CN106183212A - Structure/heating integral composite and preparation method thereof - Google Patents
Structure/heating integral composite and preparation method thereof Download PDFInfo
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- CN106183212A CN106183212A CN201610546596.4A CN201610546596A CN106183212A CN 106183212 A CN106183212 A CN 106183212A CN 201610546596 A CN201610546596 A CN 201610546596A CN 106183212 A CN106183212 A CN 106183212A
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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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
-
- 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
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0253—Polyolefin fibres
-
- 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
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
-
- 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
- B32B2262/101—Glass fibres
-
- 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
Abstract
The invention provides a kind of structure/heating integral composite and preparation method thereof；Described composite is the multiple structure including reinforcement layer, carbon nano-tube film/resin compounded layer；Described reinforcement layer, carbon nano-tube film/resin compounded layer laying successively.Described method is to be connected with electrode by carbon nano-tube film/resin compounded layer, then as heater block lay in reinforcement interlayer or surface, prepares composite by integrated forming technique.Composite prepared by the present invention has mechanical property and the electrical heating characteristic of excellence, has boundless application prospect in fields such as survey of deep space, polar region observation, civil electronic devices.Hot strength and the modulus of structure prepared by the present invention/heating integral composite are respectively increased more than 3% compared with the structural composite material of respective material system, any heating-up temperature within 150 DEG C all can reach balance within 5 minutes, and laser heating 200 hours at 150 DEG C, resistance variations is less than 5%.
Description
Technical field
The present invention relates to technical field of composite materials, be specifically related to the preparation method of a kind of composite, particularly relate to one
Plant structure/heating integral composite and preparation method thereof.
Background technology
Composite especially advanced composite material, it is prominent excellent to have that specific strength is high, specific modulus high, thermal coefficient of expansion is low etc.
Gesture, has been used widely.In recent years, along with the fast development in the fields such as survey of deep space, polar region observation, composite
The working environment of parts constantly deteriorates, and ambient temperature is to the lowest trend development.In order to keep payload, critical component
Normal work, not only need composite to have good mechanical property, and require that composite has heating function.Mesh
Before, it is achieved composite heating function mainly has two ways: 1, composite material surface pastes heater block；2, composite wood is utilized
The conductive fiber of material inside self carries out electrified regulation.
The heater block material that composite material surface is pasted mainly has metal forming or the conventional conductive such as tinsel, carbon fiber felt
Material, also has the novel conductive material that graphene film and carbon nano-tube film etc. develop in recent years.Wherein, carbon nano-tube film tool
There is the characteristic of ultra-thin, flexible, mechanics and excellent electric conductivity, thus its application in terms of composite heating is increasingly closed
Note.Carbon nano-tube film is that CNT is intersected by Van der Waals force, tangle the membranaceous macroscopic body of self-supporting formed, its system
Preparation Method has: solution suction method, array membrane method, electrochemical deposition method, be coated with method, chemical gaseous phase deposition floating catalytic method
Deng.The carbon nano-tube film lay that Massachusetts Polytechnics utilizes array membrane method to prepare can realize stably adding in composite material surface
Heat.But, the technics comparing that composite material surface pastes heater block is complicated, needs first forming composite then to paste, and
And heater block can affect its surface type surface accuracy on surface, thus can not in the composite material component of a lot of high-precision requirement
Application.
The conductive fiber utilizing composite inner self carries out electrified regulation, and this method is limited by conductive fiber
Can only heat for carbon fibre composite, and fiber is relatively difficult with being fully connected of electrode, heats uneven.With
Time, fiber is relatively big so that its mechanical property reduces substantially on composite material interface impact after being energized for a long time.Therefore, compel to be essential
Want composite that is a kind of simple to operate and that can simultaneously have structure/heating integral.
Summary of the invention
For defect of the prior art, it is an object of the invention to provide a kind of structure/heating integral composite and
Its preparation method.
