CN108656652A - Carbon nano-tube fibre composite material and preparation method - Google Patents
Carbon nano-tube fibre composite material and preparation method Download PDFInfo
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- CN108656652A CN108656652A CN201710205685.7A CN201710205685A CN108656652A CN 108656652 A CN108656652 A CN 108656652A CN 201710205685 A CN201710205685 A CN 201710205685A CN 108656652 A CN108656652 A CN 108656652A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
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Abstract
The invention discloses a kind of carbon nano-tube fibre composite material and preparation methods.The preparation method includes：One-dimensional carbon nano-tube fibre is provided；Using the methods of winding layer by layer, stacking, and reinforcement is added, carbon nano-tube fibre stacked in multi-layers is made to arrange, forms the composite material presoaked body of carbon nano-tube fibre with layered composite structure；And forming processes are carried out to the composite material presoaked body of carbon nano-tube fibre, to obtain carbon nano-tube fibre composite material.The present invention passes through the regulation and control between each spread parameter between the carbon nano-tube fibre to use, interlayer arrangement mode is regulated and controled, realize carbon nano-tube fibre in the interspersed of multiple interlayers, the carbon nano-tube fibre composite material of gained has many advantages, such as that interlaminar action is strong, high convenient for being molded, being convenient for size design, preparation efficiency, the mechanical property advantage of carbon nano-tube fibre can be played, while its electrically and thermally performance can also be kept.
Description
Technical field
The present invention relates to a kind of carbon nano-tube fibre composite material, more particularly to a kind of carbon nano-tube fibre composite material and
Preparation method belongs to nanocomposite technical field.
Background technology
Carbon nanotube be presently found quality is most light, intensity it is highest integrate mechanics, electricity, thermal property it is more
Function one-dimensional linear material, tensile strength are 50~200GPa, and conductivity theory value reaches 108s/m, carrier transport ability
It is 1000 times of copper, therefore is considered as ideal composite material reinforcement body always.Current existing carbon nano tube compound material
Form be mainly the following：
1) carbon nanotube dust reinforcing material, mainly by by carbon nanotube dust directly as reinforcement and polymer or
The mode of other materials mixing prepares carbon nano tube compound material.For example, Advanced material, 1999,11:937-
941, it was recently reported that a kind of new material；Application No. is 201010202618.8 Chinese patents to disclose a kind of carbon nano tube polyurethane
The preparation method of composite material；Application No. is 200810067169.3 Chinese patent, to disclose a kind of carbon nano tube/conducting poly-
Compound composite material；Application No. is 201410768106.6 Chinese patents to disclose a kind of carbon nano tube enhanced aluminium base composite wood
The continuous preparation method etc. of material.
2) carbon nano-tube film composite material obtains carbon nanotube by suction method, array membrane method or floating catalyst system
Then film is compounded to form carbon nano-tube film composite material with other materials.For example, application No. is 201310353806.4
Chinese patent discloses a kind of preparation method of carbon nano-composite material and corresponding carbon nano-composite material；Application No. is
200810065181.0 Chinese patent disclose a kind of carbon nano tube compound material and preparation method thereof；Application No. is
200610062034.9 Chinese patent disclose a kind of preparation method of carbon nano-tube/polymer composite material；And
Carbon,2011,49(14):A kind of 4786-4791, it was recently reported that carbon material etc..
3) other carbon nano tube compound materials, including the composite material and inorganic matter of carbon carbon that carbon nanotube is combined with carbon
In conjunction with composite material, complex method includes coating is compound, growth in situ is compound etc., such as application number is respectively
201410140709.1,201610543033.X, 201380038990.1,201210567302.8,201280049216.6
Carbon nano tube compound material etc. disclosed in Chinese patent.
Above-mentioned several methods for preparing carbon nano tube compound material, it is intended to which, by compound with carbon nanotube, raising is compound
Mechanics, electricity, the thermal property of material.From the point of view of the effect of above-mentioned several method：
Powder composite algorithm is basic material with carbon nanotube dust, usually by powder and other materials mixed-forming, carbon
The degree of scatter of nanotube has larger impact to molding effect, and the mutual agglomeration between carbon nanotube is weaker and content is relatively low
(being generally less than 10%), therefore the performance enhancement effect of gained composite material is also very limited, therefore the preparation of powder suction method
Composite materials property is poor.
The performance of film composite material prepared by Array Method and floating method is heavily dependent on carbon nano-tube film certainly
The performance of body.
