol, methanol, acetone or dichloroethane, or other volatile solvents.
d) C, heating, solidifying and forming the single-layer carbon nano tube film composite material obtained in the step c through a heating device 7.
e) And along with the movement of the conveyor belt 3 along the closed circulation track, overlapping the conveyor belt layer by layer for a certain time to finally obtain the carbon nano tube film composite material with adjustable thickness and area.
In the collecting process of layer-by-layer superposition, each layer of carbon nanotube film is directly infiltrated with a polymer matrix, so that the technical problem that a compact structure formed by the carbon nanotube film is unfavorable for the infiltration of the polymer matrix is solved, the three-dimensional network structure formed by mutually connecting carbon nanotubes is fully utilized, wherein the polymer matrix is uniformly coated between the carbon nanotubes and the tube bundles, and the carbon nanotube film is well infiltrated and can well fill the three-dimensional network gaps; the continuous pressure of the pressing part in the stacking process of the carbon nano tube thin films layer by layer is added to enable the formed carbon nano tube composite material to be more compact; and then the subsequent heating device 7 is used for fixing the polymer matrix around the carbon nano tubes and the tube bundles thereof in the collecting process to prevent the solution from flowing and falling off, so that each carbon nano tube can be fully combined with the polymer matrix, and the comprehensive properties of electric conduction, heat conduction and the like of the finally prepared carbon nano tube film composite material are obviously improved.
Example 5:
the main technical scheme of the embodiment is the same as that of embodiment 4, except that:
in step a, the reactants are reacted at a constant temperature of 1100 ℃ to produce carbon nanotube aggregates 8. The carbon source is ethanol, a catalyst and an accelerator are dissolved in the ethanol, the content of the catalyst is 2% of the total mass of the reactants, the accelerator is 3% of the total mass of the reactants, the catalyst is nickel dichloride, the accelerator is thiophene, and the carrier gas is mixed gas of hydrogen and helium, wherein the volume percentage of the hydrogen is 30%; the gas flow rate of the carrier gas was 5L/min.
The reactant also comprises an auxiliary agent, wherein the auxiliary agent accounts for 1% of the total mass of the reactant, and specifically, the auxiliary agent is water which is used as an oxidant.
In the step c, the polymer matrix is an epoxy resin solution prepared from epoxy resin and acetone, wherein the content of the epoxy resin is 10%. In step d, the heat curing temperature was set to 120 ℃.
Example 6:
the main technical scheme of the embodiment is the same as that of embodiment 5, except that:
in step a, the reactants are reacted at a constant temperature of 1600 ℃ to form carbon nanotube aggregates 8. The carbon source is isopropanol, a catalyst and an accelerator are dissolved in the isopropanol, the content of the catalyst is 3% of the total mass of the reactants, the accelerator is 1% of the total mass of the reactants, the catalyst is ferrocene, the accelerator is elemental sulfur, the carrier gas is helium, and the gas flow of the carrier gas is 8L/min.
The reactant also comprises an auxiliary agent, wherein the auxiliary agent accounts for 1% of the total mass of the reactant, and specifically, the auxiliary agent is a heteroatom precursor.
In the step c, the polymer matrix is an epoxy resin solution prepared from epoxy resin and acetone, wherein the content of the epoxy resin is 5%. In step d, the heat curing temperature was set to 110 ℃.
Example 7:
the main technical scheme of the embodiment is the same as that of embodiment 5, except that:
in step a, the reactants are reacted at a constant temperature of 1200 ℃ to produce carbon nanotube aggregates 8. The carbon source is ethanol, a catalyst and an accelerator are dissolved in the ethanol, the content of the catalyst is 2% of the total mass of the reactants, the accelerator is 2% of the total mass of the reactants, the catalyst is nickel dichloride, the accelerator is elemental sulfur, and the carrier gas is a mixed gas of hydrogen and argon, wherein the volume percentage of the hydrogen is 60%; the gas flow rate of the carrier gas was 10L/min.
In the step c, the polymer matrix is an epoxy resin solution prepared from epoxy resin and acetone, wherein the content of the epoxy resin is 20%. In step d, the heat curing temperature was set to 130 ℃.