It is an object of the invention to be achieved through the following technical solutions:
The invention provides a kind of structure/heating integral composite, described composite is for including reinforcement layer, carbon
The multiple structure of nanotube films/resin compounded layer.
Preferably, described reinforcement layer, carbon nano-tube film/resin compounded layer laying successively.
Preferably, one or more during described reinforcement layer includes resin bed, fibrous layer, resin/fiber composite bed.
Preferably, described fiber includes carbon fiber, glass fibre, poly-p-phenylene-benzobisoxazole fiber, polyester fiber, gathers
Any one in vinyl fiber, polypropylene fibre.
Preferably, described resin includes epoxy resin, bismaleimide resin, phenolic resin, polyimides, polyethylene, poly-second
The mixing of one or more in enol, polyester, polypropylene, polystyrene and polyurethane.
Preferably, described carbon nano-tube film includes the film unit of tens to hundreds of layer of 100nm, in described film unit
CNT crosses one another formation network structure.
It is highly preferred that described carbon nano-tube film uses chemical gaseous phase deposition floating catalytic method to be prepared.
Preferably, in described carbon nano-tube film/resin compounded layer, the content of resin is 2wt%～35wt%.
Preferably, the preparation method of described carbon nano-tube film/resin compounded layer comprises the steps: to put carbon nano-tube film
Enter and resin solution impregnates 30～60min, take out post-drying and get final product.Resin content is controlled by the concentration changing resin solution,
Thus its resistivity is regulated and controled.
It is prepared from it is highly preferred that described resin solution is dissolved in solvent by resin.In resin solution, the quality of resin contains
Amount is 1～20%.
It is highly preferred that described resin includes epoxy resin, bismaleimide resin, phenolic resin, polyimides, polyethylene, poly-second
Any one in enol, polyester, polypropylene, polystyrene and polyurethane；Solvent includes ethanol, acetone, benzene, toluene, tetrahydrochysene
One or more kinds of mixing in furan, dimethylformamide, methyl pyrrolidone and dimethyl sulfoxide.
Preferably, gelling temp (thermosetting resin) or the heat decomposition temperature of described drying temperature resin to be less than are (warm
Plastic resin).Carbon nano-tube film after dipping can be put in vacuum drying oven to improve the rate of volatilization of solvent in resin solution
In, the resin content of preimpregnation film can be controlled 2%～35% by the mass content of regulation and control resin solution kind resin
In the range of, corresponding resistor rate can be controlled in 1 × 10-3Ω cm～8 × 10-3In the range of Ω cm.
Preferably, described carbon nano-tube film/resin compounded layer two ends connect electrode respectively.
Present invention also offers the preparation method of a kind of structure/heating integral composite, described method includes as follows
Step: according to specifically applying needs reinforcement layer, carbon nano-tube film/resin compounded layer will be carried out laying, more heated, add
Molded i.e. obtain described composite.
Through structure/heating integral composite that the integrated molding method of the present invention obtains, there is high mechanics
Performance, high electrical heating efficiency and stability, wherein hot strength and modulus are divided compared with the structural composite material of respective material system
You can well imagine high by more than 3%, any heating-up temperature within 150 DEG C all can reach balance within 5 minutes, and connects at 150 DEG C
Continuous heating 200 hours, resistance variations is less than 5%.
Structure prepared by the present invention/heating integral composite has mechanical property and the electrical heating characteristic of excellence,
The fields such as survey of deep space, polar region observation, civil electronic device have boundless application prospect.
Compared with prior art, the present invention has a following beneficial effect:
(1) present invention use the chemical gaseous phase deposition carbon nano-tube film prepared of floating catalytic method as calandria, this carbon
Nanotube films has ultra-thin, flexible and excellent mechanics and an electrology characteristic, and has low cost, is prone to the allusion quotation of large-scale production
Type advantage.