Array Method is basic material with carbon nano-tube film, can be adjusted to the content of carbon nanotube in composite material
Control, can also obtain the carbon nano pipe array film composite material of high content of carbon nanotubes, and mechanics, electric property are preferable, but
Although being carbon nano pipe array film and being formed by way of stacked in multi-layers, monolayer film thickness is too small (nanoscale),
Preparation efficiency is relatively low.
Floating method is basic material with carbon nano-tube film, although can be prepared with large area, its carbon nanometer prepared
Pipe film be usually carried out again after film forming it is compound, it is relatively strong due to interacting between carbon pipe after molding, be not easy in single thin layer
Carry out that depth is compound between film, when MULTILAYER COMPOSITE it is mutual effect it is also relatively low, interlaminar action is poor.
Fibrous composite is the important component of composite material, and carbon nano-tube fibre composite material is also considered always
It is one of following important potential application direction of carbon nanotube, but the office of yield and preparation method due to carbon nano-tube fibre etc.
It is sex-limited, therefore the related content of carbon nano-tube fibre composite material is never prepared in existing report at present.
Invention content
The main purpose of the present invention is to provide a kind of carbon nano-tube fibre composite material and preparation methods, existing to overcome
There is the deficiency in technology.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
An embodiment of the present invention provides a kind of preparation methods of carbon nano-tube fibre composite material comprising：
One-dimensional carbon nano-tube fibre is provided；
Using winding method layer by layer, and reinforcement is added during winding layer by layer, makes the carbon nano-tube fibre layer by layer
Stacked arrangement forms the composite material presoaked body of carbon nano-tube fibre with layered composite structure；
Forming processes are carried out to the composite material presoaked body of the carbon nano-tube fibre, to obtain the carbon nano-tube fibre
Composite material.
One of preferably, the preparation method includes：Carbon nano-tube fibre is wound into fiber by yarn guiding wheel
It collects on axis, is moved back and forth by making fiber collect axis, winding layer by layer stacks, and collects the reciprocating motion of axis by regulating and controlling fiber
Speed, the radial section width of carbon nano-tube fibre and thickness, winding angle, winding spacing, to regulate and control in layer and interlayer
The mutual stacked arrangement situation of carbon nano-tube fibre, and reinforcement is added during stacked in multi-layers arranges, form tool
There is the composite material presoaked body of the carbon nano-tube fibre of layered composite structure.
Preferably, in the winding method layer by layer, winding tension is 500mN~1.2N, adjacent two windings line in same layer
Winding spacing between circle is 100~300 μm, and the winding angle is that carbon nano-tube fibre length direction collects axis edge with fiber
The angle of direction of axis line, especially preferred, the winding angle is 30~90 °, and speed of wrap is 1~30m/min；It is preferred that
, the radial section width of the carbon nano-tube fibre is 0.1~5mm, and thickness is 1~10 μm.
The embodiment of the present invention additionally provides the carbon nano-tube fibre composite material prepared by preceding method, including by carbon nanometer
The layered composite structure of pipe fiber and reinforcement stacked in multi-layers arrangement form；Layered composite construction includes stacking setting extremely
Few two carbon nano-tube fibre layers, the carbon nano-tube fibre layer include at least one-dimensional carbon nanotube fibre for being orientated arrangement
It ties up, the carbon nano-tube fibre in the carbon nano-tube fibre layer is arranged in parallel by setting spacing.
Compared with prior art, advantages of the present invention includes：
1. the preparation method of carbon nano-tube fibre composite material provided by the invention, the carbon nano-tube fibre composite wood of gained
The one-dimensional carbon nanotube fiber that material is assembled with carbon nanotube is basic material, have interlaminar action it is strong, convenient for being molded, be convenient for
Size design, the advantages that preparation efficiency is high are carried out, the mechanical property advantage of carbon nano-tube fibre can be played, while can also protect
Hold its electrically and thermally performance；
2. the preparation method of carbon nano-tube fibre composite material provided by the invention passes through the carbon nano-tube fibre to use
Between regulation and control between each spread parameter, interlayer arrangement mode is regulated and controled, realizes carbon nano-tube fibre in multiple interlayers
Interspersed, the composite material interlayer of formation interts with obvious effects；It is higher to prepare rate, can reach 10m/min or more, and can basis
Demand carries out molding design.