Example 8:
the main technical scheme of the embodiment is the same as that of embodiment 5, except that:
in step a, the reactants are reacted at a constant temperature of 1500 ℃ to produce carbon nanotube aggregates 8. The carbon source is ethanol and methanol according to the volume ratio of 1: the mixed solution of 1, wherein a catalyst and a promoter are dissolved in ethanol, the content of the catalyst is 3% of the total mass of reactants, the content of the promoter is 2% of the total mass of reactants, the catalyst is a mixed solution of nickel-dicyclopentadienyl and ferrocene according to the volume ratio of 2:1, the promoter is a mixed solution of thiophene and elemental sulfur according to the volume ratio of 1:2, and the carrier gas is a mixed gas of hydrogen and argon, wherein the volume percentage of the hydrogen is 80%; the gas flow rate of the carrier gas was 3L/min.
In the step c, the polymer matrix is an epoxy resin solution prepared from epoxy resin and methanol, wherein the content of the epoxy resin is 15%. In step d, the heat curing temperature was set to 125 ℃.
Example 9:
the main technical scheme of the embodiment is the same as that of embodiment 5, except that:
in the step a, the carbon source is ethanol and methanol according to the volume ratio of 1: the mixed solution of 1, wherein a catalyst and an accelerator are dissolved in ethanol, the content of the catalyst is 3% of the total mass of reactants, the accelerator is 2% of the total mass of reactants, the catalyst is a mixed solution of nickel-dicyclopentadienyl and ferrocene according to the volume ratio of 2:1, the accelerator is a mixed solution of thiophene and elemental sulfur according to the volume ratio of 1:2, and the carrier gas is a mixed gas of hydrogen and helium, wherein the volume percentage of hydrogen is 10%; the gas flow rate of the carrier gas was 3L/min.
In the step c, the polymer matrix is an epoxy resin solution prepared from epoxy resin and ethanol, wherein the content of the epoxy resin is 15%. In step d, the heat curing temperature was set to 120 ℃.
Example 10:
the main technical scheme of the embodiment is the same as that of embodiment 5, except that:
in step a, the reactants are reacted at a constant temperature of 1300 ℃ to produce carbon nanotube aggregates 8. The carbon source is ethanol and isopropanol according to the volume ratio of 2:1, a catalyst and an accelerator are dissolved in a carbon source, the content of the catalyst is 1% of the total mass of the reactants, the accelerator is 2% of the total mass of the reactants, the catalyst is ferrocene, the accelerator is a mixed solution of thiophene and elemental sulfur according to a volume ratio of 2:1, and the carrier gas is nitrogen; the gas flow rate of the carrier gas was 6L/min.
In the step c, the polymer matrix is an epoxy resin solution prepared from epoxy resin and ethanol, wherein the content of the epoxy resin is 20%. In step d, the heat curing temperature was set to 120 ℃.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The preparation device for preparing the carbon nano tube film composite material in one step is characterized in that: the device comprises a reaction chamber for synthesizing the carbon nanotube aggregate and a collecting chamber communicated with the reaction chamber, wherein the collecting chamber is provided with a conveyor belt for collecting the carbon nanotube aggregate, and the conveyor belt can be driven to move along a closed circulation track and can move along the axial direction of a transmission shaft so that the carbon nanotube aggregate is wound on the surface of the conveyor belt layer by layer in a superposition manner and forms a carbon nanotube film with adjustable thickness and width;
the collecting chamber is also provided with an infiltration component which can infiltrate the surface of the carbon nano tube film formed on the conveyor belt by the macromolecule matrix and a pressing component matched with the conveyor belt, the macromolecule matrix infiltrates the surface of the carbon nano tube film through the infiltration component, and meanwhile, the pressing component presses the surface of the carbon nano tube film to combine the carbon nano tube film and the macromolecule matrix to form a compact carbon nano tube film composite material;
the collecting chamber is also provided with a heating device for solidifying and forming the carbon nano tube film composite material;
the pressing part and the infiltration part are integrated into a roller with a hollow structure, the surface of the roller is provided with holes, the macromolecule base can flow out of the holes and infiltrate the surface of the carbon nano tube film formed on the conveying belt, and meanwhile, the roller rolls the surface of the carbon nano tube film to enable the carbon nano tube film to be fully combined with the macromolecule base to form a compact carbon nano tube film composite material.