(2) present invention can be controlled by the resistance of resin solution concentration of carbon nanotube film heating body；
(3) CNT film heating body can be imbedded composite interlayer by the present invention according to specific needs, and can be not
Spread into multilayer carbon nanotube film with interlayer, also CNT film heating body can be plated in composite material surface；
(4) present invention is not affected by Fiber In Composite Material and resin system, for conductive fiber, non-conductive fibre, heat
Plastic resin, heat-curing resin all can realize structure/heating integral；
(5) present invention uses integrated molding technology to prepare structure/heating composite；
(6) present invention can be on the basis of keeping composite excellent mechanical performance, it is achieved efficiently, stablizes electrical heating merit
Energy.
Accompanying drawing explanation
By the detailed description non-limiting example made with reference to the following drawings of reading, the further feature of the present invention,
Purpose and advantage will become more apparent upon:
Fig. 1 is chemical gaseous phase deposition floating catalyst system CNT environmental microbes in the present invention；
Fig. 2 is that in the present invention, resin quality mark is the CNT preimpregnation environmental microbes of 10%；
Fig. 3 is that in the present invention, resin quality mark is the CNT preimpregnation environmental microbes of 35%；
Fig. 4 is present configuration/heating integral composite structure figure；Wherein, 1-carbon nano-tube film/resin compounded
Layer；2-electrode；3-reinforcement layer.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in the technology of this area
Personnel are further appreciated by the present invention, but limit the present invention the most in any form.It should be pointed out that, the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement.These broadly fall into the present invention
Protection domain.
The present invention provides a kind of structure/heating integral composite and preparation method thereof, described composite such as Fig. 4 institute
Show, be the multiple structure including reinforcement layer 3, carbon nano-tube film/resin compounded layer 1.
Described reinforcement layer 3, carbon nano-tube film/resin compounded layer 1 laying successively.
Described reinforcement layer 3 includes one or more in resin bed, fibrous layer, resin/fiber composite bed.
Described preparation method comprises the steps:
The first step, prepares carbon nano-tube film, and this film uses chemical gaseous phase deposition floating catalytic method to be prepared.Carbon nanometer
The concrete preparation process of periosteum is: under the protective effect of the noble gas such as argon, hydrogen, by dehydrated alcohol, ferrocene catalysis
Agent and thiophene accelerator mixed liquor inject high-temperature tubular reacting furnace with certain speed.In the relatively low collecting region of temperature along tube wall shape
Become the continuous hollow Nano carbon periosteum of similar sock.It is complete that this hollow Nano carbon periosteum being formed in situ has preferably machinery
Property, therefore directly can be wound on the wind of the reacting furnace other end from mouth of pipe blowout with air-flow.Single hollow Nano carbon
Periosteum subsides and forms two-layer carbon nano-tube film, and the thickness of every layer of carbon nano-tube film is 100nm.The time being wound around by regulation
Obtain the multilayer carbon nanotube film of different-thickness.If air enters high temperature system hydrogen and easily reaches explosion limit, therefore
High-temperature tubular reacting furnace and collecting region are in enclosed environment, and system is maintained at an atmospheric pressure.
Second step, prepares CNT preimpregnation film (i.e. carbon nano-tube film/resin compounded layer 1), in order to carbon nano-tube film
Resistivity regulate and control, and in subsequent step, improve the adhesive property of carbon nano-tube film and reinforcement layer 3, the present invention exists
Carbon nano-tube film introduces resin-made and presoaks film for CNT.This process includes following step:
A resin is dissolved in solvent and is prepared as certain density resin solution by (), in solution, the mass content of resin controls
1% to 20%, described resin is consistent with the bulk resin of fibrous composite in subsequent step, and resin is: epoxy resin,
Appointing in bismaleimide resin, phenolic resin, polyimides, polyethylene, polyvinyl alcohol, polyester, polypropylene, polystyrene and polyurethane
Meaning one, solvent is ethanol, acetone, benzene, toluene, oxolane, dimethylformamide, methyl pyrrolidone and dimethyl sulfoxide
In one or more kinds of mixing；
B carbon nano-tube film be impregnated in resin solution and keeps 30 minutes by (), for the resin solution concentration that viscosity is higher
Dip time extends to 1 hour, carries out in hermetic container for easy volatile solvent dipping process；
(c) take out carbon nano-tube film and carry out drying obtain CNT preimpregnation film, dry temperature resin be less than coagulate
Glue temperature (thermosetting resin) or heat decomposition temperature (thermoplastic resin).In order to improve the rate of volatilization of solvent in resin solution
Carbon nano-tube film after dipping can be put in vacuum drying oven, can will be presoaked by the mass content of regulation and control resin solution kind resin
The resin content of film controls in the range of 2%～35%, and corresponding resistor rate can be controlled in 1 × 10-3Ω cm～8 ×
10-3In the range of Ω cm.