Description of the drawings
Fig. 1 is the flow signal of the preparation method of the carbon nano-tube fibre composite material in an exemplary embodiments of the invention
Figure；
Fig. 2 is that carbon nano-tube fibre flat filament/resin composite materials in an exemplary embodiments of the invention prepare schematic diagram；
Fig. 3 a and Fig. 3 b are the carbon nano-tube fibre flat filament composite material that an exemplary embodiments of the invention are prepared
Electron microscope after laminated tearing；
Fig. 4 is carbon nano-tube fibre flat filament resin composite materials section electron microscope prepared by one embodiment of the present invention；
Fig. 5 a are the fracture figure of the carbon nano-tube fibre circle wire composite material in comparative example 1 of the present invention；
Fig. 5 b are the fracture figure of carbon nano-tube fibre flat filament resin composite materials prepared by one embodiment of the present invention；
Fig. 6 a, Fig. 6 c are the sectional view of the carbon nano-tube fibre circle wire composite material in comparative example 1 of the present invention；
Fig. 6 b, Fig. 6 d are the section of carbon nano-tube fibre flat filament resin composite materials prepared by one embodiment of the present invention
Figure.
Specific implementation mode
In view of deficiency in the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical solution is predominantly that basic material is received by regulating and controlling in layer with interlayer carbon using winding method layer by layer with carbon nano-tube fibre
The mutual arranging situation of mitron fiber obtains carbon nano-tube fibre composite material, and is aided with other power during arrangement
Enhancing or function reinforcing material are learned, is a kind of novel carbon nanotube composite for being different from having carbon nano tube compound material structure
Material.The technical solution, its implementation process and principle etc. will be further explained as follows.
The one side of the embodiment of the present invention provides a kind of preparation method of carbon nano-tube fibre composite material, packet
It includes：
One-dimensional carbon nano-tube fibre is provided；
Using winding method layer by layer, and reinforcement is added during winding layer by layer, makes the carbon nano-tube fibre layer by layer
Stacked arrangement forms the composite material presoaked body of carbon nano-tube fibre with layered composite structure；
Forming processes are carried out to the composite material presoaked body of the carbon nano-tube fibre, to obtain the carbon nano-tube fibre
Composite material.
Among some exemplary embodiments, the carbon nano-tube fibre is the shape with existing for one-dimensional fibers form
Formula can be to have to twist fiber, non-twist fiber, any one or two or more combinations in flat filament, but not limited to this.
More preferably, the carbon nano-tube fibre is flat filament, because flat filament is forming stratiform than the fiber of other forms
When structure, can more smooth out, layer structure arrangement can more closely, smooth-going, gapless.
Preferably, the cross sectional shape of the carbon nano-tube fibre can be regular shape or irregular shape.
Further, the regular shape include it is round, rectangular, oval in any one or two or more groups
It closes, but it is not limited to this.
One of preferably, the preparation method includes：Carbon nano-tube fibre is wound into fiber by yarn guiding wheel
It collects on axis, is moved back and forth by making fiber collect axis, winding layer by layer stacks, and collects the reciprocating motion of axis by regulating and controlling fiber
Speed, the radial section width of carbon nano-tube fibre and thickness, winding angle, winding spacing, to regulate and control in layer and interlayer
The mutual stacked arrangement situation of carbon nano-tube fibre, and reinforcement is added during stacked in multi-layers arranges, form tool
There is the composite material presoaked body of the carbon nano-tube fibre of layered composite structure.
To winding arrangement layer by layer, winding tension is less than the tension failure power of carbon nano-tube fibre, and generally 500mN~
1.2N is tightly combined degree by control that winding tension can control Fiber In Composite Material to a certain extent.Wind spacing
For the distance between adjacent two wound around coil in same layer, it is according to carbon nano-tube fibre diameter or flat filament width design, generally
In the case of be designed as fiber width more than half, generally 100~300 μm.
Preferably, the winding angle is the folder that carbon nano-tube fibre length direction collects axis along direction of axis line with fiber
Angle, especially preferably 30~90 ° are combined with ensureing that interlayer can fully interlock, and speed of wrap is 1~30m/min, winds the time
Depending on the length of prepared composite material, width and thickness.
Preferably, the radial section width of the carbon nano-tube fibre is 0.1~5mm, and thickness is 1~10 μm.
Preferably, the setting that can be arranged parallel to each other between layers that the carbon nano-tube fibre is formed, can also shape
At set angle, for example, the range of angle can be 0~60 °.
Preferably, by the regulation and control of winding angle and the cross-sectional width and thickness of carbon nano-tube fibre, regulate and control composite material
Layer in and interlayer overlapping degree.