2. The apparatus for one-step preparation of carbon nanotube film composite material according to claim 1, wherein: the pressure applying component is movably connected with the collecting chamber so that the pressure between the pressure applying component and the conveyor belt can be adjusted.
3. The apparatus for one-step preparation of carbon nanotube film composite material according to claim 1, wherein: and the width of the pressing part is larger than that of the carbon nano tube film along the axial direction of the transmission shaft.
4. The apparatus for one-step preparation of carbon nanotube film composite material according to claim 2, wherein: and the surfaces of the conveying belt and the rolling device are respectively coated with a polytetrafluoroethylene material layer or the conveying belt and the rolling device are both formed by polytetrafluoroethylene in a processing mode.
5. The preparation method for preparing the carbon nano tube film composite material in one step is characterized by comprising the following steps: the production method is carried out by using the production apparatus according to any one of claims 1 to 4, and comprises the steps of:
a) Injecting reactants into a reaction chamber, and simultaneously introducing carrier gas, wherein the reactants react at the constant temperature of 1100-1600 ℃ to generate carbon nano tube aggregates; the reactants comprise a carbon source, a catalyst and a promoter;
b) The carbon nanotube aggregate generated in the step a enters a collecting chamber under the action of carrier gas and is deposited on a conveyor belt, the carbon nanotube aggregate is wound on the surface of the conveyor belt along with the movement of the conveyor belt to form a single-layer carbon nanotube film with a certain thickness, and the single-layer carbon nanotube film with a certain width is obtained by adjusting the axial movement distance of the conveyor belt along a transmission shaft;
c) C, infiltrating the surface of the single-layer carbon nanotube film obtained in the step b through an infiltration component by the prepared polymer matrix, attaching a pressing component to a conveyor belt, and pressing the carbon nanotube film along with the movement of the conveyor belt, so that the carbon nanotube film and the polymer matrix are further combined to form a compact single-layer carbon nanotube film composite material;
d) C, heating, solidifying and forming the single-layer carbon nano tube film composite material obtained in the step c through a heating device;
e) And along with the movement of the conveyor belt along the closed circulation track, the carbon nano tube film composite material with adjustable thickness and area is finally obtained through layer-by-layer superposition.
6. The method of manufacturing according to claim 5, wherein: in the step a, the carbon source is at least one of methanol, ethanol and isopropanol;
the catalyst is at least one of ferrocene and nickel dichloride, and accounts for 0.1-3% of the total mass of the reactants;
the accelerator is at least one of thiophene and elemental sulfur, and accounts for 0.1-3% of the total mass of the reactants;
the carrier gas is hydrogen, nitrogen or mixed gas of hydrogen and inert gas, wherein the volume percentage of the hydrogen is 10-100%, and the inert gas is argon or helium; the gas flow of the carrier gas is 1-10L/min.
7. The method of manufacturing according to claim 5, wherein: in the step c, the polymer matrix is thermosetting or thermoplastic resin.
8. The method of manufacturing according to claim 7, wherein: the polymer matrix is a mixed solution prepared from epoxy resin and a solvent according to the mass ratio of (4-19), wherein the solvent is ethanol, methanol, acetone or dichloroethane; in the step d, the heating curing temperature is 110-130 ℃.
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| CN108047471B (en) * | 2018-01-10 | 2020-12-29 | 中国航发北京航空材料研究院 | Continuous preparation method of graphene film prepreg |
| CN114571653A (en) * | 2022-02-23 | 2022-06-03 | 武汉市碳翁科技有限公司 | Carbon nanotube film winding device and using method thereof |
| CN115678304B (en) * | 2022-12-29 | 2023-06-30 | 北京碳垣新材料科技有限公司 | Carbon nanotube composite material, preparation method and preparation device |
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