3rd step, CNT preimpregnation film is connected with electrode 2, utilizes CNT preimpregnation film intrinsic viscosity directly and electrode
2 bond, it is not necessary to any conductive adhesive, can ensure the low contact resistance of carbon nano-tube film and electrode 2, detailed process
For: the electrode material of 10 μm～30 μ m-thick is cut into strip, 1.2 times of a length of CNT of electrode 2 preimpregnation film width with
On, the width of electrode 2 is the 1/30～1/10 of CNT preimpregnation film length.Electrode material is appointing in copper, platinum, aluminum, graphite
Meaning one.With sand paper, electrode material surface is polished, to improve the caking property of itself and CNT preimpregnation film.Electrode is long
Bar is put on the surface at CNT preimpregnation film two ends, it is ensured that the length direction of electrode 2 presoaks the width side of film with CNT
To parallel.CNT is presoaked film two ends and carries out 180 ° of bendings, thus realize the cladding completely to electrode 2.To at room temperature
Have sticking CNT preimpregnation film, by compaction treatment, it is got up with electrode 2 tight bond, pressure limit be 0.1～
3MPa, is not less than 10 minutes pressing time.To not having sticking CNT preimpregnation film, will by hot-pressing processing
It gets up with electrode 2 tight bond, and temperature is gel point (thermosetting resin) or the fusing point of resin in CNT preimpregnation film
(thermoplastic resin), pressure limit is 1～5MPa, and hot pressing time is 5～10 minutes.
4th step, CNT preimpregnation film carries out laying, if dried layer reinforcement layer 3 can first be spread, at its table with reinforcement layer 3
Face is plated in one layer of CNT preimpregnation film, if then repaving dried layer reinforcement layer 3, according to final composite above preimpregnation film
The needs of the efficiency of heating surface can be at different interlayer paving multilayer carbon nanotube preimpregnation films.If also can directly spread dried layer reinforcement layer 3, then
Its surface spreads one layer of CNT preimpregnation film again.Reinforcement layer 3 can be fibrous layer or resin bed or fiber/resin composite bed,
Wherein fiber is carbon fiber, glass fibre, poly-p-phenylene-benzobisoxazole fiber, polyester fiber, polyethylene fibre, polypropylene fibre
Any one in dimension, resin is epoxy resin, bismaleimide resin, phenolic resin, polyimides, polyethylene, polyvinyl alcohol, poly-
Any one in ester, polypropylene, polystyrene and polyurethane.But, when reinforcement layer 3 is carbon fiber layer, its carbon fiber
Electric conductivity can upset CNT preimpregnation film circuit.Therefore, need during laying CNT preimpregnation film both sides paving
Entering insulating barrier, insulating barrier includes: ultra-thin glass fiber felt, ultra-thin glass fiber cloth, resin molding.
5th step, composite integrated molding, laying reinforcement layer 3 after good is added with CNT preimpregnation film
Heat, extrusion forming.For the composite heat pressing process molding of thermoplastic resin, the composite for thermosetting resin is used
Any one in the outer vacuum forming of autoclave molding, hot-forming, tank.When the forming temperature system higher than 200 DEG C, for reducing
The oxidation of electrode, composite molding under vacuum.