In some embodiments, at least one continuous carbon nano-tube fibre is distributed in a carbon nano-tube fibre layer or extremely
The different fragments of a few continuous carbon nano-tube fibre are respectively arranged at least two carbon nano-tube fibre layers.
Preferably, at least in a carbon nano-tube fibre layer, at least tail end of a carbon nano-tube fibre and another carbon nanometer
The head end non junction of pipe fiber docks, in this way can be to avoid the fault of construction caused by knotting, overlapping etc..
Preferably, the carbon nano-tube fibre in each layer even can be separated by one or more layers carbon nanometer with adjacent layer
Pipe is connected, and forms interlayer cross structure.
The carbon nano-tube fibre used in the present invention by the regulation and control between each spread parameter, to interlayer arrangement mode into
Row regulation and control realize carbon nano-tube fibre in the interspersed of multiple interlayers, the mutual effect enhancing of each fiber, interlaced degree
Pass through the state modulator in stacking process.
Further, the shape formed after the carbon nano-tube fibre stacked arrangement can be plate shaped, cylindrical shape etc.
Regular shape or other irregular shapes, are convenient for size design.
Among some exemplary embodiments, the present invention also adds reinforcement during stacked in multi-layers, can have
Help improve the substance of the performances such as Compound Material Engineering, electricity, calorifics, such as polymer solution, polymer monomer solution, resin
Monomer solution, metal salt, conducting polymer, acid etc..
Preferably, the polymer monomer solution includes polymer monomer solution, and the acid includes gold chloride, chloroplatinic acid
Deng.
Among some exemplary embodiments, the present invention answers carbon nano-tube fibre also according to the characteristic of addition reinforcement
Condensation material prepreg carries out forming processes, such as：If reinforcement is polymer monomer, polymerization processing is carried out to it；If
It is resin monomer, then carries out curing process；If reinforcement is to improve gold chloride, the chloroplatinic acid etc. of electric conductivity, can pass through
Heat treatment promotes the deposition of nano Au particle and platinum particles；Addition nano metal particles reach power simultaneously in a polymer solution
And electricity enhancing etc..
One of preferably, the preparation method further includes：It is wound layer by layer by the carbon nano-tube fibre
Before, first the carbon nano-tube fibre is placed on thread guide devices.
Among some more specifically case study on implementation, as shown in fig.1, the preparation method specifically includes following step
Suddenly：
(1) lead：Carbon nano-tube fibre is positioned on pay off rack, then by tension bracket, is wound on shaping axle.
(2) it winds layer by layer：By the way that the parameters such as winding tension, winding spacing, winding angle are arranged, twining for composite material is designed
Around structure；Pass through the thickness of speed of wrap and time control composite material.Reinforcement, such as polymer are added during winding
Solution, polymer monomer solution, metal salt, conducting polymer etc..
(3) the composite material presoaked body of carbon nano-tube fibre is formed：After winding reaches the size of needs, taken from winding axis
Under, obtain the composite material presoaked body of carbon nano-tube fibre.
(4) composite molding：According to the characteristic of actual interpolation reinforcement, forming processes are carried out to prepreg, obtain carbon
Nanotube fibers composite material.
Wherein, in the case of carbon nano-tube fibre amount abundance, which is convenient for and industrialization fiber composite
Material integrates with.
More specifically, Fig. 2 shows being basic material with carbon nano-tube fibre flat filament, using resin as the composite wood of reinforcement
The preparation flow schematic diagram of material.The preparation method of the composite material is specially：
Carbon nano-tube fibre flat filament (CNT flat filaments) is wound in by guide roller on wireline reel, by be arranged winding tension,
The parameters such as spacing, winding angle are wound, the winding arrangement of composite material is designed；Pass through speed of wrap and time control composite material
Thickness, and during winding be added resin solution as reinforcement.After winding reaches the size of needs, by composite wood
Material is removed from wireline reel, obtains carbon nano-tube fibre flat filament/resin composite material presoaked body.It is finally flat to carbon nano-tube fibre
Silk/resin composite material presoaked body carries out curing molding processing, obtains carbon nano-tube fibre flat filament/resin composite materials.