Embodiment 1
Present embodiments providing a kind of structure/heating integral composite and preparation method thereof, described composite is
Including carbon fiber/AG80 reinforcement layer, the multiple structure of carbon nano-tube film/resin compounded layer.
Described preparation method, uses and makes between a flexible carbon nano tube film embedment carbon fiber/AG80 resin prepreg bed of material
Standby structure/heating integral composite, specifically comprises the following steps that
The first step, prepares carbon nano-tube film
Under the protective effect of argon, by dehydrated alcohol, ferrocene catalyst and thiophene accelerator mixed liquor with 0.5ml/
The speed of min injects high-temperature tubular reacting furnace, and the flow of argon is 16000sccm, and whole system is maintained at an atmospheric pressure.?
Being wound carbon nano-tube film of the reacting furnace other end, the thickness of every layer of carbon nano-tube film is 100nm.Continuous winding 2 is little
Time obtain long 1.5m, wide 1m and the carbon nano-tube film of thick 10 μm.Scalpel is utilized to cut length from the carbon nano-tube film obtained
80mm, the rectangular specimens of wide 40mm.As it is shown in figure 1, carbon nano-tube film is interweaved by CNT forms network mechanism, Qi Zhongcun
Pore structure in several nanometers to several tens of nanometers.
Second step, prepares CNT preimpregnation film
Resin solution infusion process is used to prepare CNT preimpregnation film, by AG80 resin, DDS firming agent and BF3MEA with
The quality of 100:30:1 forms resin system than mix homogeneously, is then mixed with the mass ratio of 5:100 with acetone by this resin system
Conjunction is formed uniformly resin solution.Carbon nano-tube film immerses in resin solution 30 minutes, takes out carbon nano-tube film and is placed in vacuum and dries
Case keeps 2 hours under the vacuum of-0.1MPa at 60 DEG C, obtains CNT preimpregnation film, and its resinite fraction is
10%, resistivity is 2 × 10-3Ω·cm.As in figure 2 it is shown, the partial hole gap structure in carbon nano-tube film is filled by resin.
3rd step, CNT preimpregnation film is connected with electrode
Utilize shears to cut long 60mm, wide 5mm, the copper foil electrode of thick 20 μm, and use 1000# sand paper that copper foil electrode is entered
Row polishing.Electrode strip is put on the surface at CNT preimpregnation film two ends, it is ensured that the length direction of electrode and CNT
The width of preimpregnation film is parallel.At away from CNT preimpregnation film two ends 5mm, carry out 180 ° of bendings respectively, thus realize electricity
The cladding completely of pole.Then it is put on press, is kept 30 minutes under the pressure of 1MPa, thus by carbon nano-tube film and electricity
Pole tight bond.
4th step, CNT preimpregnation film carries out laying with carbon fiber/AG80 reinforcement layer
Cut long 80mm, the T700/AG80 prepreg 8 pieces and long 80mm of wide 40mm, wide 40mm surface density 30g/m2Glass
Glass fiber felt two pieces.By 4 pieces of T700/AG80 prepreg layings successively, then one piece of glass mat is plated in 4 layers of T700/
AG80 prepreg surface.Secondly the CNT preimpregnation film connecting electrode is plated in glass mat surface, then by one piece
Glass mat is plated in CNT preimpregnation film surface.Finally by remaining 4 pieces of T700/AG80 prepregs at glass mat
Surface is plated in successively.In order to ensure fitting tightly of different interlayer, above-mentioned laying is carried out under the effect of 0.1MPa pre-compacted
30 minutes.
5th step, composite integrated molding
Above-mentioned laying employing autoclave technique is carried out curing molding, and concrete curing cycle is: 90 DEG C keep 30 minutes,
115 DEG C keep 30 minutes, and 180 DEG C keep 3 hours.Start pressurization when temperature rises to 115 DEG C, compression rate is 0.04MPa/
Min, pressure rises to stop pressurization during 0.7MPa.The hot strength of prepared structure/heating integral composite and modulus
It is respectively increased 5.1% and 3.4% relative to T700/AG80 structural composite material.When power supply input power is 3W；Structure/heating
Integrated composite surface after powered up within 240 seconds, i.e. can reach 150 DEG C, and at 150 DEG C continuously after energising 200 hours
Resistance generation minor variations, increases to 2.49 Ω from 2.43 Ω.
Embodiment 2
Present embodiments providing a kind of structure/heating integral composite and preparation method thereof, described composite is
Including glass fibre/E51 reinforcement layer, the multiple structure of carbon nano-tube film/resin compounded layer.
Described preparation method, uses preparation knot between three flexible carbon nano tube film embedded in glass fiber/E51 prepreg
Structure/heating integral composite, specifically comprises the following steps that
The first step, prepares carbon nano-tube film
Under the protective effect of argon, by dehydrated alcohol, ferrocene catalyst and thiophene accelerator mixed liquor with 0.5ml/
The speed of min injects high-temperature tubular reacting furnace, and the flow of argon is 16000sccm, and whole system is maintained at an atmospheric pressure.?
Being wound carbon nano-tube film of the reacting furnace other end, the thickness of every layer of carbon nano-tube film is 100nm.Continuous winding 1.5
Hour obtain long 1.5m, wide 1m and the carbon nano-tube film of thick 7.5 microns.Scalpel is utilized to cut from the carbon nano-tube film obtained
Take the rectangular specimens three of long 200mm, wide 80mm.
Second step, prepares CNT preimpregnation film
Resin solution infusion process is used to prepare CNT preimpregnation film, by E51 resin, 2-ethyl-4 Methylimidazole. with 100:
The quality of 7 forms resin system than mix homogeneously, then this resin system and acetone is compared with the quality of 20:100 and mixs homogeneously
Form resin solution.Carbon nano-tube film immerses in resin solution 30 minutes, take out carbon nano-tube film be placed in vacuum drying oven in-
Keeping 2 hours at 60 DEG C under the vacuum of 0.1MPa, obtain CNT preimpregnation film, its resinite fraction is 35%, electricity
Resistance rate is 6.5 × 10-3Ω·cm.As it is shown on figure 3, the most of pore structure in carbon nano-tube film is filled by resin.
3rd step, CNT preimpregnation film is connected with electrode
Utilize shears to cut long 120mm, wide 8mm, the foil electrode of thick 10 μm, and use 600# sand paper that foil electrode is entered
Row polishing.Electrode strip is put on the surface at CNT preimpregnation film two ends, it is ensured that the length direction of electrode and CNT
The width of preimpregnation film is parallel.At away from CNT preimpregnation film two ends 8mm, carry out 180 ° of bendings respectively, thus realize electricity
The cladding completely of pole.Then it is put on press, is kept 30 minutes under the pressure of 1MPa, thus by carbon nano-tube film and electricity
Pole tight bond.
4th step, CNT preimpregnation film carries out laying with glass fibre/E51 resin bed
Cut long 200mm, the glass fibre/E51 prepreg 12 pieces of wide 80mm.3 blocks of glass fibre/E51 prepreg is depended on
Secondary laying, is then plated in prepreg surface, by 3 blocks of glass fibre/E51 prepreg by the CNT preimpregnation film connecting electrode
It is plated in CNT preimpregnation film surface successively.Again the CNT preimpregnation film connecting electrode is plated in prepreg surface, by 3
Block glass fibre/E51 prepreg is plated in CNT preimpregnation film surface successively.Finally will connect the CNT preimpregnation of electrode
Film is plated in prepreg surface, and 3 blocks of glass fibre/E51 prepreg is plated in CNT preimpregnation film surface successively.In order to protect
Fitting tightly of the different interlayer of card, carries out pre-compacted 1 hour by above-mentioned laying under the effect of 0.1MPa.