The embodiment of the present invention another aspect provides the carbon nano-tube fibre composite material prepared by preceding method, packet
It includes by the layered composite structure of carbon nano-tube fibre and reinforcement stacked in multi-layers arrangement form；Layered composite construction includes heap
At least two carbon nano-tube fibre layers of folded setting, the carbon nano-tube fibre layer include at least one-dimensional carbon for being orientated arrangement
Nanotube fibers, the carbon nano-tube fibre in the carbon nano-tube fibre layer are arranged in parallel by setting spacing.
Preferably, the carbon nano-tube fibre layer includes at least a carbon nano-tube fibre.
Preferably, the carbon nano-tube fibre has flat radial section structure.
Preferably, in two neighboring carbon nano-tube fibre layer, at least carbon nanometer in a carbon nano-tube fibre layer
Pipe fiber is embedded in the gap between the two neighboring carbon nano-tube fibre in another carbon nano-tube fibre layer, in this way can be into one
Step increases the bond strength of layer and layer.
Preferably, at least in a carbon nano-tube fibre layer, at least tail end of a carbon nano-tube fibre and another carbon nanometer
The head end non junction of pipe fiber docks, in this way can be to avoid the fault of construction caused by knotting, overlapping etc..
Preferably, the carbon nano-tube fibre in same layer or between different layers is attracted each other connection by Van der Waals force.
Preferably, the thickness of the carbon nano-tube fibre composite material is 10 μm or more, and thickness does not set the upper limit, length and width
Degree does not also set the upper limit.
Preferably, the spacing that sets is 100~300 μm.
Preferably, the reinforcement is set to the surface of carbon nano-tube fibre or at least partly penetrates into carbon nano-tube fibre
Inside forms the boundary layer between carbon nano-tube fibre and reinforcement or the articulamentum between fiber and fiber.
Preferably, the carbon nanotube includes single-walled carbon nanotube and/or multi-walled carbon nanotube.
Among some exemplary embodiments, the carbon nano-tube fibre is the shape with existing for one-dimensional fibers form
Formula can be to have to twist fiber, non-twist fiber, any one or two or more combinations in flat filament, but not limited to this.
More preferably, the carbon nano-tube fibre is flat filament, because flat filament is forming stratiform than the fiber of other forms
It when structure, can more smooth out, layer structure arrangement can more compact, smooth-going, gapless.
Preferably, the cross sectional shape of the carbon nano-tube fibre can be regular shape or irregular shape.
Further, the regular shape include it is round, rectangular, oval in any one or two or more groups
It closes, but it is not limited to this.
Preferably, being arranged parallel to each other between layers for carbon nano-tube fibre formation is arranged or mutually forms setting
Angle is arranged.
Preferably, the same carbon nano-tube fibre is set to one layer or is staggered between at least two layers.
Fig. 3 a and Fig. 3 b show the carbon nano-tube fibre flat filament composite wood that an exemplary embodiments of the invention are prepared
Electron microscope after the laminated tearing of material.Fig. 4 shows carbon nano-tube fibre flat filament resin prepared by one embodiment of the present invention
Composite material section electron microscope.The carbon nanotube that Fig. 5 a and Fig. 5 b respectively illustrate the preparation of comparative example 1 justifies wire composite material and this
Invent the fracture figure of the carbon nanotube flat filament resin composite materials of preferred embodiment preparation.Fig. 6 a, 6b respectively illustrate comparison
The carbon nanotube flat filament composite material of carbon nanotube circle wire composite material and one embodiment of the present invention preparation prepared by example 1
Side cross-sectional view, Fig. 6 c and 6d respectively illustrate carbon nanotube circle wire composite material prepared by comparative example 1 and the present invention one is preferred in fact
Apply the cross-sectional view of the carbon nanotube flat filament composite material of example preparation.
Below by way of several embodiments and the technical solution that present invention be described in more detail in conjunction with attached drawing.However, selected
Embodiment be merely to illustrate the present invention, and do not limit the scope of the invention.
Embodiment 1
One axis of carbon nano-tube fibre flat filament is taken, approximately more than 100 meters long, about 200 μm of width, 10 μm of thickness, tension failure load
Lotus 1N or so.Carbon nano-tube fibre axis is placed on paying out reel first, drawing carbon nano-tube fibre makes it pass through guide axis, guide
The quantity of axis can be selected according to yarn (i.e. carbon nano-tube fibre) tension, then twine carbon nano-tube fibre on collection axis
Around the winding spacing between adjacent two coil is set as 100 μm, and winding angle is 30 degree, and yarn tension 500-600mN is twined
It is 10cm around width, speed of wrap 1m/min, the winding time is 20min, and it is 5% ring to use mass concentration during the winding process
Oxygen resin/acetone soln infiltration, forms composite material presoaked body, is removed from collection axis later, then 130 under 7MPa pressure
DEG C hot pressing 1 hour forms carbon nano-tube fibre composite material.The carbon nano-tube fibre thickness of composite material that the present embodiment obtains is
15-20 μm, tensile break strength 500-600MPa.