5th step, composite integrated molding
By above-mentioned laying employing heat pressing process carry out curing molding, concrete curing cycle is: 60 DEG C keep 30 minutes, 80 DEG C
Keeping 1 hour, 120 DEG C keep 3 hours.Start pressurization when temperature rises to 80 DEG C, pressure is 3MPa.Prepared structure/add
Hot strength and the modulus of heating integrated composite are respectively increased 13.4% relative to glass fibre/E51 structural composite material
With 7.8%.Three CNT membrane electrodes connect power supply with parallel way, when power supply input power is 3W, and structure/heating one
Change composite material surface after powered up within 150 seconds, i.e. can reach 150 DEG C, and continuously resistance after energising 200 hours at 150 DEG C
There is minor variations, increase to 19.05 Ω from 18.27 Ω.
Embodiment 3
Present embodiments providing a kind of structure/heating integral composite and preparation method thereof, described composite is
Including glass fibre/polypropylene reinforcement layer, the multiple structure of carbon nano-tube film/resin compounded layer.
Described preparation method, uses a flexible carbon nano tube film to be plated in glass fibre/polypropylene prepreg surface
Preparation structure/heating integral composite, specifically comprises the following steps that
The first step, prepares carbon nano-tube film
Under the protective effect of argon, by dehydrated alcohol, ferrocene catalyst and thiophene accelerator mixed liquor with 0.5ml/
The speed of min injects high-temperature tubular reacting furnace, and the flow of argon is 16000sccm, and whole system is maintained at an atmospheric pressure.?
Being wound carbon nano-tube film of the reacting furnace other end, the thickness of every layer of carbon nano-tube film is 100nm.Continuous winding 6 is little
Time obtain long 1.5m, wide 1m and the carbon nano-tube film of thick 30 microns.Scalpel is utilized to cut from the carbon nano-tube film obtained
Long 200mm, the rectangular specimens one of wide 80mm.
Second step, prepares CNT preimpregnation film
Using resin solution infusion process to prepare CNT preimpregnation film, thermoplastic polyurethane stirs molten under conditions of 80 DEG C
In dimethylformamide, solution, the mass fraction of polyurethane is 1.5%.Carbon nano-tube film is immersed in polyurethane solutions 1 little
Time, taking-up carbon nano-tube film is put into and is kept 6h at vacuum drying oven 130 DEG C under the vacuum of-0.1MPa, it is thus achieved that CNT
Compound preimpregnation film, its resinite fraction is 24%, and resistivity is 3.8 × 10-3Ω·cm。
3rd step, CNT preimpregnation film is connected with electrode
Utilize shears to cut long 120mm, wide 8mm, the copper foil electrode of thick 20 μm, and use 1000# sand paper to copper foil electrode
Polish.Electrode strip is put on the surface at CNT preimpregnation film two ends, it is ensured that the length direction of electrode and carbon nanometer
The width of pipe preimpregnation film is parallel.At away from CNT preimpregnation film two ends 8mm, carry out 180 ° of bendings respectively, thus realize right
The cladding completely of electrode.Then be put on hot press, temperature be 180 DEG C, pressure be 3MPa under conditions of keep 5 points
Clock, thus carbon nano-tube film is bondd with electrode seal.
4th step, CNT preimpregnation film carries out laying with glass fibre/polypropylene reinforcement layer
Cut the glass fibre/thermoplastic polyurethane prepreg 8 pieces of long 200mm, wide 80mm.By 8 pieces of glass fibre/thermoplastics
Property polyurethane prepreg laying successively, then by connect electrode CNT preimpregnation film be plated in prepreg surface.
5th step, composite integrated molding
Being shaped by above-mentioned laying employing heat pressing process, concrete moulding process is: 245 DEG C keep 10 minutes, apply pressure
Power is 4MPa.The hot strength of obtained structure/heating integral composite and modulus are relative to glass fibre/thermoplasticity
Polyurethane structural composite is respectively increased 3.6% and 3.1%.When power supply input power is 3W, structure/heating integral is combined
Material surface after powered up within 120 seconds, i.e. can reach 150 DEG C, and at 150 DEG C continuously after energising 200 hours resistance occur micro-
Little change, increases to 2.73 Ω from 2.66 Ω.
The concrete application approach of the present invention is a lot, and the above is only the preferred embodiment of the present invention.It should be pointed out that, above
Embodiment is merely to illustrate the present invention, and is not limited to protection scope of the present invention.Common skill for the art
For art personnel, under the premise without departing from the principles of the invention, it is also possible to make some improvement, these improvement also should be regarded as this
Bright protection domain.
Claims (10)
1. structure/heating integral composite, it is characterised in that described composite is for including that reinforcement layer, carbon are received
The multiple structure of mitron film/resin compounded layer.
2. structure/heating integral composite as claimed in claim 1, it is characterised in that described reinforcement layer, carbon nanometer
Periosteum/resin compounded layer laying successively.
3. structure/heating integral composite as claimed in claim 1, it is characterised in that described reinforcement layer includes tree
One or more in lipid layer, fibrous layer, resin/fiber composite bed.
4. structure/heating integral composite as claimed in claim 3, it is characterised in that described fiber include carbon fiber,
Any one in glass fibre, poly-p-phenylene-benzobisoxazole fiber, polyester fiber, polyethylene fibre, polypropylene fibre.
5. the structure as described in any one of claim 1-3/heating integral composite, it is characterised in that described resin
Including epoxy resin, bismaleimide resin, phenolic resin, polyimides, polyethylene, polyvinyl alcohol, polyester, polypropylene, polystyrene
Mixing with one or more in polyurethane.
6. structure/heating integral composite as claimed in claim 1 or 2, it is characterised in that described carbon nano-tube film bag
Including the film unit of tens to hundreds of layer of 100nm, the CNT in described film unit crosses one another formation network structure.
7. structure/heating integral composite as claimed in claim 1 or 2, it is characterised in that described carbon nano-tube film/
In resin compounded layer, the content of resin is 2wt%～35wt%.
8. structure/heating integral composite as claimed in claim 1 or 2, it is characterised in that described carbon nano-tube film/
The preparation method of resin compounded layer comprises the steps: to put into carbon nano-tube film dipping 30～60min in resin solution, takes out
Post-drying and get final product.
9. structure/heating integral composite as claimed in claim 1 or 2, it is characterised in that described carbon nano-tube film/
Resin compounded layer two ends connect electrode respectively.
10. a preparation method for the structure as described in any one of claim 1-9/heating integral composite, its feature
Being, described method comprises the steps:, according to specifically applying needs, reinforcement layer, carbon nano-tube film/resin compounded layer to be entered
Row laying, more heated, extrusion forming i.e. obtains described composite.
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| CN106643464A (en) * | 2016-12-27 | 2017-05-10 | 北京航空航天大学 | Method for monitoring stress of composite material in all directions based on carbon nanotube film |
| CN107260390A (en) * | 2017-07-17 | 2017-10-20 | 苏州捷迪纳米科技有限公司 | A kind of beauty mask and preparation method thereof |
| CN109769314A (en) * | 2019-03-13 | 2019-05-17 | 中航复材（北京）科技有限公司 | A kind of flexibility carbon composite electric heating film and its application |
| CN109808196A (en) * | 2019-02-26 | 2019-05-28 | 中国人民解放军国防科技大学 | Fiber laminated composite material containing high-orientation-degree carbon nano tubes between layers and preparation method thereof |
| CN113696513A (en) * | 2021-09-03 | 2021-11-26 | 上海交通大学 | Carbon nano material-based non-autoclave electroformed composite material method |
| CN115197599A (en) * | 2017-01-09 | 2022-10-18 | 纳米复合技术股份有限公司 | Intumescent nanostructured materials and methods of making the same |
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Application publication date: 20161207 |