Embodiment 2
One axis of carbon nano-tube fibre flat filament is taken, approximately more than 100 meters long, about 500 μm of width, about 10 μm of thickness, tension failure
Load 3N or so.Carbon nano-tube fibre axis is placed on paying out reel first, drawing fiber makes it pass through guide axis, the number of guide axis
Amount can be selected according to yarn tension, be then placed in yarn and collected on axis, the winding spacing between adjacent two coil is set as
250 μm, winding angle is 85 degree, yarn tension 1-1.2N, winding width 10cm, speed of wrap 2m/min, when winding
Between be 50min, during the winding process use mass concentration be 5% epoxy resin/acetone soln infiltration, formed it is composite material presoaked
Body is removed on axis from collecting later, and then 130 DEG C of hot pressing 1 hour under 7MPa pressure, forms carbon nano-tube fibre composite wood
Material.The carbon nano-tube fibre thickness of composite material that the present embodiment obtains is 60-70 μm, tensile break strength 400-500MPa.
Embodiment 3
One axis of carbon nano-tube fibre flat filament is taken, approximately more than 100 meters long, 200-300 μm of width, 2-4 μm of thickness, tension failure
Load 1N or so.Carbon nano-tube fibre axis is placed on paying out reel first, drawing fiber makes it pass through guide axis, the number of guide axis
Amount can be selected according to yarn tension, be then placed in yarn and collected on axis, the winding spacing between adjacent two coil is set as
120 μm, winding angle is 60 degree, yarn tension 600-800mN, winding width 10cm, speed of wrap 2m/min, winding
Time is 50min, uses bismaleimide resin/acetone soln infiltration that mass concentration is 1% during the winding process, it is pre- to form composite material
Body is soaked, is removed on axis from collecting later, then 200 DEG C of hot pressing 1 hour under 7MPa pressure, forms carbon nano-tube fibre composite wood
Material.The carbon nano-tube fibre thickness of composite material that the present embodiment obtains is about 10-15 μm, tensile break strength 1.5-
2.0GPa。
Embodiment 4
One axis of carbon nano-tube fibre flat filament is taken, approximately more than 100 meters long, 200-300 μm of width, 2-4 μm of thickness, tension failure
Load 1N or so.Carbon nano-tube fibre axis is placed on paying out reel first, drawing fiber makes it pass through guide axis, the number of guide axis
Amount can be selected according to yarn tension, be then placed in yarn and collected on axis, the winding spacing between adjacent two coil is set as
120 μm, winding angle is 80 degree, yarn tension 600-800mN, winding width 10cm, and speed of wrap 10m/min is twined
It is 10min around the time, uses bismaleimide resin/acetone soln infiltration that mass concentration is 1% during the winding process, form composite material
Prepreg is removed on axis from collecting later, and then 200 DEG C of hot pressing 1 hour under 7MPa pressure, it is compound to form carbon nano-tube fibre
Material.The carbon nano-tube fibre thickness of composite material that the present embodiment obtains is about 10-15 μm, tensile break strength 1.5-
2.0GPa。
Embodiment 5
One axis of carbon nano-tube fibre flat filament is taken, approximately more than 100 meters long, about 500 μm of width, about 10 μm of thickness, tension failure
Load 3N or so.Carbon nano-tube fibre axis is placed on paying out reel first, drawing fiber makes it pass through guide axis, the number of guide axis
Amount can be selected according to yarn tension, be then placed in yarn and collected on axis, the winding spacing between adjacent two coil is set as
250 μm, winding angle is 90 degree, yarn tension 1-1.2N, winding width 10cm, speed of wrap 2m/min, when winding
Between be 50min, infiltrate the aqueous solution of chloraurate that golden mass content is 2% first during the winding process, heat treatment makes nano-scale gold particle
Son deposition, then the epoxy resin/acetone soln for being 5% with mass concentration infiltrate, and composite material presoaked body are formed, later from collection
It is removed on axis, then 130 DEG C of hot pressing 1 hour under 7MPa pressure, forms carbon nano-tube fibre composite material.The present embodiment obtains
Carbon nano-tube fibre thickness of composite material be 60-70 μm, tensile break strength 400-500MPa, electric conductivity can be increased to
Originally 2 times or so.
Comparative example 1：
Carbon nano-tube fibre circle one axis of silk prepared by twisting method is taken, carbon is prepared into using method same as Example 1
Nanotube fibers composite material measures its mechanical stretch intensity distribution between 130MPa-140MPa after molding, low strength,
In terms of Fig. 5 a, Fig. 6 a, Fig. 6 c, the composite inner gap that circular fiber is formed is more, and fault of construction is apparent.
In addition, inventor is referring also to embodiment 1 to the mode of embodiment 5, with the other originals listed in this specification
Material and condition etc. are tested, and it is strong to be equally made interlaminar action, mechanics, electrically and thermally carbon nanotube of good performance
Fibrous composite.In addition, carbon nano-tube fibre can also form the knots such as 2-dimensional interleaving, 3 D weaving by conventional woven method
Then structure infiltrates to form prepreg with reinforcement, then carry out forming processes and form composite material.
In conclusion by test it can be found that the carbon nano-tube fibre obtained by the above-mentioned technical proposal of the present invention
Composite material has interlaminar action strong, and structural advantage is apparent, while having convenient for molding, being convenient for size design, preparation effect
The advantages that rate is high, can play the mechanical property advantage of carbon nano-tube fibre, while can also keep its electrically and thermally performance.
It should be appreciated that above-described is only some embodiments of the present invention, it is noted that for the common of this field
For technical staff, under the premise of not departing from the concept of the present invention, other modification and improvement and performance can also be made
Optimization etc., these are all within the scope of protection of the present invention.
Claims (22)
1. a kind of preparation method of carbon nano-tube fibre composite material, it is characterised in that including：
One-dimensional carbon nano-tube fibre is provided；
At least the carbon nano-tube fibre stacked in multi-layers is set to arrange using winding method layer by layer, while into each carbon nano-tube fibre layer
Reinforcement is added between portion and each carbon nano-tube fibre layer, forms the carbon nano-tube fibre composite material with layered composite structure
Prepreg；
Forming processes are carried out to the composite material presoaked body of the carbon nano-tube fibre, it is compound to obtain the carbon nano-tube fibre
Material.
2. preparation method according to claim 1, it is characterised in that：The carbon nano-tube fibre includes to twist fiber, nothing
Twist any one in fiber, flat filament or two or more combinations；Preferably, the carbon nano-tube fibre is flat filament.
3. preparation method according to claim 1, it is characterised in that：The cross sectional shape of the carbon nano-tube fibre includes rule
Then shape and/or irregular shape；Preferably, the regular shape include it is round, rectangular, oval in any one or two
Kind or more combination.
4. preparation method according to claim 1, which is characterized in that the winding method layer by layer includes：By carbon nanotube fibre
It ties up and collects on axis that winding is stacked layer by layer in the fiber that moves axially in reciprocal fashion, and axis is collected in an axial direction at least through regulation and control fiber
Move back and forth speed, the radial section width of carbon nano-tube fibre and thickness, winding tension, winding angle, winding spacing, winding
The combination of any one condition or more than two conditions in speed, to regulate and control carbon nano-tube fibre in each carbon nano-tube fibre layer
Stacking and/or spread pattern and/or each carbon nano-tube fibre interlayer carbon nano-tube fibre stacking and/or spread pattern,
Described in winding angle be that carbon nano-tube fibre length direction and fiber collect angle between axis axis direction, between the winding
Away from the spacing between adjacent carbon nanotubes fiber in same carbon nano-tube fibre layer；Preferably, the winding tension is 500mN
~1.2N；Preferably, the winding spacing is 100~300 μm；Preferably, the winding angle is 30~90 °；Preferably, institute
It is 1~30m/min to state speed of wrap；Preferably, the radial section width of the carbon nano-tube fibre is 0.1~5mm, and thickness is
1~10 μm.
5. preparation method according to claim 4, it is characterised in that：At least two carbon nano-tube fibre layers, which are mutually parallel, to be set
Set or at least two carbon nano-tube fibre layers between be formed with set angle；Preferably, the set angle is 0~60 °.
6. preparation method according to claim 4, it is characterised in that：Pass through the section of winding angle and carbon nano-tube fibre
The regulation and control of width and thickness, regulate and control in the layer of the carbon nano-tube fibre composite material and interlayer overlapping degree.
7. preparation method according to claim 4, it is characterised in that：At least one continuous carbon nano-tube fibre is distributed in one
In carbon nano-tube fibre layer or the different fragments of at least one continuous carbon nano-tube fibre are respectively arranged at least two carbon nanometers
In pipe fibrous layer；Preferably, at least in a carbon nano-tube fibre layer, at least the tail end of a carbon nano-tube fibre is received with another carbon
The head end non junction of mitron fiber docks.
8. preparation method according to claim 1, it is characterised in that：It is formed after the carbon nano-tube fibre stacked arrangement
Shape includes regular shape or irregular shape；Preferably, the regular shape includes plate shaped and/or cylindrical shape.
9. preparation method according to claim 1, it is characterised in that：The reinforcement includes polymer solution, polymer
Any one in monomer solution, resin monomer solution, metal salt, conducting polymer and acid or two or more combinations.
10. preparation method according to claim 9, it is characterised in that：The polymer monomer solution includes high polymer list
Liquid solution；And/or the acid includes gold chloride and/or chloroplatinic acid.
11. preparation method according to claim 10, it is characterised in that：The forming processes include to polymer monomer into
Row polymerization processing carries out resin monomer curing process, carries out heat treatment to metal salt or add in a polymer solution to receive
Rice metallic.
12. preparation method according to claim 1, it is characterised in that further include：It is carried out by the carbon nano-tube fibre
Before winding layer by layer, first the carbon nano-tube fibre is placed on thread guide devices；And/or carbon nano-tube fibre is passed through into guide
It takes turns to collect in the fiber moved axially in reciprocal fashion and is wound stacking layer by layer on axis.
13. a kind of carbon nano-tube fibre composite material, it is characterised in that including by carbon nano-tube fibre and reinforcement stacked in multi-layers
The layered composite structure of arrangement form；Layered composite construction includes at least two carbon nano-tube fibre layers for stacking setting,
The carbon nano-tube fibre layer includes being orientated at least one-dimensional carbon nanotube fiber arranged, in the carbon nano-tube fibre layer
Carbon nano-tube fibre by setting spacing it is arranged in parallel.
14. carbon nano-tube fibre composite material according to claim 13, it is characterised in that：The carbon nano-tube fibre layer
Including at least a carbon nano-tube fibre；Preferably, the carbon nano-tube fibre has flat radial section structure.
15. carbon nano-tube fibre composite material according to claim 13, it is characterised in that：In two neighboring carbon nanotube
In fibrous layer, at least carbon nano-tube fibre in a carbon nano-tube fibre layer is embedded in the phase in another carbon nano-tube fibre layer
In gap between adjacent two carbon nano-tube fibres.
16. carbon nano-tube fibre composite material according to claim 13, it is characterised in that：At least in carbon nanotube fibre
It ties up in layer, at least the tail end of a carbon nano-tube fibre is docked with the head end non junction of another carbon nano-tube fibre.
17. carbon nano-tube fibre composite material according to claim 13, it is characterised in that：In same layer or different layers it
Between carbon nano-tube fibre attracted each other connection by Van der Waals force；Preferably, the thickness of the carbon nano-tube fibre composite material
Degree is 10 μm or more；Preferably, the spacing that sets is 100~300 μm；Preferably, it is fine to be set to carbon nanotube for the reinforcement
The surface of dimension or the inside at least partly penetrating into carbon nano-tube fibre.
18. carbon nano-tube fibre composite material according to claim 13, it is characterised in that：The carbon nanotube includes single
Wall carbon nano tube and/or multi-walled carbon nanotube.
19. carbon nano-tube fibre composite material according to claim 13, it is characterised in that：The carbon nano-tube fibre packet
Include any one in twirl fiber, non-twist fiber, flat filament or two or more combinations；Preferably, the carbon nano-tube fibre
For flat filament.
20. carbon nano-tube fibre composite material according to claim 13, it is characterised in that：The carbon nano-tube fibre
Cross sectional shape includes regular shape and/or irregular shape；Preferably, during the regular shape includes round, rectangular, oval
Any one or two or more combinations.
21. carbon nano-tube fibre composite material according to claim 13, it is characterised in that：The carbon nano-tube fibre shape
At be arranged parallel to each other between layers setting or mutually form set angle setting.
22. carbon nano-tube fibre composite material according to claim 13, it is characterised in that：The same carbon nanotube is fine
Dimension is set to one layer or is staggered between at least two layers.
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